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Magnetic and dielectric properties of cadmium
substituted nickel cobalt nanoferrites
ARTICLE in JOURNAL OF MATERIALS SCIENCE MATERIALS IN ELECTRONICS · MARCH 2012
Impact Factor: 1.97 · DOI: 10.1007/s10854-012-0878-3

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Venkataraju Chidambaram

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0 to 0. Chemical coprecipitation affords greater control over the size and the shape of the particles in the range of 10 nm and results in highly uniform morphologies.5-X)Co0. Anna University Chennai. CoCl2.edu.5-X) Co0.5Fe2O4 nano particles Nano particles of CdXNi(0.1 Preparation of CdXNi(0. Analytical Grade of FeCl3. sol gel.1. CdCl2.1007/s10854-012-0878-3 Magnetic and dielectric properties of cadmium substituted nickel cobalt nanoferrites G.6H2O and NaOH6H2O were used as the starting materials.2 and 0.in C. Sathishkumar • C.5Fe2O4 (x = 0.5-X)Co0. Sivakumar • Received: 16 June 2012 / Accepted: 18 August 2012 Ó Springer Science+Business Media. CoCl2. India unique magnetic properties due to their reduced particle size below 100 nm. It is then transferred immediately into a boiling 123 . The dielectric constant increases with increase in Cd concentration. 0. Chennai 600044.J Mater Sci: Mater Electron DOI 10. The magnetic and electrical properties are reported to be highly sensitive to the cation distribution which in turn depends on the material of synthesis and sintering conditions. 1. India e-mail: sathishkumar. moderate to high permittivity and low losses at frequencies from dc to submillimeter wavelengths. Madhurantakam 603308. Magnetic nanoparticles are important class of materials which posses G. Chennai 600025.5 Fe2O4 nano particles prepared through coprecipitation method. Then the solutions were mixed thoroughly using magnetic stirrer at 80 °C. India K. Stoichiometric proportions of aqueous solutions of FeCl3.5Fe2O4 (where x = 0. The lattice constant and distribution of cation in A-site and B-site have been deduced through X-ray ´˚ diffraction (XRD) data analysis. The lattice constant (A ) was found to increase with increase in Cd2? concentration in the spinel structure of Ni–Co ferrites.5-X)Co0.5 times when cadmium is substituted in Ni–Co perminvar ferrite. Many work have been carried out by the substitution of Cd ion in spinel structure of ferrite [4–6]. aerosol reactions have been used in the preparation of nanoscale materials [3]. Sivakumar Department of Physics. 0. Saha [7] has reported that there is an increase in the dielectric constant by 3. Sathishkumar (&) Department of Physics. This prompted us to carry out the present work to study the effect of cadmium substitution on the properties of CdX Ni(0. A variety of methods such as co-precipitation. NiCl2. 1 Introduction Ferrite materials are unique because they posses moderate value of magnetization. CdCl2 and NiCl2 are taken separately. high permeability. gas condensation. Venkataraju Department of Physics. In recent years nanocrystalline ferrites have attracted much interest because of unusual magnetic properties and their promising technological applications.6H2O. with potential use in device fabrication [2]. It is observed that the Curie temperature (Tc) is higher than in bulk counterpart. Venkataraju K. Each technique has some unique advantages. LLC 2012 Abstract Nano particles of CdXNi(0. These properties of ferrites suit them for high frequency application [1]. Sri Sairam Engineering College. The saturation magnetization was found to decrease with increase in Cd concentration for all the samples.0.8H2O.phy@ssec.3) were synthesized by chemical coprecipitation method. The bulk properties of ferrites changes as its dimensions are changed to nanoscale. This increase in dielectric constant is attributed to the formation of Fe3? ion in the octahedral site which increases the hopping between Fe3? and Fe2?.3) were prepared by coprecipitation method. Karpaga Vinayaga College of Engineering and Technology.

