Materials Research Bulletin 48 (2013) 14151419

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Materials Research Bulletin

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Electrical and dielectric properties of nano crystalline NiCo spinel ferrites

V.L. Mathe *, R.B. Kamble
Novel Materials Research Laboratory, Department of Physics, University of Pune, Ganeshkhind, Pune 411 007, M.S., India

A R T I C L E I N F O

A B S T R A C T

Article history: Received 5 June 2012 Received in revised form 6 December 2012 Accepted 9 December 2012 Available online 19 December 2012 Keywords: A. Magnetic materials C. X-ray diffraction D. Dielectric properties D. Electrical properties

Nanocrystalline samples of NixCo1xFe2O4, where x = 1, 0.8, 0.6, 0.4, 0.2 and 0, were synthesized by chemical co-precipitation method. The spinel cubic phase formation of NiCo ferrite samples was conrmed by X-ray diffraction (XRD) data analysis. All the Bragg lines observed in XRD pattern belong to cubic spinel structure of ferrite. Scanning Electron Microscopy (SEM) technique was used to study the surface morphology of the NiCo ferrite samples. Nanocrystalline size of NiCo ferrite series was observed in SEM images. Pellets of NiCo ferrite were used to study the electrical and dielectric properties. The resistivity measurements were carried out on the samples in the temperature range 300 900 K. Ferrimagnetic to paramagnetic transition temperature (Tc) for all samples was noted from resistivity data. The activation energy below and above Tc was calculated. The dielectric constant (e0 ) measurements with increasing temperature show two peaks in the temperature range of measurements for all samples under investigation. The peaks observed show frequency and compositional dependences as a function of temperature. Electrical and dielectric properties of nanocrystalline NixCo1xFe2O4 samples show unusual behavior in temperature range of 500750 K. To our knowledge, nobody has discussed such anomalies for nanocrystalline NixCo1xFe2O4 at high temperature. Here, we discuss the mechanism responsible for electrical and dielectric behavior of nanocrystalline NixCo1xFe2O4 samples. 2012 Elsevier Ltd. All rights reserved.

1. Introduction Nanocrystalline magnetic materials have attracted large number of researchers due to their unusual physical and chemical properties compared to bulk. Nanomaterials, particularly with magnetic properties, are of great interest for their applications in home appliances, electronic products, communication and data processing devices, radio, television, microwave and satellite communication, etc. [15]. Magnetic nanomaterials also nd applications in a variety of areas such as magnetic refrigeration at high temperature [6], high density information storage [7], color imaging [8], ferrouids [9], bioprocessing [10], medical diagnosis [11], electromagnetic wave absorption [12], etc. Mixed ferrites usually have better performance than simple ferrites and show properties and stability depending on the stoichiometry and nature of the metallic ions in the nal composition. NiCo ferrites have been used extensively since few decades in the electrical and electronic industries. NiCo ferrites are soft magnetic materials that have spinel congurations based on a facecentered cubic lattice of the oxygen ions, with the unit cell consisting of 8 formula unit of the type [Fe3+]tetra [Ni2+Fe3+]octa

* Corresponding author. Tel.: +91 020 25692678; fax: +91 020 25691684. E-mail addresses: vlmathe@physics.unipune.ernet.in, dearvikas_2000@yahoo.com (V.L. Mathe). 0025-5408/$ see front matter 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.materresbull.2012.12.019

