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The effect of Mn substitution on the magnetic and dielectric properties of cobalt ferrite synthesized by an autocombustion route

This content has been downloaded from IOPscience. Please scroll down to see the full text. 2009 Smart Mater. Struct. 18 115028 (http://iopscience.iop.org/0964-1726/18/11/115028) View the table of contents for this issue, or go to the journal homepage for more

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IOP PUBLISHING Smart Mater. Struct. 18 (2009) 115028 (7pp)

SMART MATERIALS AND STRUCTURES doi:10.1088/0964-1726/18/11/115028

The effect of Mn substitution on the magnetic and dielectric properties of cobalt ferrite synthesized by an autocombustion route
R C Kambale1 , P A Shaikh1, C H Bhosale1 , K Y Rajpure1 and Y D Kolekar2
Composite Materials Laboratory, Department of Physics, Shivaji University, Kolhapur 416004 (MS), India 2 Department of Physics, University of Pune, Ganeshkhind, Pune 411007 (MS), India E-mail: rckambale@gmail.com and ydkolekar@gmail.com
1

Received 12 May 2009, in nal form 21 September 2009 Published 16 October 2009 Online at stacks.iop.org/SMS/18/115028 Abstract Co1.2x Mnx Fe1.8 O4 (0 x 0.4) compositions were synthesized by the autocombustion route by keeping the oxidizer to fuel ratio ( e ) at 1. Thermogravimetric analysis (TGA) shows the stable phase formation takes place at a temperature above 600 C. Structural characterization of all the samples was carried out by the x-ray diffraction technique. Room temperature magnetization measurements showed that, for the substitution of Co by Mn, there is an initial increase in the saturation magnetization ( Ms ) for lower concentrations (i.e. x = 0.1 and 0.2); and then the magnetization decreases for higher concentrations (i.e. x = 0.3 and 0.4). Also, it is observed that the coercivity ( Hc ) goes on decreasing with the substitution of Mn content, except for x = 0.3 which shows a slight increase in coercivity as compared to x = 0.4. Room temperature dielectric properties, namely relative dielectric permittivity ( ), dielectric loss (tan ) and ac conductivity (ac ), for all the samples were studied as a function of applied frequency in the range from 20 Hz to 1 MHz. These studies indicate that the relative dielectric permittivity goes on increasing with the increase of Mn content in Co ferrite and also all the samples show the usual dielectric dispersion which is due to the MaxwellWagner-type interfacial polarization. The ac conductivity measurement suggests that the conduction is due to small polaron hopping. (Some gures in this article are in colour only in the electronic version)

1. Introduction
Ferrites are well-studied materials, but due to the large interest in various potential applications and in order to understand the ongoing physical processes to tailor these materials for modern technology, there has been a growing interest in the study of the magnetic, electric and structural properties of mixed spinel ferrites [17]. Fine particles of magnetic materials exhibit interesting magnetic properties and recently ne particles of spinel ferrites synthesized by chemical methods were shown to have magnetic properties markedly different from those prepared by the ceramic
0964-1726/09/115028+07$30.00

method [8, 9]. CoFe2 O4 belongs to the family of spineltype ferrites and is one of the technologically important ferrites with high coercivity, moderate magnetization and very high magnetocrystalline anisotropy. Further, CoFe2 O4 is being investigated as an alternative ceramic material for developing novel magnetostrictive smart materials [10]. The previous studies have shown that Mn-substituted Co ferrites are excellent candidates for stress sensors due to a large magnetomechanical effect and high sensitivity to stress [1113]. Yan et al had prepared nanophased Co ferrite by the combustion method using glycine as a fuel [14]. It has been reported by Bhame and Joy that the studies on
1
2009 IOP Publishing Ltd Printed in the UK

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Co1.2x Mnx Fe1.8 O4 and Co1.2 Fe1.8x Mnx O4 (0 x 0. 4) systems showed a marked dependence of magnetostriction on the substitution of both Fe and Co by Mn and they concluded that a higher magnetostriction is obtained for the substitution of Co by Mn whereas the magnetostriction is reduced substantially on the substitution of Fe by Mn [15]. Nowadays a highly magnetostrictive and resistive ferrite phase has became an essential part of ferriteferroelectric magnetoelectric (ME) composites which show the magnetoelectric effect [16, 17]. It has been reported by Devan et al that, in order to obtain a good magnetoelectric response in ME composites, the ferrite phase should be highly magnetostrictive possessing high resistivity [18]. Focusing on these objectives we have prepared ne particles of the Co1.2x Mnx Fe1.8 O4 system (with x ranging from 0.0 to 0.4 in steps of 0.1) for the rst time by using the autocombustion route and reporting their structural, magnetic and dielectric properties.