28 Fe3? 0. rA and rB are where R0 is the radius of oxygen ion (1.385 10.01 B-site cation distribution Co2? 0. a portion of the material is pelletized at 3 ton pressure for 3 min.19 Fe0.1 Ni0.3 Ni0. The ionic radius of ˚ ) is greater than ionic radius of Ni2? ions Cd2? ions (0.18 Ni0. 0. Replacement of larger Cd2? cations for smaller Ni2? cations in the nickel cobalt ferrite causes an increase in the lattice constant.38 Co2? 0.3 Fe0. These diffraction lines provide clear evidence for the formation of ferrite phase in all the samples.2 Ni0. The lattice parameter ‘a’ is found to increase with increase in Cd concentration for all the compounds.5Ni0. 1.2 Co0.5Fe2O4 (with x = 0.405 9. The values of lattice parameter ‘a’ and particle size as deduced from the X-ray data are given in the Table 1. Washing and filtering are repeated with deionised water until the pH of the solution becomes neutral and finally the sample is dried in a heating oven for about 5 h.35 10. The lattice parameter for ˚ . The pH of the solution is maintained at 12 throughout the reaction.J Mater Sci: Mater Electron solution of NaOH at 100 °C.5 Fe2O4 8.35 A value is similar to the values reported by Singhal [9]. i pffiffiffi 8 h ath ¼ pffiffiffi ðrA þ R0 Þ þ 3ðrB þ R0 Þ ð1Þ 3 3 ˚ ).4 Co0.5 Cd0.12 Fe1. then precipitation takes place.01 Cd0.42 Co0. respectively.12 Fe1.22 2? 2? 3? 2? Cd2? 0. r(Ni2?). 2.02 Cd2? 0.12 Fe1.5-X)Co0.2Ni0.5 Ni0.1.58 Fe3? 0. r(Co2?) and r(Fe3?) are the radius of the Cd2?. 2.3 Co0.97 A ˚ (0. Co2? and Fe2? ions respectively.54 Cd2? 0.3) the ionic radius of tetrahedral (A-site) and octahedral (Bsite).12 Fe1.38 2? 3? 2? Ni2? 0.28 Co0.0 to 0. The broad XRD line indicates that the ferrite particles are of nanosize.5-X)Co0.08 Ni0.32 A Fig.5 Fe2O4 8. The agreement between ath and aexp obtained from X-ray data indirectly supports the cation distribution.3Co0.79 A).38 Fe0.5 123 Ni2? 0.5Fe2O4 (with x = 0. 1 XRD pattern for the composition CdXNi(0.6 2? 2? 3? 2? Cd2? 0.425 8.2.29 Ni0.5Fe2O4 in the present investigation is 8. The average particle size is around 10 nm. The average crystalline size of each composition are calculated from XRD line width of the (311) peak using Scherrer equation [8].5 2? 3? Ni2? 0. The entire solution is stirred using mechanical stirrer for about 60 min until the reaction is complete.0. The ionic radius for each site was calculated according to the following expression       CACd r Cd2þ þ CANi r Ni2þ þ CACo r Co2þ   þ CAFe r Fe3þ ð2Þ   2þ   2þ   2þ  þ CBNi r Ni þ CBCo r Co rB ¼ CBCd r Cd  3þ   2þ  þ CBFe r Fe 2 ð3Þ þCBFe r Fe rA ¼  where r(Cd2?). All the peaks in the diffraction pattern have been indexed and the refinements of the lattice parameter were done using powderX software.38 Co2? 0.2 Transmission electron microscopy analysis The particle size and morphology of the compound Cd0. TEM analysis revealed that the particles are nearly spherical.5 Fe2O4 8.04 Ni2? 0.02 Cd2? 0. The dried powder is grounded using agate mortar.5 Fe2O4 8.5Fe2O4 is shown in Fig.25 2? 2? 3? 2? Cd2? 0. 0.36 Co0. Ni2?. Table 1 Parameters deduced from XRD studies Composition Lattice ˚ constant A Particle size nm A-site cation distribution Co0.56 Fe3? 0.3) is shown in Fig.1 . The pelletized samples were coated with silver paste on either side followed by heating of the samples up to 200 °C for 1 h to ensure good electrical contact. 0. The particle size determined from TEM was found to be in close agreement with that obtained from XRD studies.02 Ni2? 0. This Co0. The pellet and the powder were then sintered in furnace at 550 °C for 5 h.2 Fe0.1 XRD analysis The X-ray diffraction pattern for CdXNi(0. The lattice constant can be calculated theoretically by the relation suggested by Mazen et al.18 Fe0.19 Co0.3 Cd0.8 Co0. 2 Experimental analysis 2.