O42 or [Fe3+]tetra [Co2+Fe3+]octa O42 or mixed Ni and Co ferrite. In this formula tetra represents tetrahedral site and octa represents octahedral site. The structural, electrical, dielectric and magnetic properties of ferrite are very much sensitive to technique adopted for the synthesis, preparative parameters, initial ingredients, heat treatment, etc. Due to the above mentioned parameters there may be change in cation distribution which may result into unexpected electrical, dielectric and magnetic properties. Ferrites are commonly produced by a ceramic process; which consists of rather large and non uniform sized grains being prepared at high temperatures [13]. These non uniform grains on compaction result in the formation of voids leading to low density. These materials also can be prepared by various chemical techniques such as, chemical co-precipitation [14], solgel [15], soft chemical route [16], etc. Interest in preparing nano crystalline ferrites is avoiding energy losses associated with the synthesis of bulk material. Also the need of obtaining the materials near to theoretical density is raised so as to further improve physical properties [5]. The chemical co-precipitation has been considered as a good method for production of homogeneous, ne grained and reproducible ferrite systems [17]. In this work, we have studied synthesis of nanosized ferrimagnetic NixCo1xFe2O4 powder by coprecipitation technique followed by heat treatment. The series of NiCo ferrite having nominal compositions NiFe2O4, Ni0.8Co0.2Fe2O4, Ni0.6Co0.4Fe2O4, Ni0.4Co0.6Fe2O4, Ni0.2Co0.8Fe2O4 and CoFe2O4 are refereed as A, B, C, D, E and F respectively. These

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_ Fe 2 3

(220)

(222)

(400)

compositions have been investigated for their structural, electrical and dielectric properties. 2. Experimental

(422)

(511)

(440)

(311)

Intensity ( A.U.)

2.1. Material preparation Chemical co-precipitation route was used for synthesis of nanocrystalline powder of NixCo1xFe2O4 series, where x = 1, 0.8, 0.6, 0.4, 0.2, 0. Nickel nitrate [Ni(NO3)26H2O], ferric nitrate [Fe(NO3)39H2O] and cobalt acetate (CH3COO)2Co4H2O were taken as ingredients in desired molar proportion and mixed together in distilled water. It was then heated at 90 8C with constant stirring for 2 h to get the clear solution. Drop by drop addition of 1 M NaOH to above solution resulted into precipitate. The co-precipitation reaction was carried out at 90 8C and pH = 12. The precipitate was washed several times using hot distilled water and ltered until the pH of the ltrate became 7. Finally the wet slurry was dried at 100 8C for 3 h to obtain dry powder. All the samples under investigation were synthesized in similar manner. The dried powders were shaped into pellets and subjected to various heat treatments as given in Table 1. The powders were characterized at several stages using Xray diffraction technique. X-ray diffractometer Advanced Bruker D-8 was machine having Cu-Ka radiation of wavelength l = 1.5418 A used to record X-ray diffractogram. 2.2. Pellet formation The powder obtained by drying the slurry at 100 8C for 3 h was used to make pellets of desired size. An organic binder Poly Vinyl Alcohol (PVA) was added to the ne powder, and this mixture was crushed to mix PVA uniformly in the powder. The powder was then used to make pellets with the die-punch having diameter 10 mm. A hand press machine was used to apply pressure of about 5 ton. Powder was pressed and compacted in a die to form a pellet. In order to enhance actual density, measured experimentally, the samples in the form of pellet were sintered at high temperature as given in Table 1. Scanning Electron Microscope (Model JEOL, JSM-6360A) was used to study surface morphology. Two at faces of a pellet were polished, and silver paint was applied to make ohmic contact. These pellets were used for electrical and dielectric measurements. DC electrical resistivity measurements were carried out using two probe method, where Keithley multimeter model 2000 was used to measure current at constant voltage, at different temperatures in the range 300900 K. The dielectric measurements were carried out using HIOKI 3532-50 LCR Hi tester at xed frequencies as a function of temperature in the range 300900 K. 3. Results and discussion 3.1. X-ray diffraction analysis X-ray diffractogram recorded on the powders co-precipitated and dried at 100 8C does not show any Bragg lines, which is indication of amorphous nature of the material. All the powders

E D C B A

20

30

40

50 2 (deg.)

