Research Article  Open Access
M. A. Mohshin Quraishi, M. H. R. Khan, "Synthesis and Characterization of LithiumSubstituted CuMn Ferrite Nanoparticles", Indian Journal of Materials Science, vol. 2013, Article ID 910762, 7 pages, 2013. https://doi.org/10.1155/2013/910762
Synthesis and Characterization of LithiumSubstituted CuMn Ferrite Nanoparticles
Abstract
The effect of Li substitution on the structural and magnetic properties of Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} (x = 0.00, 0.10, 0.20, 0.30, 0.40, and 0.44) ferrite nanoparticles prepared by combustion technique has been investigated. Structural and surface morphology have been studied by Xray diffractometer (XRD) and highresolution optical microscope, respectively. The observed particle size of various Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} is found to be in the range of 9 nm to 30 nm. XRD result confirms singlephase spinel structure for each composition. The lattice constant increases with increasing Li content. The bulk density shows a decreasing trend with Li substitution. The real part of initial permeability () and the grain size (D) increase with increasing Li content. It has been observed that the higher the is, the lower the resonance frequency in Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites is.
1. Introduction
Ferrite nanoparticles have attracted a growing interest due to their potential applications such as magnetic recording [1], storage [2], and biotechnology [3]. In the most recent years, the interest in the use of nanoparticles in biomedical applications has greatly increased [4, 5]. The size and composition of nanoparticles influence the bioapplication of the magnetic nanoparticles [6]. It is well known that the physical and chemical properties of the nanosized magnetic materials are quite different from those of the bulk ones due to their surface effect and quantum confinement effects. These nanoparticles can be obtained through precipitation of metallic salts in different media as polymers [7], organic acid or alcohol [8], sugars [9], and so forth. In particular, solgel, autocombustion, thermal decomposition, hydrothermal, ball milling, reverse micelle synthesis, solidphase reaction, thermally activated solid state reaction, and pulsed laser deposition have been developed to prepare the singledomain MnFe_{2}O_{4 }nanoparticles [10–23]. Manganese ferrite (MnFe_{2}O_{4}) nanoparticles have become very popular due to their wide range of magnetic applications, such as recording devices, drug delivery, ferrofluid, biosensors, and catalysis [10, 24–27]. Recently, Deraz and Alarifi [28] have studied structural and magnetic properties of MnFe_{2}O_{4} nanoparticles by combustion route. Till now, no other report has been found in the literature for Lidoped CuMn ferrite. Lithium ferrites are lowcost materials which are attractive for microwave device applications. Hence, there has been a growing interest in Lisubstituted CuMn ferrite for microwave applications and high permeability with low magnetic loss. Therefore, this paper is devoted to study the effect of Li^{+} substitution on the physical and magnetic properties of Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites prepared by combustion technique.
2. Experimental
2.1. Sample Preparation and Characterization
The Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites were prepared by autocombustion technique. The analytical grade of Li(NO_{3})_{2,} MnCl_{2}·4H_{2}O, Cu(NO_{3})_{2}·3H_{2}O, and Fe(NO_{3})_{3}·9H_{2}O was taken as raw material and weighted according to the stoichiometric amount and then dissolved in ethanol. The mixture was placed in a magnetic heating stirrer at 80°C, followed by an ignition, the combustion takes place within a few seconds, and fine nanosized powders were precipitated. These powders were crushed and ground thoroughly. The fine powders of the composition were then calcined at 900°C for 5 h for the final formation of Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites nanoparticles. Then, the fine powders were granulated using polyvinyl alcohol (PVA) as a binder and pressed uniaxially into diskshaped (about 13 mm outer diameter, 1.5 mm–2.0 mm thickness) and toroidshaped (about 13 mm outer diameter, about 6.5 mm inner diameter and 2 mm thickness) samples. The samples prepared from each composition were sintered at 1200°C for 1 hour in air. The temperature ranges for sintering was maintained at 5°C/min for heating and 10°C/min for cooling. All sintered samples were polished and thermal etching was performed. Xray diffraction was carried out with an Xray diffractometer (Model: D8 Advance, Bruker AXS) for each sample. For this purpose, monochromatic Cu radiation was used. The lattice parameter for each peak of each sample was calculated by using the formula where , , and are the indices of the crystal planes. To determine the exact lattice parameter for each sample, NelsonRiley method was used. The NelsonRiley function is given as
The values of lattice constant “” of all the peaks for a sample are plotted against . Then, using a leastsquare fit method exact lattice parameter “” was determined. The point where the leastsquare fit straight line cuts the axis (i.e., at or ) is the actual lattice parameter of the sample.