The saturation magnetization for all the samples is reported in the Table 2. As a result the magnetization at the B site decreases resulting in overall decrease in magnetization of the sample.3) 123 .J Mater Sci: Mater Electron Fig.1.5-X)Co0. 2 TEM images for the composition Cd0.5-X)Co0.2Ni0.1. Figure 4 shows the hysteresis loop curve for all the compounds CdXNi(0.0 to 0.5-X)Co0.620 cm-1 are due to O–H stretching vibration interacting through H bonds. The band at 590 cm-1 corresponds to intrinsic stretching vibrations of the metal at the tetrahedral site.0. 0. 3 FTIR spectrometer graph for the composition CdXNi(0.5Fe2O4 (x = 0.420 cm-1 and the less intensive band at 1. This may be due to occupation of non magnetic Cd2? ion in the B site.2.1 Magnetic studies 3 FTIR studies Figure 3 Shows the FTIR spectra of the nanocrystalline CdXNi(0.3). 0.000 cm-1. The presence of tetrahedral vibrations indicates the formation of ferrite phase. 0. 0.3) Fig.3). & 0. Hence the band for octahedral vibrations t11 observed at 420 cm-1 is absent [10] in the present study.5Fe2O4 (with x = 0.0 to 0. Similarly the coercivity values also decreases linearly with increasing in the Cd2? ion concentration.2.3. 0. The linear decrease in coercivity (Hc) in nano-crystalline system is strongly correlated to their size dependence. The presence of bands in the range 591 cm-1 is due to the tetrahedral vibration t1.5Fe2O4 (x = 0. It is observed that the saturation magnetization decreases from x = 0 to 0. This forces the Fe3? ions from B site to A site.3Co0. 4 Hysteresis loop at room temperature for the composition CdXNi(0.5Fe2O4 (where x = 0.5-X)Co0.5Fe2O4 3. In our case a decrease in Fig. The measurements were taken in the range from 450 to 4. The intensive broadband at 3. Azizi [11] has reported a value of 25 emu/g at 10 KOe which matches our result.0.

6 that the dielectric constant for all the samples is lower than the corresponding bulk value at room temperature. Any further increase in magnetic field has an effect only on the surface causing a slowdown of magnetization.0.3) are shown in Fig. 0. The values of the saturation magnetization Ms obtained in the present investigation is lower than the corresponding values of bulk ferrite.1.5-X)Co0. This low value of dielectric constant is attributed to homogeneity.1.5Fe2O4 25. In addition to this.5Fe2O4 (with x = 0. According to the Core–shell morphology of nanoparticles. Smaller grains contain large surface boundaries and are the regions of high resistance.5-X)Co0. The Tc values of the samples were deduced from the graph by extrapolation of the graph along x axis in the M (Vs) T graph.5Fe2O4 25. Coey [12] attributed the smaller value of Ms in nanoparticles to the existence of random canting of particles surface spins caused by competing anti ferromagnetic exchange interactions due to asymmetry in the environment of the spins. 0. This is due to the substitution of the non-magnetic Cd2? in place of Ni2? ion. This decrease in the Ms value can be explained based on the cation distribution.20 1.33 20.4Co0.45 25. Pankhurst [13] claimed that the lower magnetization values are due to non saturation effects because of random distribution of the small particles with enhanced values of magneto-crystalline anisotropy. It is clearly seen from Fig.2Ni0. Smaller grains have larger surface to volume ratio.13088 48. 0.99 515 15.29 51.J Mater Sci: Mater Electron Table 2 Parameters deduced from magnetic and dielectric studies Composition Saturation magnetization (emu/gms) Ms Coercivity (Oe) Mc Remanent magnetisation (emu/gms) Mr Curie temperature Tc K Dielectric constant at 1 kHz e9 Co0. There is a systematic decrease in the value of the Curie temperature (Tc) as the cadmium concentration increases except for the Cd content x = 0. The change in Tc may be positive or negative depending on the boundaries. Temperature dependence of magnetization at constant applied field of 500 Oe for the samples CdXNi(0. 0.2 and 0.1. This is the reason all our samples do not reach saturation magnetization under an applied field of 15 KOe.11407 Cd0.5Fe2O4 (x = 0.5Fe2O4 23.66978 Cd0. The value of Tc is found to be higher than that of 123 Fig.3Co0. uniform and smaller grains [16]. This reduces the interfacial polarization which decreases the dielectric constant in the present investigation when compared with the bulk .2.85256 particle size was observed with increasing the Cd2? ion concentration. Size effect in nanoparticles can cause a reduction in the magnetization value in comparison with the bulk counterpart.589 497 385 35. 0.5 76. The core magnetic moment aligns with the applied magnetic field and gets saturated at a particular value of magnetic field.2Co0. better symmetry. 5 M-T curve for the composition CdXNi(0. the other factors reported in the literature by other researchers may contribute to the reduction of Ms in nanoparticles.39 35.1Ni0.21 0.3) its bulk counterpart.5Ni0. The deviation of Tc for the sample with Cd concentration x = 0.3Ni0.620 413 27. 3.5-X)Co0. geometry and interaction.90 1. Spin disorder at the surface of the nanoparticles increases especially when the surface to volume is large. may be due to variation in the cation distribution. In the present investigation a dielectric constant of 15 is obtained.0.2 Dielectric studies Figures 6 and 7 shows the variation of dielectric constant (e9) and dielectric loss factor tan (d) as a function of applied angular frequency (x) for the composition CdXNi(0. It is also possible that Tc decreases due to some unknown surface effect [14]. Kambale [15] have reported a dielectric constant of 200–400 at 300 K measured at a frequency of 1 kHz for Ni–Co ferrite in bulk prepared by double sintering ceramic method. 5 Magnetization decreases with increase in temperature and attains constant after a particular temperature. at a frequency of 1 kHz at 308 K.5Fe2O4 Cd0.1.5Fe2O4 (x = 0. the core consists of ferrimagnetically aligned spins and a surface with disordered spins.70 0.0 to 0.3) respectively at room temperature 308 K.