60

70

80

Fig. 1. (a)(f) X-ray diffractograms for NixCo1xFe2O4, for x = 1, 0.8, 0.6, 0.4, 0.2 and 0 AF respectively. The samples x = 0 & 1 were sintered at 400 8C and the samples x = 0.2, 0.4, 0.6 & 0.8 were sintered at 600 8C for 8 h.

were calcined at 400 8C for 8 h and characterized using X-ray diffraction technique. Only samples A and F (i.e. NiFe2O4 and CoFe2O4) show Bragg lines while other samples do not show any Bragg line. Therefore, samples B, C, D and E were again calcined at 600 8C for 8 h and examined again using X-ray diffraction technique. Now these samples show presence of Bragg lines. Xray diffraction patterns of all the samples are shown in Fig. 1(a)(f). The XRD patterns were analyzed for the phase identication. Inter planar distance d for all the diffraction lines was found in good agreement with that of JCPDS data of NiFe2O4 [18]. Slight shift in d values is observed with increasing Co content. Normally the ferrites prepared by chemical method show presence of a-Fe2O3 phase due to loss of one of the divalent elements. In Fig. 1, there is a diffraction line having very small intensity corresponding to aFe2O3 between the (2 2 0) and (3 1 1) reections for CoFe2O4. However, the diffraction peak intensity of the peak belong to a Fe2O3 is negligibly small in comparison with the ferrite peak. This indicates there is insignicant loss of Ni2+ or Co2+ions. Thus from X-ray diffraction pattern, it is clear that the sample under study is monophase spinel cubic ferrite. The crystallite size was calculated from the XRD line width of (3 1 1) line using Scherrer formula, t = 0.9l/b cos u, where t crystallite size, l wavelength of X-ray, b full width at half maximum and u Bragg angle. X-ray density was calculated using the formula (XD) = 8 M/Na3 for the spinel ferrite, where M molecular weight of ferrite, N is Avagadro number and a is the lattice parameter. Experimental density measurements were carried out using Archimedes principle. The values of lattice constant a and crystallite size t, X-ray density, experimental density and % porosity for nanocrystalline samples are given in Table 1. The lattice parameter obtained is in closely agreement with the literature [19].

Table 1 Sintering temperature, structural and morphological data on nanocrystalline NixCo1xFe2O4. Sample name A B C D E F Sintering temp. (8C) 400, 600, 600, 600, 600, 400, 8 h. 8 h. 8 h. 8 h. 8 h. 16 h. Lattice ) const. a (A 8.338 8.347 8.353 8.362 8.372 8.381 Cryst. size from XRD (nm) 8.3 12.8 12.8 13.9 11.9 8.3 Grain size from SEM (nm) 33 40 40 50 50 33 X-ray density (gm/cm3) 5.37 5.35 5.34 5.32 5.30 5.29 Experimental density (gm/cm3) 4.32 2.94 3.08 3.28 3.21 3.38 Pore fraction (f) 0.19 0.45 0.42 0.38 0.39 0.36 % porosity 19 45 42 38 39 36

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3.2. Scanning electron microscopy The micrographs of samples A F obtained using SEM technique are shown in Fig. 2(a)(f) respectively. It is clearly seen in the micrographs that the grain size of the ferrites is at nano scale. The grain size and their distribution are found to be almost uniform in all the samples. The average grain size determined from SEM images is noted as 3350 nm for NiCo ferrites, which is large than the crystallite size from XRD data. This is due to the agglomeration of the particles during processing of the samples. The grain size data for all the samples under investigation are given in Table 1. 3.3. Electrical properties The electrical resistivity of the samples in the form of pellet was measured using two probe method in the temperature range 300 900 K. It was observed from density data that the highest observed density was less than the X-ray density of the material. Therefore, a correction for pore fraction has to be applied to obtain the

crystalline value of electrical resistivity. This has been done using the relation [20]:

r r p 1 f 1 f 2=3

1 1

(1)

where r is corrected value, rp is measured value of dc resistivity and f is pore fraction as given in Table 1. Fig. 3 shows variation of resistivity (ln r) as a function of the reciprocal of absolute temperature for NiCo ferrite sample. Plots in Fig. 3 mainly show three regions as 300425 K (rst region), 425 Ktransition temperature (second region), above transition temperature (third region). This is analogous to resistivity behavior observed for spinel ferrites in literature [21,22]. The rst region from 300 to 425 K showed almost no variation in r with temperature. The second region, which extend from 425 K to transition temperature, shows temperature dependence. The third region covers the rest of the temperature range. In all linear region, it follows an Arrhenious relation r = ro exp(DE/kT), where ro = pre-exponent factor, DE = activation energy, k = Boltzmann constant and T = absolute

Fig. 2. (a)(f) SEM micrographs of NixCo1xFe2O4, for x = 1, 0.8, 0.6, 0.4, 0.2 and 0 AF respectively.

