Materials Chemistry and Physics 85 (2004) 104112

Effect of diamagnetic substitution on the structural, electrical and magnetic properties of CoFe2 O4
M.A. Gabal a, , S.S. Ata-Allah b
b a Chemistry Department, Faculty of Science, Benha University, Benha, Egypt Reactor and Neutron Physics Department, Nuclear Research Center, Atomic Energy Authority, Cairo, Egypt

Received 11 June 2003; received in revised form 7 December 2003; accepted 17 December 2003

Abstract Polycrystalline samples with the general formula Co1x Cdx Fe2 O4 (0 x 1) were synthesized by calcining the respective oxalates mixtures at 1000 C for 5 h. Their structural, electrical and magnetic properties are studied using X-ray diffraction, Fourier transform infrared and Mssbauer spectroscopy, and electrical conductivity and magnetic susceptibility techniques. With cadmium ion substitution, the lattice parameter, X-ray density, oxygen parameter, inversion factor and radii of tetrahedral and octahedral sites are calculated. The Fourier transform infrared spectra showed two dominant bands in the high- and low-frequency range which are assigned to the tetrahedral and octahedral complexes, respectively. The relationship between bands position and cadmium content was also investigated. The Mssbauer spectroscopy was carried out to study the cation distribution in this system. It was found that ions at octahedral site moved to the tetrahedral site, and that this system varied from an inverse to a normal spinel structure. The temperature variation of the conductivity showed a denite kink, except for the CdFe2 O4 sample, which corresponds to the ferrimagnetic to paramagnetic transitions. The effective magnetic moment of the samples and their Curie temperature were observed to decrease by the substitution effect. 2004 Elsevier B.V. All rights reserved.
Keywords: CoFe2 O4 ; CdFe2 O4 ; Mssbauer spectroscopy; Electrical conductivity; Magnetic properties

1. Introduction Ferrites, i.e. ferrimagnetic cubic spinels possess the combined properties of magnetic materials and insulators. They have been extensively investigated and being the subject of great interest because of their importance in many technological applications. The important structural, electrical and magnetic properties of these spinels, responsible for their applications in various elds, are found to depend on the magnetic interaction and the distribution of cations among the two sublattices, tetrahedral (A) and octahedral (B) sites. The compounds capable of crystallizing in the spinel system can present in either of two structure: the normal spinel or inverse spinel. In the normal spinel (such as CdFe2 O4 ), cadmium ions are located in the tetrahedral site and are symmetrically surrounded by four O2 ions. In the inverse spinel (like CoFe2 O4 ), half of Fe3+ ions are
Corresponding author. Present address: Institut fr Mechanische Verfahrenstechnik und Mechanik, Gas-Partikel-Systeme, Universitt Karlsruhe, 76128 Karlsruhe, Germany. Tel.: +49-176-2001-9090; fax: +49-721-608-2405. E-mail address: mgabalabdo@yahoo.com (M.A. Gabal). 0254-0584/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.matchemphys.2003.12.013

located in the tetrahedral positions whereas the other half are in the octahedral positions. Therefore, a normal ferrite can be described as (M2+ )[Fe2 3+ ]O4 and an inverse ferrite as (Fe3+ )[M2+ Fe3+ ]O4 [1]. X-ray diffraction and Mssbauer spectroscopy techniques have been devised to study the cation distribution in spinel ferrites. Generally [2], the cation distribution calculated from X-ray intensity data agrees with the Mssbauer results. Cobalt ferrite is ordinarily an almost inverse cubic spinel in which the degree of inversion is critically determined by the preparation conditions [3]. The partial replacement of diamagnetic ions (e.g. zinc or cadmium) in such ferrites is expected to weaken the magnetic coupling which may be reected in a decrease of the magnetic hyperne eld as well as the Curie temperature [2]. A little work was found in the literature on mixed CoCd ferrites. Ghani et al. [4] have been studied the magnetic behavior of mixed CoCd ferrites. Vasambekar et al. [3] were interested in understanding the magnetic behavior of the Cd2+ and Cr3+ substituted cobalt ferrites prepared by standard ceramic method. Nikumbh et al. [5] have been prepared the compounds of the system Cd1x Cox Fe2 O4 (0 x 1) by the tartrate coprecipitation technique and attempted