The physical or bulk densities of the samples were determined by Archimedes principle with water medium using the following expression: where is the weight of the sample in air, is the weight of the sample in the water, and is the density of water in room temperature.
The theoretical density was calculated using the following expression: where is Avogadro's number (6.02 × 10^{23} mol^{−1}) and is the molecular weight.
The optical micrographs for various Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites have been taken by using highresolution optical microscope (Model: NMM800TRF). Average grain sizes of all samples were determined from optical micrographs by linear intercept technique [29]. The frequencydependent initial permeability for each sample was measured by using a Wayne Kerr Impedance Analyzer (Model: 6500B). The complex permeability measurement on toroidshaped samples was carried out at room temperature in frequency range 10 KHz–100 MHz. Both the and of the complex permeability were calculated using the following relations: where is the selfinductance of the sample core and is derived geometrically. Here, is the inductance of the winding coil without the sample core, is the number of turns of the coil , and is the area of crosssection of the toroidal sample as follows: where , = inner diameter, = outer diameter, = Height and is the mean diameter of the toroidal sample as follows: The Loss factor, , was determined from the ratio = /.
3. Results and Discussion
3.1. XRay Diffraction Analysis
The XRD analysis was performed to verify the formation of spinel structure of various Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites, in which Mn^{2+} is replaced with Li^{+ }and Fe^{3+}. The XRD patterns of these Li^{+}substituted Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} (with = 0.00, 0.10, 0.20, 0.30, 0.40, and 0.44) ferrites sintered at 1200°C in air for 1 h are shown in Figure 1. The patterns indicated that these materials have a welldefined single crystalline phase and formation of cubic spinel structure for each composition. Analyzing the XRD patterns, it is observed that the positions of the peaks comply with the reported value [30] and some traces of raw materials were found for = 0.00, = 0.10 and = 0.20 and = 0.30).
3.2. Lattice Constant
The values of lattice constant obtained from each plane are plotted against NelsonRiley function [31]. The values of lattice constant were estimated from the extrapolation of these lines to or °. It is noticed from Figure 2 that increases with the increase of Li^{+} content in Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} (with = 0.00, 0.10, 0.20, 0.30, 0.40, and 0.44) ferrites. Values of for various Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites are presented in Table 2. The increase in with Li content indicates that the present system obeys Vegard’s law [32]. This increase of can be attributed to the ionic size. The ionic radius of Li^{+} (0.76 Å) is greater than that of Mn^{2+} (0.67 Å) [29, 33]. When the larger Li^{+}and Fe^{3+} ions enter the lattice, the unit cell expands while preserving the overall cubic symmetry.
3.3. Average Particle Size
The average particle size was estimated by using DebyeScherrer [34] formula from the broadening of the highest intensity peaks (311) of XRD patterns: where is the average particle size, is the wavelength of the radiation used as the primary beam of CuK_{α} ( Å), is the angle of the incident beam in degree, and β is the full width at half maximum (FWHM) of the fundamental reflection (311) in radian of the FCC ferrites phase. DebyeScherer formula assumes approximation and gives the average particle size if the grain size distribution is narrow and straininduced effects are quite negligible.