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30

25

20

ln

15

10

A B C D E F

0 1 1.5 2 2.5 3 3.5

1000/T(K )
Fig. 3. Plots of ln r vs 1/T for NixCo1xFe2O4, for x = 1, 0.8, 0.6, 0.4, 0.2 and 0 AF. Inset: Plots of ln r vs 1/T for Ni0.6Co0.4Fe2O4. Tc is marked by arrow for one of the samples as a representative plot.

-1

temperature. More than one straight line obtained with break in slope for the resistivity data, as depicted in Fig. 3, indicates more than one conduction mechanism in the temperature range of measurements. The hopping model is the most predominant one. The hopping process may be due to either electron hopping between same ions of different valences (Fe2+ Fe3+ + e) or hole hopping between Ni and Co ions (Ni3+ Ni2+ + e+, Co3+ Co2+ + e+). At ferrimagnetic to paramagnetic transition temperature (Tc), as reported in literature, change in slope of the plots is observed [23]. The values of Tc and activation energies are given in Table 2. Careful observation of Fig. 3 revealed that the second region (425 Ktransition temperature) is not linear throughout. Such anomalous behavior was observed even for samples of NiZn family prepared by co-precipitation method [24]. This is unusual behavior observed in ferrites, which need explanation. To answer this anomaly let us look into the aspect of cation distribution. It is expected that in NiCo ferrite both Ni2+ and Co2+ ions occupy octahedral site and Fe3+ ions are expected to occupy tetrahedral ssbauer spectra analysis and octahedral site. Kim et al. based on Mo reported that part of divalent ions may occupy tetrahedral site in NiCo ferrite [25]. Altering the cation distribution between the chemically inequivalent sites will not lead to change in crystal structure and chemical composition but will affect the electrical properties. The present study therefore indicates that a ferrite with a particular composition may have different cation distribution in its bulk phase than in its nanoparticle phase. When temperature is increased above 500 K, slow migration of Fe3+ ions from A site to the B site starts. Migration of Fe3+ ion to B site increases Fe3+Fe2+
Table 2 Ferrimagnetic to paramagnetic transition temperature and activation energy data on nanocrystalline NixCo1xFe2O4. Sample A B C D E F Tc (K) 863 853 843 833 813 793

hopping probability at octahedral site, which results in decreased resistivity values. The amount of Fe3+ ions migration increases up to 700 K and afterwards it saturates [25]. This results into an anomaly in the resistivity behavior in second region. Temperatures above 800 K are noted as Curie temperature of the samples. Activation energy below Tc i.e. in ferrimagnetic region is small as compared to that of activation energy above Tc i.e. in paramagnetic region. This is because ferrimagnetic region is an ordered state, while paramagnetic is disordered state hence it requires more energy for the activation of the charge carrier. 3.4. Dielectric properties Fig. 4(a) shows variation of e0 with temperature at xed frequencies for one of the samples C as a representative plot. The value of dielectric constant is quite low at room temperature; which is about 104 times lower than those obtained for ferrite samples prepared by the conventional ceramic method [26,27]. The value of dielectric constant is high at low frequencies and low at high frequencies. Moreover, increase in value of e0 with increasing temperature is more at low frequencies, when compared it with high frequencies. The dielectric constant of any material, in general, is due to dipolar, electronic, ionic, and interfacial polarizations. At low frequencies dipolar and interfacial polarizations are known to play most important role. Both of these polarizations are strongly temperature dependent. The interfacial polarization increases with temperature due to creation of crystal defects and dipolar polarization. The rapid increase in the dielectric constant with increase in temperature at low frequencies suggests that the effect of temperature is more pronounced on the interfacial than that of dipolar polarization. At high frequencies, electronic and ionic polarizations are the main contributors and their temperature dependence is insignicant [28]. Fig. 4(b) shows variation of e0 with temperature at 1 kHz for the A, B, C, D, E and F. Careful observation of Fig. 4(a) and (b) shows following main features. (i) The e0 increases slowly at all frequencies up to 700 K; above 700 K, it increases rapidly. (ii) In the temperature range of measurements, two peaks are observed; one around 773 K and other around Tc of the sample except for CoFe2O4 (F) sample. For the sample F one peak is observed at