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to determine the effect of cadmium ferrite spinel formation and the role of cobalt content on its structural, magnetic and electrical properties. However, there is no reported work in the literature for the preparation of mixed CoCd ferrites through the thermal decomposition of mixed oxalates. Accordingly, the present communication attempts to prepare the compounds of CoCd ferrites through the thermal decomposition reactions of their corresponding metal oxalates. The aim of the present study is to understand the effect of diamagnetic substitution of cadmium ions on structural, electrical and magnetic properties of cobalt ferrite spinel by means of X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and Mssbauer spectroscopy, and electrical conductivity and magnetic susceptibility measurements. The Mssbauer spectroscopy was also undertaken to investigate the probable cation distribution of the ferrite samples.

The temperature dependence of electrical properties as a function of the applied frequency (101000 kHz) were measured with a Hioki 3531 LCR bridge (Japan) using the two-probe method [8]. The samples were palletized using a cylindrical dye of diameter 1 cm by applying a pressure of 2 t cm2 . The thickness of the discs was about 1 mm. Pellets of the samples were then annealed at 900 C for 2 h and cooled to room temperature. The two surfaces of each pellet are polished, coated with silver paste and checked for good conduction. A K-type thermocouple connected to a digi-sense thermometer was used to measure the sample temperature with an accuracy better than 1 C. The temperature dependence of magnetic susceptibility as a function of magnetic eld intensities was performed using Faradays method.

3. Results and discussion 2. Experimental procedure 3.1. Thermal decomposition studies of the oxalate mixtures 2.1. Materials and preparation procedure The starting materials were solids of CoC2 O4 2H2 O, CdC2 O4 3H2 O and FeC2 O4 2H2 O. These metal oxalates were prepared by precipitation from aqueous solution of their salts sulfate using analytical grade oxalic acid. For the preparation of the mixed metal oxalates, seven mixtures of these respective metal oxalates with calculated mole ratios, equivalent to the formation of Co1x Cdx Fe2 O4 ferrite system (x = 0.0, 0.2, 0.4, 0.5, 0.6, 0.8 and 1.0) after their thermal decomposition, were prepared by the impregnation technique previously described [6]. Mixed CoCd ferrites, Co1x Cdx Fe2 O4 (0 x 1), were prepared by annealing the oxalates mixtures in a mufe furnace at 1000 C for 5 h under static air atmosphere. Then, the samples were quenched to room temperature and kept in desiccator. 2.2. Characterization techniques Simultaneous differential thermal analysis-thermogravimetry (DTATG) behavior of the oxalate mixtures was investigated using a Shimadzu DT-60 thermal analyzer (Japan) in the temperature range from room temperature up to 1000 C at a heating rate of 5 K min1 . The experiments were proceeded in owing air atmosphere (50 ml min1 ). XRD of the samples were performed at room temperature using a Philips PW 1370 diffractometer, with monochromated Cu K1 radiation wavelength ( = 1.5406 ). FT-IR spectra were measured in the frequency range 1000200 cm1 with KBr disc technique using a Jasco model FT-IR 310 (Japan). The Mssbauer spectra were obtained at room temperature in transmission geometry with a source of 50 mCi 57 Co (Rh matrix) and a constant acceleration transducer. Spectra were analyzed using the least square tting computer program (Mos-90) [7]. Fig. 1 shows a typical DTATG curves for the thermal decomposition of CoC2 O4 2H2 OCdC2 O4 3H2 OFeC2 O4 2H2 O (0.5: 0.5: 2 molar ratios) in air. The DTA curve implies a sharp endothermic peak at 103 C, closely corresponds to the rst weight loss step (4.3%) observed in the TG curve. This step is attributed to the dehydration of CdC2 O4 3H2 O in the mixture (expected weight loss = 4.5%). Two overlapped TG steps occurred in the range from 155 to 240 C and are accompanied by 15.8 and 22.2% weight loss, i.e. a total weight loss of 38.0%. The rst one is characterized by an endothermic DTA peak at 202 C and is attributer to the loss of two water molecules from hydrated cobalt oxalate and four water molecules from hydrated ferrous oxalate (theoretically 5H2 O is equivalent to 15.5% of the molecular weight of the mixture) with the formation of anhydrous oxalates mixture. The endothermic DTA peak was swamped by a sharp exothermic DTA peak maximized at 226 C and is ascribed to the oxidative decomposition of FeC2 O4 Fe2 O3 (calculated weight loss = 22.1%). The two successive weight loss steps follows immediately after the decomposition of FeC2 O4 are attributed to the oxidative decomposition of CoC2 O4 and CdC2 O4 contents to Co3 O4 and CdO, respectively. The two steps exhibit a weight loss of 5.5 and 6.6% (closely corresponds to theoretically calculated weight loss of 5.8 and 6.5%) and accompanied by two exothermic DTA peaks maximized at 280 and 365 C, respectively. Upon raising the temperature a further very small weight loss (0.5%) characterized by a very small endothermic DTA peak at 935 C was obtained. This step is attributed to the reduction of Co3 O4 CoO (expected weight loss = 0.5%). The total weight loss after complete decomposition of the mixture, was calculated to be 54.9% of the molecular mass of the mixture which closely corresponds to the formation of Co0.5 Cd0.5 Fe2 O4 ferrite. Thus, the minimum temperature needed for the calcination process (which

