Research Article  Open Access
R. L. Dhiman, S. P. Taneja, V. R. Reddy, "Preparation and Characterization of Manganese Ferrite Aluminates", Advances in Condensed Matter Physics, vol. 2008, Article ID 703479, 7 pages, 2008. https://doi.org/10.1155/2008/703479
Preparation and Characterization of Manganese Ferrite Aluminates
Abstract
Aluminum doped manganese ferrites with have been prepared by the double ceramic route. The formation of mixed spinel phase has been confirmed by Xray diffraction analysis. The unit cell parameter `' is found to decrease linearly with aluminum concentration due to smaller ionic radius of aluminum. The cation distributions were estimated from Xray diffraction intensities of various planes. The theoretical lattice parameter, Xray density, oxygen positional parameter, ionic radii, jump length, and bonds and edges lengths of the tetrahedral (A) and octahedral (B) sites were determined. ^{57}Fe Mössbauer spectra recorded at room temperature were fitted with two sextets corresponding to Fe^{3+} ions at A and Bsites. In the present ferrite system, the area ratio of Fe^{3+} ions at the A and Bsites determined from the spectral analysis of Mössbauer spectra gives evidence that Al^{3+} ions replace iron ions at Bsites. This change in the site preference reflects an abrupt change in magnetic hyperfine fields at A and Bsites as aluminum concentration increases, which has been explained on the basis of supertransferred hyperfine field. On the basis of estimated cation distribution, it is concluded that aluminum doped manganese ferrites exhibit a 55% normal spinel structure.
1. Introduction
Spinel ferrites have been the subject of great interest for the past five decades, because of their wide range of applications in transformers, inductors, choke coils, noise filters magnetic recording heads, and so forth [1]. These ferrites possessing cubic closepacked structure of oxygen ions, are described by the formula , where (A) and [B] represent tetrahedral and octahedral sites, respectively. The site occupancy is often depicted in the chemical formula as , where round and square brackets denote the A and Bsites, respectively, M represents a metal cation, and ‘’ is the inversion parameter. The degree of inversion ‘’ for spinel ferrites is defined as the fraction of tetrahedral (A)sites occupied by trivalent cations. Accordingly, for a normal spinel and for a completely inverse spinel, . The magnetic and the electronic properties of such a ferrite system depend upon the type of metal cations and their distribution among the two interstitial sites, that is, A and Bsites. Therefore, the knowledge of cation distribution is essential to understand the magnetic behavior of spinel ferrites. Manganese ferrite is early known to be a mixed inverse spinel, and the degree of inversion mainly depends upon the method of preparation. The presence of nonmagnetic ions in these spinel ferrites is found to alter their magnetic and electronic properties. The addition of metal cations such as trivalent or tetravalent influences the electronic and magnetic properties of the ferrite system [2–6]. Various studies showed that heating might change the distribution of metal cations at the A and Bsites of . It has been reported that by using neutron diffraction technique, the degree of inversion, that is, the distribution of the cationic ions between the tetrahedral and octahedral sites of prepared by usual ceramic route was determined 81% normal [7]. However, this value reduced to 33%, when was prepared by wet chemical method [8]. Thus, the method of preparation may play a crucial role in order to obtain the desired electronic and magnetic properties. Extensive investigations regarding the substitution of metal cations, for example, Cu^{2+}, Zn^{2+}, Ti^{2+}, Co^{3+}, and Ni^{2+} in manganese ferrites have been reported, giving useful information about the influence of such metal cations [9–13]. However, no systematic results regarding the estimation of cation distribution on substitution of aluminum ion in was available. In the present studies, the cation distribution in tetrahedral and octahedral sites of aluminum substituted manganese ferrites synthesized via double ceramic route has been determined by Xray diffraction and Mössbauer spectroscopic measurements.
2. Experimental
Samples of the mixed spinel ferrites for , and 1.0 were synthesized by usual double ceramic processing technique. The starting materials were highpurity analytical reagent grade oxides, , MnO, and . The required compositions were weighed and mixed in a mortar and pestle. The mixed powders were presintered at for 10 hours in the air and allowed to cool to room temperature at the rate of about /min. In the final sintering process, the samples were placed in a furnace at for 10 hours in the air and then cooled slowly to room temperature at the rate of /min. The finally sintered materials were well grounded. To ensure their singlephase nature, the powder Xray diffraction studies were made on Regaku Xray diffractometer by using CuK_{α} radiation of wave length 1.54060 Å. Mössbauer absorption spectra were recorded in transmission geometry at room temperature using a multichannel analyzer with a drive in constant acceleration mode. A source with initial activity of 20 mCi was used. The spectrometer was periodically calibrated using a natural iron foil as a standard.