Figure 3 shows the XRD patterns of Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites sintered at 1200°C for 1 h, where (311) peak is shown in expanded form to understand the variation of FWHM of the Bragg peaks with the Li content. From Figure 3, it is seen that the value of FWHM decreases with the increase of lithium content. The particle size of the sample is inversely proportional to FWHM according to DebyeScherrer formula. The observed particle size is in the range from 9 to 30 nm which has been listed in Table 1.


3.4. Theoretical and Bulk Density
The values of and for the various Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites (with = 0.00, 0.10, 0.20, 0.30, 0.40, and 0.44) are tabulated in Table 2. It is noticed from Figure 4 that both and decrease with the increase of Li substitution in Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites for constant sintering temperature. This phenomenon could be explained in terms of the atomic weight.The atomic weight of Mn (54.94 amu) is greater than that of combined atomic weight of the Li (6.941 amu) and Fe (55.845 amu) [33].
3.5. Microstructure
The optical micrographs of Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites (where = 0.00, = 0.10, = 0.20, = 0.30, = 0.40, and = 0.44) are shown in Figure 5 sintered at 1200°C. The grain size is significantly dependent on Li substitution. The increases with increasing Li substitution for fixed sintering temperature which is shown in Figure 5. This is probably due to the lower melting temperature of Li (180°C) compared to Mn (1245°C). The values of for various Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites are presented in Table 2.
3.6. Complex Initial Permeability
The compositional variations of complex initial permeability spectra for the various Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} samples sintered at 1200°C are shown in Figure 6. It is observed that the remains fairly constant in the frequency range up to some critical frequency which is called resonance frequency, . A sharp decrease in and increase in are observed above the . The increases with the increase of Li^{+} content for various Li_{x}Cu_{0.12} Mn_{0.88−2x}Fe_{2+x}O_{4}. On the other hand, was found to decrease with Li substitution. It was observed that of Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites sintered at 1200°C increases from 18 to 55. Figure 7 shows both and as a function of Li content for various Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites. According to Globus and Duplex model [35], the can be explained as , where is the saturation magnetization and is the magnetocrystalline anisotropy constant. This increase in permeability is expected, because grain size of all samples increases with Li content. It is known that the mobility of domain walls is greatly affected by the microstructure of ferrites. Therefore, in the present case, variation of the initial permeability may be influenced by its grain size.
(a)
(b)
The variation of loss factor, with frequency for all samples, has been studied. The variation of initial loss with frequency for the various Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} samples sintered at 1200°C is shown in Figure 8. At lower frequencies magnetic loss is observed and remains constant up to, a certain frequency, 9 MHz; this frequency limit depends upon the sintering temperatures. The lag of domain wall motion with respect to the applied magnetic field is responsible for magnetic loss and this is accredited to lattice imperfections [36]. At higher frequencies, a rapid increase in loss factor is observed. A resonance loss peak is shown in this rapid increase of magnetic loss. At the resonance, maximum energy transfer occurs from the applied field to the lattice which results in the rapid increases in loss factor.
4. Conclusion
The Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ( = 0.00 to = 0.44) nanoparticles have been successfully synthesized by the combustion technique. The observed particle size is in the range from 9 nm to 30 nm. The XRD patterns confirm that the compositions are single phase and form cubic spinel structure. The lattice parameter increases linearly with increasing Li content and obeys Vegard’s law. The study of microstructure shows that grain size increases with increasing Li content. The bulk density decreases with increasing Li substitution in Li_{x}Cu_{0.12}Mn_{0.88−2x}Fe_{2+x}O_{4} ferrites. The real part of initial permeability increases with increase of Li content for a fixed sintering temperature. This result may be explained with the help of average grain size. The highest was found 55 for = 0.44 which is three times greater than that of parent composition. It was also observed that the resonance frequency, , and real part of initial permeability, , are inversely proportional which confirms Snoek’s relation, = constant.
Acknowledgments
The authors are grateful to the BUET authority for providing financial support for this research. The authors are also thankful to the authority of BCSIR for using their equipment.
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Copyright
Copyright © 2013 M. A. Mohshin Quraishi and M. H. R. Khan. 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.