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Fig. 1. DTATG curves of a CoC2 O4 2H2 OCdC2 O4 3H2 OFeC2 O4 2H2 O (0.5:0.5:2 molar ratios) mixture in air at a specied heating rate of 5 K min1 .

is enough to obtain the corresponding ferrite) was selected at 1000 C on the basis of this decomposition course. From the thermal decomposition course of the metal oxalates in their mixture, it is appeared that the decomposition behavior of the metal oxalates is not much affected by their presence in a mixture since each one behaves as it is present alone [8,9]. This behavior can be attributed to their presence in a solid state mixture. 3.2. Characterization of Co1x Cdx Fe2 O4 3.2.1. X-ray powder diffraction Fig. 2 shows the X-ray powder diffraction patterns of the investigated samples. The diffraction peaks are tted by modied Gaussian functions, and the lattice parameters are obtained and reported in Table 1 by tting at least seven diffraction peaks using standard least-square methods. The results of indexing X-ray diffraction patterns showed that the nominal composition structure with different cobalt concentrations are single-phase cubic with no additional lines corresponding to any other phases, which provide clear evidence of the formation of a series of solid solutions between CdFe2 O4 and CoFe2 O4 .

The obtained values of the lattice parameter (a) agrees well with those reported in [3,5] and exhibit a linear content dependence, thus obeying the Vegards law [10] as shown in Fig. 3a. Such a remarkable change is due to the fact that the Pauling ionic radius of Cd2+ ions (1.03 ) is higher than that of Co2+ ions (0.72 ) [5], consequently, the replacement of cobalt by cadmium leads to an increase in the lattice parameter. The X-ray density (DX ) calculated using the formula DX = 8M/Na3 [10], where M is the molecular weight, N the Avogadros number, and a is the lattice parameter, increases with the increasing the cadmium content as can be seen from Table 1. Woleska et al. [11] analyzed
Table 1 Data of the Co1x Cdx Fe2 O4 system x 0.0 0.1 0.3 0.5 0.7 0.9 1.0 Lattice parameter () 8.329 8.414 8.467 8.497 8.536 8.573 8.614 DX (gm cm3 ) 5.394 5.470 5.612 5.660 5.698 5.849 5.986 1 (cm1 ) 586 585 577 576 563 561 541 2 (cm1 ) 389 388 387 382 384 378 376

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Fig. 2. Characteristic parts of the XRD patterns of the Co1x Cdx Fe2 O4 system.