DE below Tc (eV)
0.26 0.65 0.54 0.47 0.65 0.33

DE above Tc (eV)
1.13 1.13 0.94 0.92 1.16 1.36

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Fig. 4. (a) Variation of dielectric constant (e0 ) with temperature for Ni0.6Co0.4Fe2O4, at 1 kHz, 10 kHz, 100 kHz and 1 MHz as a representative plot. (b) Variation of dielectric constant (e0 ) with temperature for NixCo1xFe2O4, for x = 1, 0.8, 0.6, 0.4, 0.2 and 0 AF at 1 kHz.

around 570 K and other is around Tc of CoFe2O4. For all the samples the peak around Tc is dominant. (iii) From Fig. 4(a) it is seen that the peak temperature shows slight shift with change in frequency. Feature (i) can be explained as: up to 700 K the thermal energy given is insufcient to free the localized dipoles to be oriented in the direction of applied electric eld. Above 700 K a large number of dipoles become free due to sufciently high thermal energy and the applied electric eld aligned them in its direction. Such behavior is observed by Ahmad et al. in case of lanthanum substituted NiZn ferrite [29]. In the second feature, the peak observed at 773 K can be explained as: the migration of Fe3+ ions increases electron exchange between thermally activated Fe3+ Fe2+; hole transfer between Co3+Co2+ and Ni3+Ni2+ at octahedral site, which results into increased polarization and dielectric constant. Afterwards, migration saturates resulting e0 peak with temperature. This observation is analogous to resistivity data in the range of temperature 425800 K. For the sample F this peak is shifted to low side and observed at around 583 K. For CoFe2O4 sample, the migration starts at low temperature and saturates around 570 K as observed in case of Ni substituted CuFe2O4 [30]. The peak above 800 K for the samples A to E is attributed to ferrimagnetic (magnetically ordered) to paramagnetic (disordered) transition of the samples and for sample F this peak is observed at around 783 K. This is in agreement with dielectric behavior observed for other ferrites at Curie temperature [29,31 34]. The decrease in e0 above transition temperature is attributed to decrease in internal viscosity of the system giving rise to more degree of freedom to the dipoles, which causes increased disorder in the system and hence decreased in e0 . This is in agreement with Ahmed et al. [29]. The third feature can be explained as: The behavior observed in NiCo is due to collective contribution of two types of charge carriers; p and n to polarization. The appearance of p type carriers in the present case is due to hole transfer in Co3+Co2+ and Ni3+Ni2+ while Fe2+Fe3+ gives rise to n type charge carriers. The polarization of p type charge carriers is in the opposite direction to that of n type charge carriers. Also the mobility of p type charge carriers is low as compared to that of n type charge carriers. Therefore, the shift in peak depends upon the majority charge carriers. In the present case, the majority charge carriers are of p type, conrmed from Seebeck coefcient data with temperature (not shown). The peak in e0 shifts to low temperature side with increasing temperature. 4. Conclusions NixCo1xFe2O4 ferrites of grain size 3350 nm have been successfully synthesized using chemical co-precipitation method and characterized for their structural and morphological properties. The morphological and structural studies prove the nanocrystalline nature of the samples. The spinel cubic structure

as of NiCo series possesses lattice parameter a = 8.33 to 8.38 A conrmed from XRD data analysis. The unusual electric and dielectric behavior at high temperature is explained taking into consideration an aspect of cation distribution. Ferrimagnetic to paramagnetic transition values for NixCo1xFe2O4 ferrites lie between 863 and 793 K. Acknowledgments Authors are thankful to Center For Advanced Studies (CAS) in Materials Science, Department of Physics, University of Pune, Pune for nancial support. Also, nancial help from University of Pune under the Research Scheme RG 14 is greatly acknowledged. VLM is thankful to DST, New Delhi for the nancial support, FAST TRACK young scientist fellowship and BOYSCAST fellowship. References
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