2. Experimental details
All the samples of the Co1.2x Mnx Fe1.8 O4 system were synthesized by the chemical autocombustion route, in which the stoichiometric amount of the corresponding metal nitrates acts as an oxidizing agent and the fuel glycine as a reducing agent for the combustion reaction. The stoichiometry of the redox mixture for combustion is calculated based on the total oxidizing and reducing valencies of oxidizer (O) and fuel (F) (see the appendix), which serves as a numerical coefcient so that the equivalence ratio, i.e. e (O/F), becomes unity and the heat released is at its maximum [19, 20]. According to the principles used in propellant chemistry, the oxidizing and reducing valencies of various elements are considered as follows: C = 4, H = 1, O = 2, N = 0, M = 2, 3, + etc. Thus, typically for ferrites, i.e. M2+ Fe3 2 O4 , the oxidizing valency of a divalent metal nitrate, M(NO3 )2 , becomes 10; for trivalent Fe(NO3 )3 adding up to 15 should be balanced by the total valencies in the fuel glycine (H2 NCH2 COOH), which add up to +9. Hence, in order to release the maximum energy for the combustion reaction, the stoichiometric composition of the redox mixture requires 40 + 9n = 0 or n = 4.44 mol of glycine. Therefore, the molar ratio, i.e. e (O/F), of the oxidizing metal nitrate to the reducing fuel (glycine) is 40/9 = 4.44 (i.e. the proportion of M2+ :Fe3+ :fuel should be 1:2:4.44). Thus, a mixture of Co(NO3 )2 6H2 O, Mn(NO3 )2 4H2 O and Fe(NO3 )3 9H2 O in an appropriate molar proportion was taken in a 300 cm3 capacity Pyrex dish and was melted by heating on a magnetic stirrer at 80 C for 1015 min. Further, glycine was added to the melt and the slurry formed was introduced into a furnace which is preheated to 400 C. After evaporation of the water content, the mixture frothed and ignited to combust with a ame, giving a voluminous and foamy Co1.2x Mnx Fe1.8 O4 as a product. A typical owchart for the preparation of the CoMnFe ferrite system by the autocombustion method is shown in gure 1. The resulting powder was further characterized by thermogravimetric analysis (TGA) by means of SDT 2960 simultaneous DSC-TGA TA instruments USA at a heating 2

Figure 1. Flowchart for method of preparation.

rate of 10 C min1 in an air stream. For identication of the phase, the samples were characterized by the powder x-ray diffraction (XRD) technique (Cu K radiation, model Bruker D8 Advance). The room temperature magnetic measurements for all the compositions were performed by using a computerized high eld hysteresis loop tracer (Magenta, Mumbai) at 5 kOe magnetic eld strength. The relative dielectric permittivity ( ), dielectric loss (tan ) and ac conductivity (ac ) were measured at room temperature as a function of applied frequency in the range 20 Hz1 MHz using an LCR precision meter (HP 4284A).

3. Results and discussion

3.1. Thermogravimetric analysis (TGA) Figure 2 shows the typical TGA curve for x = 0.0 of the assynthesized powder of the Co1.2x Mnx Fe1.8 O4 system. There are two weight-losing processes present at temperatures 33 280 C and 280600 C with a total weight loss of 20%. The rst step of weight loss is 2% of the total weight, corresponding to the volatilization of the organic solvent and water of crystallization. In the second step of weight loss, the weight loss is 18% ascribed to the decomposition of nitrate and complex ferrite precursors into oxides. Also, from the TGA curve it is seen that after 690 C there is little increase in the weight observed (1%) up to 1000 C. This little increase in weight loss might be due to the oxidation process involved at the particular temperature because the measurement was taken in an air steam so there is a possibility to increase the weight loss. It can be inferred that the ne particles of complex ferrite could be obtained by calcination of their precursors at 600 C. For temperatures higher than 600 C there is approximately no weight loss process, which shows the stable phase formation above 600 C. Accordingly the samples of the Co1.2x Mnx Fe1.8 O4 system were sintered at 700 C for 4 h at a heating rate of 2 C min1 in an air stream.