Fig. 3. (a) Variation of the lattice parameter as a function of Cd content. (b) The ratio of observed intensities of X-ray line I2 2 0 /I2 2 2 and I4 2 2 /I2 2 2 as a function of Cd content. (c) Variation of 1 FT-IR band with composition. (d) Variation of 2 FT-IR band with composition.

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Table 2 Mssbauer parameters of the Co1x Cdx Fe2 O4 system x 0.0 0.2 0.4 0.5 0.6 0.8 1.0 Site A B A B B Area (%) 70 30 50 50 (mm s1 ) 0.39 0.68 0.43 0.46 0.43 0.58 0.44 0.44 0.44 (mm s1 ) EQ (mm s1 ) 0.02 0.08 0.05 0.07 0.07 0.28 0.83 0.84 0.79 0.58 0.68 0.65 0.72 2.27 7.08 0.56 0.42 0.36 Hn (kOe) 493 502 411 463 364 192

the intensity ratios of the (2 2 0) and (4 2 2) X-ray diffraction lines, dependently on the tetrahedral site, to the weak (2 2 2) lines, dependently only on the cations on the octahedral site, because these ratios are very sensitive to the residence of cadmium ions in the tetrahedral site. The observed values of these intensity ratios are represented in Fig. 3c. It is observed that these ratios are increased as x increases since the electronic conguration of Cd2+ ions have a special preference for tetrahedral coordination. This observation is similar to the lattice parameter as a function of x. 3.2.2. FT-IR spectroscopy The results of FT-IR spectroscopic measurements obtained in the present work are summarized in Table 1. The two dominant bands observed at 586 and 389 cm1 for the CoFe2 O4 sample (x = 0) are entirely consistent with those reported in [9]. The change in the bands position on going from one concentration to another may be due to the change in the internuclear distance of Fe3+ O2 in the equivalent lattice sites. The band 1 is attributed to the stretching vibration of Fe3+ O2 in the tetrahedral complexes and the 2 to that of the octahedral complexes [13]. From Table 1, it is clear that on going to the CdFe2 O4 side the position of 1 band changes with composition while that of 2 band slightly changed. The two bands appeared at 541 and 367 cm1 for the sample with x = 1 agrees well with those reported for CdFe2 O4 [14]. The variation of the 1 and 2 bands with cadmium concentration is shown in Fig. 3c and d. 3.2.3. Mssbauer spectral studies The representative Mssbauer spectra for CoCd ferrites at room temperature are shown in Fig. 4. The spectra were tted with Lorentzian-shaped lines by the method of least squares. The Mssbauer spectral data, including isomer shift (), quadrupole splitting ( EQ ), line width ( ) and hyperne magnetic eld (Hn ), are summarized in Table 2. The Mssbauer spectra of Co1x Cdx Fe2 O4 with x 0.2 exhibit normal Zeeman split sextets, one due to Fe3+ ions at the tetrahedral site and the other due to Fe3+ ions at the octahedral site. The compound with x = 0.4 showed a relaxed spectrum which was tted with one sextet. On the other hand, the compound with x 0.5 shows paramagnetic doublet, i.e. no distinct evaluation of the hyperne eld observed.

Fig. 4. The Mssbauer spectra at room temperature of the Co1x Cdx Fe2 O4 system.