J Mater Sci: Mater Electron Fig.0 to 0. The shifting of relaxation peak towards lower frequency side with increase in cadmium concentration (x) is due to strengthening of the dipole–dipole interactions causing hindrance to the rotation of the dipoles [20].5-X)Co0. This dielectric structure is supposed to be composed of two layers [19]. The conduction mechanism can be explained on the basis of hopping in B-site between the charge carriers Fe2? and Fe3?. The appearance of relaxation peak can be explained according to the Debye relaxation theory [20].5Fe2O4 (with x = 0. 18]. [21] have observed a similar relaxation at a frequency of 1 kHz for Cd substituted Ni–Co ferrites synthesized by the co precipitation method. 7 Variation of dielectric loss with frequency for the composition CdXNi(0. The decrease in dielectric constant at higher frequency can be explained on the basis of Maxwell & Wagner theory which is a result of the homogeneous nature of dielectric structure.c conductivity (rac) with frequency for the composition CdXNi(0. It is observed that the loss tangent decreases initially with frequency followed by appearance of the relaxation peak. The decrease is quite rapid at low frequencies and becomes quite slow at higher frequencies. 6 Variation of dielectric constant with frequency for the composition CdXNi(0.5Fe2O4 (with x = 0. It is seen that the ac conductivity found to increase with increase in frequency and an increase in cadmium concentration. 8 Variation of a. Hence the resonance between rotation of the dipoles and applied field takes place at lower frequency. Increase in the frequency of the applied field increases the hopping mechanism and hence there is an increase in ac conductivity.5Fe2O4 (with x = 0.0 to 0. 7.3) material. The composition dependence of dielectric constant is observed to increase with increase in cadmium concentration for all the samples. the electrons cannot follow the alternating field. This decreases the probability of electrons reaching the grain boundary and as a result polarization decreases.5-X)Co0.0 to 0. The variation of dielectric loss factor (tan d) is shown in Fig. The increase in Fe3? ions in the B-site increases the hopping between the charge carriers Fe2? and Fe3? and hence there is an increase in conductivity rac with increase in cadmium concentration. Singh et al. 6 the value of dielectric constant decreases with increasing frequency showing usual dielectric dispersion which is due to Maxwell–Wagner type interfacial polarization [17. where x = 2gf.3) Fig. The loss peak occurs when the applied field is in phase with the dielectrics and the condition xs = 1 is satisfied. when Cd2? ions is replaced by Ni2? ions in B-site. f is the frequency of the applied field. electrons pile up at the boundaries and produce polarization. It results in the formation of Fe3? ions in the B site and hence increases the electron hopping between Fe2? and Fe3? ions. 123 . However as the frequency of the applied field is increased beyond a certain value. where first layer is the large ferrite grains of fairly well conducting materials which is separated by the second thin layer (grain boundaries) of relatively poor conducting grain boundaries. The electrons reach the grain boundary through hopping and if the resistance of the grain boundaries is high enough.5-X)Co0. The increase in rac with the increase in cadmium concentration may be due to the increase in Fe3? in B-site. Therefore polarization increases and hence the dielectric constant increases. The Figure 8 shows the variation of ac conductivity log(rac) with frequency at 308 K. It is observed from the Fig. In Cd–Ni–Co ferrites.3) Fig.