3. Results and Discussion
3.1. XRay Diffraction Analysis
The Xray diffraction patterns of mixed spinel ferrites ( for , and 1.0) are shown in Figure 1.
The positions of diffraction peaks from various planes were identified using JCPDS file no. 742403. It is evident from Figure 1 that each ferrite sample exhibits singlephase cubic spinel structure with Fd3m (227) space group. The value of the lattice constant ‘a_{O}’ for all the samples was determined from the position of principal (311) peak using where h, k, and l are the miller indices.
The observed values of lattice constant ‘a_{O}’ listed in Table 1 are slightly smaller than the JCPDS table value of 8.518 Å. The lattice constant ‘a_{O}’ is found to decrease linearly with aluminum concentration (x) as shown in Figure 2(a), thereby obeying Vegard’s law [14].

The decrease in lattice constant is attributed to the fact that the Pauling ionic radius of Al^{3+} (0.50 Å) is smaller than that of Fe^{3+} (0.64 Å), which causes the shrinking in the unit cell dimensions. The decrease in ‘a_{O}’ and the shift of reflections toward higher angle with the increasing aluminum concentration (x) show that aluminum atoms have been incorporated into the spinel structure [15].
The Xray density ‘d_{x}’ was calculated using the formula [16] where ‘M’ is the molecular weight, ‘N’ is the Avogadro's number, and ‘a_{O}’ is the lattice constant of the spinel ferrite. The calculated values of Xray density are listed in Table 1. The Xray density decreases with increasing aluminum concentration (x), as shown in Figure 2(b). The decrease in Xray density is due to the decrease in mass, which overtakes the decrease in volume of the unit cell.
The cation distribution in the various spinel ferrite systems has been estimated from Xray diffraction [5, 6], Mössbauer’s effect [17, 18], and magnetization measurements [19, 20]. It has been reported [21, 22] that the best information in estimation of cation distribution can be achieved by comparing the experimental and theoretical intensity ratios for reflections (220), (422), and (400). However, the intensities of (220), (422), and (400) planes are more sensitive to cations on A and Bsites [23, 24]. The Xray diffraction intensity of the respective planes was calculated using the formula [25] where is the relative integral intensity; is the structure factor; P is the multiplicity factor; Lp is the Lorentz factor. The structural factors were calculated by using the equation suggested by Porta and Furuhashi et al. [26, 27]. The multiplicity factor and the Lorentz factors were taken from the literature [16]. The ionic scattering factor reported in the international tables for Xray crystallography [28] is used for the calculation of structural factor. It is well established that the intensity ratios / and / are considered to be sensitive to cation distribution [29]. Therefore in the present ferrite system, intensity ratios of these planes have been used in estimation of cation distribution. The intensity ratios of these planes were calculated for various cation distributions using the following expression suggested by Bertaut [21]: For all the samples, the calculated values, those closest to the experimental observed values, are given in Table 2. The theoretical lattice constant ‘a_{t}’ for all composition was calculated on the basis of estimated cation distribution by using the relation [30] where and are the radii of the  and the sites, respectively, and is the radius of the oxygen ion O^{2−} (1.48 Å). The calculated values ‘a_{t}’ are nearly equal to the experimental observed value ‘a_{O}’ which confirms the estimated cation distribution (see Table 2). The site radii and used above were determined using the following: The calculated values of and are listed in Table 3. The value of decreases slowly; however the value of decreases noticeably with increasing aluminum concentration. This is due to the replacement of larger ionic radii () with smaller ionic radii () and their distribution amongst the  and sites. The value of the oxygen positional parameter ‘u’ was calculated by using the following relation: The determined values of ‘u’ are listed in Table 3. The values of the tetrahedral (), octahedral bond length (), tetrahedral edge length (), and shared () and unshared octahedral edge lengths () were calculated by using the experimental values of lattice constant ‘a_{O}’ and oxygen positional parameter ‘u’ from the following [30, 31]: Various calculated Xray parameters are given in Table 3. It is observed that , , , , and decrease with increasing aluminum concentration (x). This is due to the substitution process, that is, replacement of larger ionic radii (Fe^{3+}) by smaller ionic radii (Al^{3+}) and their distribution among the  and sites. These results are in consistent with the reported data [32]. It has been reported that the jump length ‘L’ (the distance between the magnetic ions) of electrons influences the physical properties of the ferrite system [33]. Electrons those are hopping between  and sites are less probable compared to that between  and sites, because the distance between the two metal ions placed in sites is smaller than if they were placed one in sites and the other in sites [34]. ‘L’ of the  and sites is determined from the following relations [35]: It is observed that ‘L’ of  and sites decreases with increasing aluminum concentration (x) as shown in Figure 3.