The isomer shift is a useful parameter in identifying the spectra due to tetrahedral and octahedral site Fe3+ ions. Because of the difference in Fe3+ O2 distance for the two sites, isomer shift is expected to be different. The Zeeman pattern with the smaller isomer shift exhibits the smaller

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hyperne eld (in agreement with the generally accepted correlation between isomer shifts and hyperne elds in ferrites [16]) and is attributed to Fe3+ ions at tetrahedral site. On this base, the sextet obtained for the compound with x = 0.4 is assigned to the presence of Fe3+ ions in the octahedral site. On a closer look to Table 2, it can be observed that the isomer shift obtained at both sites changed with Cd2+ content in the range 0 x 0.4, indicating that the s-electron distribution of Fe3+ ions is inuenced by Cd2+ substitution. The observed decrease in the hyperne elds obtained at different sites with increasing x demonstrate a reduction in ferrimagnetic behavior by the addition of cadmium. From the table it is also apparent that compounds with higher cadmium content show high values of quadrupole splitting, while compounds with x 0.4 have practically ver small or negligible quadrupole splitting, which suggests the coexistence of chemical disorder and overall cubic symmetry causes no net quadrupole splitting. This behavior agrees well with the results obtained by Nikumbh et al. [5]. The fraction of iron ions at tetrahedral and octahedral sites were determined using the areas of the Mssbauer subspectra. For stoichiometric ferrite like CoFe2 O4 it is easy to estimate the cation distribution, but it becomes rather difcult for mixed ferrites, since they contain a mixture of more than one cation other than iron. However, if the metal ions have an exclusive preference for any particular site in the spinel, then it is possible to estimate the cation distribution in the mixed ferrites. In the present work it is found that CoFe2 O4 is a partially inverse spinel with Co2+ ions (70%) on the octahedral site and exhibits a cation distribution: (Co0.3 Fe0.7 )[Co0.7 Fe1.3 ]O4 . Since it is well known that Cd2+ ions have a strong tetrahedral site preference [1], Cd2+ will cause some migration of Fe3+ ions from tetrahedral to octahedral sites and as a result, the expected cation distribution for the sample with x = 0.2 will be (Cd0.2 Co0.3 Fe0.5 )[Co0.5 Fe1.5 ]O4 which agrees well with the calculated ratio of Fe3+ ions at tetrahedral and octahedral sites (Table 2). On this basis and considering values of the subspectra areas obtained in Table 2, the cation distribution formula which can be used to describe the system is (Cdx Coy Fe1xy )[Co1xy Fe1+x+y ]O4 , where x denotes the cadmium content and y denotes the normalcy of cobalt

ions and the inversion parameter () = 1 x y. The deduced values of the cation distribution of the system are given in Table 3. Now the values of the oxygen parameter (u) and the degree of inversion ( ) can be calculated taking into consideration the cation distribution revealed from the Mssbauer experiments (Table 3). Table 3 exhibits the calculated values as a function of cadmium content. In most oxidic spinels the oxygen ions are apparently larger than the metallic ions, and in spinel like structure the oxygen parameter has a values of about 0.375 for which the arrangement of O2 ions equals exactly a cubic closed packing, but in actual spinel lattice. This ideal pattern is slightly deformed. The higher values of oxygen parameter obtained in our work (u > 0.375) may be attributed to the small displacement of anions due to the expansion of the tetrahedral interstices [12]. Intercationic distances were calculated using experimental values of lattice constant and oxygen parameter for Co1x Cdx Fe2 O4 system using equations from [10]. The results are reported in Table 3. The cation distributions obtained from the Mssbauer experiments show that the Cd2+ ions entirely occupy the tetrahedral site and force the Fe3+ ions into octahedral site with the increasing of the cadmium content. Therefore, because of the radius of Cd2+ (tetrahedral: 0.78 ) is larger than that of Fe3+ (tetrahedral: 0.49 ) while the Co2+ (octahedral: 0.745 ) is compared to that of Fe3+ (octahedral: 0.645 ) [15], the radius of tetrahedral becomes larger and that of the octahedral slightly changed with the content. This explain why 1 FT-IR band changes with the cadmium content, while 2 band slightly changed (Fig. 3c and d). 3.2.4. Electrical conductivity and its dependence on composition Fig. 5ac show typical curves of the alternative current conductivity versus reciprocal absolute temperature as a function of the applied frequency for the Co1x Cdx Fe2 O4 system. It can be concluded that the conductivity for all the samples is frequency independent at all temperature regions (except for the low temperature region) since its values slightly changed with changing frequency. On the other hand, the conductivity of all samples was found to be temperature dependent. The curve shows that three regions are