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Table 1. The structural and magnetic parameters for the Co1.2x Mnx Fe1.8 O4 ferrite system. Ferrite compositions Co1.2 Fe1.8 O4 Co1.1 Mn0.1 Fe1.8 O4 CoMn0.2 Fe1.8 O4 Co0.9 Mn0.3 Fe1.8 O4 Co0.8 Mn0.4 Fe1.8 O4 Lattice constant (A) 8.37 8.38 8.39 8.40 8.41 X-ray density Dx (g cm3 ) 5.33 5.30 5.27 5.24 5.22 Saturation mag. Ms (emu g1 ) 106.50 123.74 138.5 124.71 97.78 Coercivity Hc (Oe) 1520.82 1300.03 1187.87 1221.53 1165.36 Remanence Mr (emu g1 ) 93.02 109.63 123.48 112.60 108.17

B (Bohr magneton)
4.48 5.20 5.81 5.22 4.09

Figure 2. Typical thermogram for Co1.2x Mnx Fe1.8 O4 system.

3.2. X-ray diffraction studies The x-ray diffraction technique was used to conrm the formation of a single-phase cubic spinel ferrite. Figure 3 show the x-ray diffraction (XRD) patterns for the Co1.2x Mnx Fe1.8 O4 system. The samples show all the characteristic reections of ferrite material with the most intense (311) reection which conrms the formation of a cubic spinel structure. The results obtained by x-ray diffraction patterns were indexed using JCPDS card nos. 22-1086 [21] and 74-2403 [22]. The lattice constant for Co1.2x Mnx Fe1.8 O4 system was calculated by using the relation 1 h2 k2 l2 = + + d2 a2 b2 c2 (1a )

Figure 3. X-ray diffraction patterns for the Co1.2x Mnx Fe1.8 O4 system.

components is observed [24, 25]. This linear increase in lattice constant may be attributed to the replacement of smaller Co2+ and Fe3+ (0.64 A) ions by the larger Mn2+ (0.83 A) (0.78 A) ions in the Co1.2x Mnx Fe1.8 O4 system [26]. The x-ray density or theoretical density was estimated by using the relation [27]

where d is interplanar spacing, (hkl) are the Miller indices and a , b , c are the lattice constants. For the cubic crystal system a = b = c, and therefore equation (1a ) becomes 1 = d2

Dx (ferrite) =

8M N a3

(2)

h2 + k2 + l 2 a2

(1b )

The concentration dependence of the lattice constant a for the Co1.2x Mnx Fe1.8 O4 system is calculated and shown in table 1. Also, from gure 4 it is observed that the lattice with constant a gradually increases from 8.37 to 8.41 A increasing Mn2+ content, obeying Vegards law [23]. Usually, in a solid solution of spinels within the miscibility range, a linear change in lattice constant a with the concentration of 3

where M is the molecular weight of the particular ferrite, N is Avogadros number and a 3 is the volume of the cubic unit cell. From gure 4, it is observed that x-ray density Dx decreases with the addition of Mn2+ ion content, which may be attributed to the ionic radii of constituent ions causing an increase in lattice constant and the densities of pure CoFe2 O4 (5.29 g cm3 ) and pure MnFe2 O4 (4.98 g cm3 ). 3.3. Magnetic properties Magnetic hysteresis loops were recorded at room temperature for all the compositions of the Co1.2x Mnx Fe1.8 O4 system

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Figure 4. Variation of lattice constant (a ) and x-ray density Dx with Mn content for the Co1.2x Mnx Fe1.8 O4 system.

Figure 6. Variation of saturation magnetization ( Ms ) and coercivity ( Hc ) with Mn content for the Co1.2x Mnx Fe1.8 O4 system.

this enhances the saturation magnetization as the magnetic moments for Co2+ and Mn2+ are 3 B and 5 B , respectively. The magnetic moment per formula unit in Bohr magnetons (B ) was calculated by using the following relation [28] and is tabulated in table 1:

B =

M Ms 5585

(3)

Figure 5. Room temperature B H hysteresis loops for the Co1.2x Mnx Fe1.8 O4 system.