The decrease in jump length is due to the decrease in the distance between the magnetic ions by the substitution of smaller Al^{3+} ions at the sites and is similar to those reported earlier [4, 32].
3.2. Mössbauer Analysis
^{57}Fe Mössbauer absorption spectra of mixed spinel ferrite system for , and 1.0 recorded at room temperature are displayed in Figure 4. The experimental data were fitted using least squarefitting (NORMOS/SITE) program [36]. Each spectrum exhibits a superposition of two Zeeman sextets, one sextet corresponding to a higher magnetic field is attributed to Fe^{3+} ions on the site, and the other sextet corresponding to lower magnetic field is attributed to Fe^{3+} ions on the site. The refined values of the hyperfine parameters computed from the Mössbauer spectra are listed in Table 4. In the present ferrite system, it is observed that on increasing Al^{3+} ions concentration, the values of isomer shift (δ) of tetrahedral sites show almost negligible change, indicating that aluminum ions do not enter in sites. The isomer shift of sites is greater than site and is in agreement with the reported data [11]. Furthermore, the observed values of isomer shift (δ) are significantly less than the expected value, 0.5 mm/s for the Fe^{2+} ions [20]. Hence, the presence of Fe^{2+} ions in the present ferrite system is ruled out. Thus the electron exchange interaction () does not occur, and hence the oxidation state of Fe^{3+} remains unchanged during synthesis process. The hyperfine field values at  and sites show a gradual decrease with increasing Al^{3+} concentration (x). This can be explained on the basis of supertransferred hyperfine field at the central cation that originates from the magnetic moments of the nearestneighbor cations, that is, from the intrasublattice contributions and and the intersublattice contributions and . In the present ferrite system, the intrasublattice contributions and are predominant. It has been reported that the intensities corresponding to (200) and (422) reflections are most sensitive to cations on Asites [23, 24]. The Xray diffraction patterns of the present ferrite system indicate that the intensity of (220) and (422) reflections remains almost constant as compared to (311) reflection, suggesting that Al^{3+} ions do not enter in the Asites. The value of isomer shift (δ) of sites remains invariant on substitution of aluminum ions suggesting that Al^{3+} ions do not replace Fe^{3+} ions from sites. The introduction of Al^{3+} ions that replaces Fe^{3+} ions from sites decreases intrasublattice contributions, which in turn decreases the hyperfine field values. As nonmagnetic Al^{3+} ions replace Fe^{3+} ions, the correct amount of Fe^{3+} ions occupying  and sites is estimated by determining the area under the Mössbauer absorption spectra through the least square fitting program. The Fe^{3+}(B)/Fe^{3+}(A) ratio obtained from the Mössbauer spectra is in good agreement with those calculated from Xray intensities. It is observed that this ratio decreases with increasing aluminum concentration (x) suggesting a decrease in ferrimagnetic behavior.
 
shift given relative to Fe. 
4. Conclusion
Aluminum substituted manganese ferrites for , and 1.0 have been prepared by double ceramic processing technique. The unit cell parameter decreases linearly with the increase of aluminum concentration (x) due to its small ionic radius. The cation distribution estimated from Xray intensity ratios has been verified by comparing the theoretical and experimental lattice parameters. It is observed that the correct amount of Fe^{3+} ions occupying  and sites obtained from Mössbauer spectra is in good agreement with those calculated from Xray intensity calculations. The hyperfine magnetic field obtained from the Mössbauer absorption spectra decreases with increasing aluminum concentration suggesting the decrease in ferrimagnetic behavior and has been explained on the basis of supertransferred hyperfine field mechanism. The Xray determined parameters, for example, lattice constant, Xray density, ionic radius, bond length, jump length of the  and sites, oxygen positional parameter, site edge length, and shared and unshared site edge lengths were determined and found affected by Al^{3+} ions substitution. On the basis of estimated cation distribution, it is concluded that the present ferrite system exhibits a 55% normal spinel structure.
Acknowledgments
One of the authors (R. L. Dhiman) is grateful to Dr. Alok Banerjee and Dr. R. J. Chaudhary, Scientists, UGCDAE, Consortium for Scientific Research, University Campus, Khandwa Road, Indore (MP), India, for providing experimental facilities.
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Copyright © 2008 R. L. Dhiman et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.