Table 3 Cation distribution, oxygen parameter, inversion parameter and cationanion distance of the Co1x Cdx Fe2 O4 system Cation distribution u rA Rb Tet. bond Oct. bond Tet. edge Oct. edge Shared (Co0.3 Fe0.7 )[Co0.7 Fe1.3 ]O4 (Cd0.2 Co0.3 Fe0.5 )[Co0.5 Fe1.5 ]O4 (Cd0.4 Co0.3 Fe0.3 )[Co0.3 Fe1.7 ]O4 (Cd0.5 Co0.3 Fe0.2 )[Co0.2 Fe1.8 ]O4 (Cd0.6 Co0.3 Fe0.1 )[Co0.1 Fe1.9 ]O4 (Cd0.8 Co0.2 )[Fe2 ]O4 (Cd)[Fe2 ]O4 0.381 0.383 0.387 0.388 0.389 0392 0.394 0.7 0.5 0.3 0.2 0.1 0.0 0.0 0.511 0.569 0.627 0.656 0.685 0.736 0.780 1.360 1.340 1.320 1.310 1.300 1.290 1.290 1.889 1.938 2.009 2.031 2.055 2.108 2.149 2.033 2.038 2.02 2.02 2.021 2.008 2.003 3.086 3.165 3.281 3.292 3.356 3.443 3.509 2.803 2.784 2.706 2.692 2.680 2.618 2.583 Unshared 2.946 2.978 3.000 3.012 3.027 3.045 3.063

rA = tet. radius, rB = oct. radius, tet. = tetrahedral, oct. = octahedral.

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Fig. 5. (a)(c) Relation between ln and reciprocal absolute temperature at different Cd contents as a function of the applied frequency for the Co1x Cdx Fe2 O4 system.

obtained by increasing the temperature. In the rst region, the electrical conductivity is hardly changed with temperature which give rise to a metallic behavior. After that the conductivity was found to increase with increasing temperature giving a kink in each curve, at temperature which corresponds to ferrimagnetic (ordered state) to paramagnetic transition (disorder state). No such a magnetic transformation was observed for CdFe2 O4 sample, suggesting that this sample is paramagnetic at room temperature. Irkhin and Turov [17] have proposed a theoretical explanation for the existence of kinks at the ferrimagneticparamagnetic transition temperature (TC ). They conclude that the activation energy and the effective mass of current-carrying excitons in ferrimagnetic semiconductors depend on the spontaneous magnetization because of a magnetizing exchange interaction between the outer and inner electrons. This leads to an additional temperature dependence of the electrical resistance which is particularly strong near TC . The electrical conductivity-temperature behavior obeys Wilsons law [18]: = 0 exp E kT

contains several constants, including the vibrational frequency of the potentially mobile ions, E the activation energy, k is Boltzmanns constant, and T is the absolute temperature. The activation energies were calculated for the two regions around the kink, rstly for the ferrimagnetic (low-temperature region: EI ) and secondly for the paramagnetic (high-temperature region: EII ). The calculated values of the activation energy are listed in Table 4. It is interesting to observe here that the activation energy in the paramagnetic region is higher than that in the ferrimagnetic one. The behavior of the activation energy on passing through TC may be explained by the double-exchange mechanism
Table 4 Values of the electrical conductivity and the activation energy at an applied frequency of 200 kHz of the Co1x Cdx Fe2 O4 system x at 500 K (
1

cm1 )

Activation energy (eV) EI EII 0.825 0.810 0.772 0.715 0.690 0.671 0.581

indicating the semiconducting nature of all the compounds under investigation. 0 is the pre-exponential factor,

0.0 0.2 0.4 0.5 0.6 0.8 1.0

2.25 1.37 9.18 6.32 5.60 1.25 2.30

105

106 107 107 109 109 1010

0.581 0.540 0.502 0.473 0.442 0.412

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Fig. 6. (a)(d) Relation between molar magnetic susceptibility and the absolute temperature as a function of different magnetic eld intensities for the Co1x Cdx Fe2 O4 system.