and are shown in gure 5. The variation of saturation magnetization ( Ms ) and that of coercivity ( Hc ) with Mn content for all the ferrites is shown in gure 6. The observed values of Ms (table 1) increase with increasing Mn content up to x = 0.2 and then decrease to a small value. The changes in the magnetization at room temperature, on the substitution of Mn for Co, may be due to the following factors such as (1) The difference in the contributions from the magnetic moment of the substituted ion on the A-site and B-site of the spinel ferrite. (2) Decreasing contribution from the magnetocrystalline anisotropy of Co after substitution of Mn. A maximum magnetization of 138.50 emu g1 is obtained for the composition with 20% Mn and which might be the most suitable constituent phase for magnetoelectric (ME) composites. The increase in magnetization with Mn content may be attributed to the substitution of Co2+ by Mn2+ and 4

where M is the molecular weight of a particular composition and Ms is the saturation magnetization (emu g1 ). The initial increase in the saturation magnetization of Co1.2x Mnx Fe1.8 O4 at lower concentrations of Mn (i.e. x = 0.1 and 0.2) indicates that initially the Mn2+ ions are substituted in the (octahedral) B-site and, at higher concentrations of Mn (i.e. x = 0.3 and 0.4), the Mn2+ ions may be distributed in the (tetrahedral) A-site of the spinel lattice [29]. Also, it is found the coercivity (coercive force) of all the samples almost decreases linearly with increasing Mn content. The observed variation in the coercivity of the Co1.2x Mnx Fe1.8 O4 system is similar to that reported in the previous studies on Mn-substituted CoFe2 O4 [3032]. However, for the composition with x = 0.3, an unexpectedly slight increase in coercivity is observed. This is probably due to some peculiar changes in the cation distribution in the octahedral and tetrahedral sites near this composition [29]. 3.4. Dielectric properties and ac conductivity Figure 7 shows the variation of relative dielectric permittivity ( ) with frequency f . It has been found that the relative dielectric permittivity decreases steeply at lower frequencies and remains constant at higher frequencies, indicating the usual dielectric dispersion. This may be attributed to the polarization due to changes in valence states of cations and space charge polarization. At higher frequencies the dielectric constant remains independent of frequency due to the inability of electric dipoles to follow the fast variation of the alternating applied electric eld. Thus the dispersion occurring in the lower frequency regime is attributed to interfacial

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R C Kambale et al

Figure 7. Variation of relative dielectric permittivity ( ) with frequency for the Co1.2x Mnx Fe1.8 O4 system.

Figure 8. Variation of dielectric loss factor (tan ) with frequency for the Co1.2x Mnx Fe1.8 O4 system.

polarization since the electronic and atomic polarizations remain, by and large, unchanged at these frequencies [33]. Such kinds of similar results were observed for other systems of ferrites [3436]. The decrease in permittivity with frequency can be explained on the basis of Koops phenomenological theory [37], which considers the dielectric structure as an inhomogeneous medium of two layers of the MaxwellWagner type [38]. According to this theory, the conductivity of grain boundaries contributes more to the dielectric value at lower frequencies. In this model, the dielectric structure is assumed to consist of well-conducting grains which are separated by poorly conducting grain boundaries. It was found that, for ferrites, the permittivity is directly proportional to the square root of conductivity [35]. Therefore the grains have higher values of conductivity and permittivity, while the grain boundaries have lower values. At lower frequencies the grain boundaries are more effective than grains in electrical conduction. Therefore the permittivity is high at lower frequencies and decreases as frequency increases. Also, the low frequency dispersion in ferrites is observed due to the space charge effect [39, 40]. In the present study, it was observed that the dielectric permittivity goes on increasing with the increase of Mn2+ concentration in cobalt ferrite. This may be due to the decrease in resistivity of cobalt ferrite with the substitution of Mn2+ concentration, as the permittivity is directly proportional to the square root of conductivity. Figure 8 shows the variation of loss tangent with frequency and possesses similar behaviour to that of dielectric permittivity ( ). This loss factor curve is considered to be caused by domain wall resonance. At higher frequencies, losses are found to be low if domain wall motion is inhibited and magnetization is forced to change by rotation [18]. Also, in ferrites it is observed that the mechanism of dielectric polarization is similar to the mechanism of electrical conduction [41]. Therefore, the variation of relative dielectric permittivity can be related to the collective behaviour of both types of electronic charge carriers, electrons and holes. 5