Trivedi. Barthwal.B. 0. Rucha Desai. Low temperature synthesis of nanosized Mn1-xCdxFe2O4 ferrites. M. vol. J.V. Anokhin.A.1.5-X)Co0. Saha. R. Chandra Prakash. The lattice constant is found to increase with increase in Cd substitution. K.Y. London.G. Hakim. Venkataraju. Can J Phys 65.N. Singh. Noncollinear spin structures. C. P. J Magn Magn Mater 322. P. Kurihara. J of solid State chem 178.J Mater Sci: Mater Electron 4 Conclusion CdXNi(0. Shaikh. Aliev. 3183–3189 (2005) 10. R. Section 328 (Oxford University Press. Coey. J Magn Magn Mater 320(3–4). Upadhyay. Sivakumar. Kulkarni. Elements of X-ray diffraction (Addison–Wesley. 230–233 (2010) 15. Mendiratta. A. The theory of incomplete dielectricity.A. J Appl Phys 91. J Bangladesh Acad Sci 32(1). Solid State Commun 48(8). C.V.5Fe2O4 (x = 0.5 to 20. Koops. Johi.C. 0. J Magn Magn Mater 322. 085014 (2009). Gul. Ahmed. G. Wagner. 248–250 (1991) 14. 688–690 (2005) 21. 1873) 18.A. Yoozbashizadeh. A.P. Preparation and Characterization of nanosize nickel-substituted cobalt ferrites (Co1-xNixFe2O4). L. Sathishkumar. 23–32 (2008) 123 8. Kolekar.2 and 0.W. Indian J Pure Appl Phys 43. O. K. Modi. Effect of cation distribution on the structural and magnetic properties of nickel substituted nanosized Mn–Zn ferrites prepared by co-precipitation method. modern microwave ferrites—advances in magnetics. A study of nano-structured Zn– Mn soft spinel ferrites by the citrate precursor method. 1.0. K. I. J.D. Aliev.K. V. Int Mater Rev 49(3–4).K. H. 125–166 (2004) 3. (6 pp) 16. J. Electricity and magnetism. 1978) 9. Kambale. Ann Phys 40. E. Goel. B. C. Brabers. R. Phys Rev 83. Chhantbar. Singh.8Ni0. Mater. M.C.H. Dielectric Properties. M. Amin Azizi. Rajesh Iyer. 10751105 (2012) 2. Appl Phys 49. S.2Fe2O4. Q. S. Mathur.A.5Fe2O4 by annealing.D. Harris. R. On the dispersion of resistivity and dielectric constant of audio frequency.A. Amarendra K.M. Dielectric properties and complex impedance spectroscopy studies of mixed Ni–Co ferrites. Kh. A. Pankhurst. It is also observed Curie temperature decreases with increase in the cadmium concentration. 1210–1232 (1987) 13. Calvin. Harris. H. Thankur. Phase formation and change of magnetic properties in mechanical alloyed Ni0. Upadhyay. R. 270–275 (2008) 4. Y. 121–124 (1951) 20. Chandra. I. 817–855 (1913) 19. Kamilov. From the cation distribution it is observed that the Cd ion occupies both the A site and B site.H. Resistivity and Curie temperature Of Co doped CdNi perminvar ferrite. 180–185 (2009) 5. K. JPET Lett 30.of Pure and.E. References 1. (6 pp) 17. Cullity.M. Maxwell.39 emu/g. 6626–6629 (2002) .G. Phys Rev Lett 67. Carpenter. Mohammadi.G.K.G. Willard. Yourdkhani. Vincent G. Low-temperature Mo¨ssbauer study of the Mg-Cd ferrite system. 045701 (2008). Frequency dependent of dielectric behavior of cadmium and chromium cosubstituted nickel ferrite. R.K. Rajpure. Pollard.T. The increase in dielectric constant with concentration is attributed due to formation of Fe3? in the octahedral site which increases the hopping between Fe3? and Fe2?. Sonal Singhal. 691–695 (1983) 7. L.3) nano particles were prepared by coprecipitation method. Dielectric properties of Mn-substituted Ni–Zn ferrites. Origin of the spin-canting anomaly in small ferrimagnetic particles. Maqsood. Bhosale. U. The saturation magnetization values were found to decrease with increase in cadmium concentration from 25. Thakur. 95 (1979) 6. IEE Trans Magn 48(3). Singh. W. Indian J.H. Phys Status Solidi b 33.J. Sh. T.5Co0. 56–59 (2010) 12. D.K. Chemically prepared magnetic nanoparticles. 563–572 (1969) 11. Iron spin relaxation in ferrite Cd0. Physica Scripta 77. Infrared Spectra of Cubic and Tetragonal Manganese Ferrites. V. Smart Mater Struct 18. London.C. M. M. Electrical and magnetic characterization of nanocrystalline Ni–Zn ferrite synthesis by coprecipitation route. K.K.