Therefore, according to Rabinkin et al [42], the polarization in ferrites is through a mechanism similar to the conduction process. The presence of Fe3+ and Fe2+ ions render ferrite materials to be dipolar. Rotational displacement of dipoles results in orientational polarization. In ferrites, rotation of Fe2+ Fe3+ dipoles may be visualized as the exchange of electrons between the ions so that the dipoles align themselves in response to the alternating eld. The existence of inertia to the charge movement would cause relaxation of the polarization. The polarization at lower frequencies results from electron hopping between Fe3+ Fe2+ ions in the ferrite lattice. The polarization decreases with increase in frequency and reaches a constant value due to the fact that beyond a certain frequency of external eld the electron exchange Fe3+ Fe2+ cannot follow the alternating eld [43]. In order to understand the conduction mechanism and the type of polarons responsible for conduction, the variation of ac conductivity as a function of frequency is represented in gure 9. In most of the disordered solids, ac conductivity is directly proportional to the frequency. It is also well known that, in large polaron hopping, the ac conductivity decreases with frequency whereas in small polaron hopping it increases with frequency [44, 45]. The electrical conduction mechanism in terms of the electron and polaron hopping model has been discussed by Austin and Mott [46]. In the present case, the plots for ac conductivity measurement are linear, indicating that the conduction is due to small polarons. It has been shown that, for ionic solids, the concept of small polaron is valid [47]. As the frequency of the applied eld increases, the conductive grains become more active, thereby promoting electron hopping between two adjacent octahedral sites (B-sites) in the spinel lattice and a transition between Fe2+ and Fe3+ ions, thereby increasing the hopping conduction. Therefore a gradual increase in conductivity was observed with frequency. As reported by Alder and Fienleib [48], the frequency-dependent conduction is mainly attributed to a small

Smart Mater. Struct. 18 (2009) 115028

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Appendix. Calculation of elemental stoichiometric coefcient (ESC) or equivalence ratio, i.e. ( e = oxidizer/fuel) of a mixture
The oxidizer/fuel molar ratio (O/F) required for a stoichiometric mixture ( e = 1) is determined by summing the total oxidizing and reducing valencies in the oxidizer compounds and dividing it by the sum of the total oxidizing and reducing valencies in the fuel compounds. In this calculation oxygen is considered as an oxidizing element, whereas carbon, hydrogen and metal cations are considered to be reducing elements and nitrogen as a neutral element. Oxidizing elements have positive valencies and reducing elements have negative valencies. In combustion calculations, the valency of the oxidizing elements was modied and considered as negative, and the reducing elements as positive, similar to the oxidation number concept familiar to chemists. The equivalence ratio of an oxidizer and fuel mixture is expressed in terms of the elemental stoichiometric coefcient or e = oxidizer/fuel ratio:
e

Figure 9. Variation of ac conductivity (ac ) with applied frequency for the Co1.2x Mnx Fe1.8 O4 system.

(coefcient of oxidizing elements in specic ( 1 ) (coefcient of

1

polaron-type hopping mechanism and the present study also reveals that the conduction mechanism in Mn2+ -substituted Co ferrite is of small polaron type due to the linear response of ac conductivity to the applied frequency.

formula) (valency)

reducing elements in specic formula) (valency)

4. Conclusion
Fine particles of Co1.2x Mnx Fe1.8 O4 (0 x 0.4) compositions were successfully synthesized by the autocombustion route. The TGA analysis reveals that the complete phase formation of the product material takes place at a temperature above 600 C. The x-ray diffraction study reveals the formation of a cubic spinel structure. The magnetic measurements lead us to conclude that the saturation magnetization of cobalt ferrite goes on increasing for lower doping levels of Mn2+ (x = 0.1 and 0.2) and decreases for higher levels of Mn2+ (x = 0.3 and 0.4). From the studied compositions, the composition x = 0.2 is the most suitable constituent phase for the magnetoelectric (ME) composite due to its higher magnetization and we hope that it will show a better magnetoelectric response and may be used as a eld sensor in future. The dielectric permittivity goes on increasing with the increase of Mn2+ concentration in the substituted Co ferrites, showing the usual dielectric dispersion with frequency. The ac conductivity measurement with frequency leads us to conclude that the conduction mechanism in the present case is of small polaron type.

A mixture is said to be stoichiometric when e = 1, fuellean when e > 1 and fuel-rich when e < 1. Stoichiometric mixtures produce maximum energy. For ferrite, i.e. (MFe2 O4 ) formation, M(NO3 )2 and Fe(NO3 )3 act as oxidizers while glycine (H2 NCH2 COOH) acts as a fuel:
e

= {[(1M 2) + (2N 0) + (6O 2) + (2Fe 3)

+ (6N 0) + (18O 2)]}{[(1){(2C 4) + (1N 0) + (5H 1) + (2O 2)}]}1 40 = 4.44. e = 9 Thus, the metal nitrate:glycine molar ratio = 4.44. For complete combustion of all the components, the required equivalence ratio e should be unity, i.e. e = 1.

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Acknowledgment
One of the authors (RCK) is grateful to the University Grant Commission (UGC), New Delhi, Government of India, for providing a UGC Research Fellowship in Sciences for Meritorious Students. 6

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