[17]. Hence, the electrical conduction in the system under investigation is due to the electron hopping in the sublattices between Fe2+ and Fe3+ ions and results in an increasing of the activation energy in the paramagnetic region. Also, the electron hopping between Co2+ and Co3+ cannot be neglected. The decrease in activation energy calculated for both regions with increasing x can be interpreted as follows [5]: for CoFe2 O4 spinel, the ratio of Co2+ and Fe3+ ions in the octahedral site was found to be nearly equal. As hopping between atoms of different metals on the octahedral sublattices needs a higher activation energy than for ions of the same metals [19]. Thus, conduction activation energy for CoFe2 O4 is higher. As can be seen from Table 3, the

addition of Cd2+ ions leads to an increase of Fe3+ ions in the octahedral site and a simultaneous decrease of Co2+ ions present at the same site. This will increase ions of the same metal (Fe3+ ions) and, consequently, decrease of the conduction activation energy. Also, it can be seen that the conductivity values (taken at 500 K and a frequency of 200 kHz) decrease with increasing cadmium content (Table 4). Since the conductivity in this temperature range is attributed to the electron hopping between iron ions (Fe2+ and Fe3+ ), cobalt ions (Co2+ and Co3+ ) or between the both, thus, the replacement of cadmium on the expense of cobalt will decrease this hopping processes and, consequently, decrease of the conductivity.

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Table 5 Magnetic data of the Co1x Cdx Fe2 O4 system at a magnetic eld intensity of 1280 G x TC (K) (BM) Observed 0.0 0.2 0.4 0.5 800 630 455 390 5.66 5.12 4.68 4.02 Calculated 5.63 6.96 8.28 8.95

3.2.5. Magnetic studies Fig. 6 correlates the molar magnetic susceptibility (M ) and absolute temperature as a function of different magnetic eld intensities for the system Co1x Cdx Fe2 O4 with 0 x 0.5. It can be observed that, by increasing either temperature or magnetic eld, the molar magnetic susceptibility decreases. The magnetic parameters at a eld intensity of 1280 G for samples with different cadmium content were calculated by plotting the reciprocal molar magnetic susceptibility versus absolute temperature (Table 4). Two regions characterized by two straight lines are obtained (the ferrimagnetic and the paramagnetic) passing through the Curie temperature TC . Since the proposed cation distribution of the system estimated from the Mssbauer data is given by (Cdx Coy Fe1xy )[Co1xy Fe1+x+y ]O4 . The magnetic moment () of the system can be calculated as [5]: [3.87(1 x y) + 5.92(1 + x + y)] [3.87y + 5.92(1 x y)], where 3.87 and 5.92 are the magnetic moments of Co2+ and Fe3+ ions in BM. The observed magnetic moment at different cadmium concentrations was compared with that calculated using the above equation (Table 5). It has been observed that in case of x = 0 (i.e. CoFe2 O4 ) the observed and calculated magnetic moments are very similar to each other. The observed values for the other samples are lower than the calculated values. This can be explained in terms of the non-collinear spin arrangement, i.e. the presence of a small canting of the octahedral site moment with respect to the direction of the tetrahedral site moment [5,20]. In agreement with the Mssbauer results, the observed magnetic moment was found to decrease with increasing cadmium content which demonstrates a reduction in the ferrimagnetic behavior.

3. The FT-IR spectra showed two fundamental bands 1 and 2 , corresponding to the tetrahedral and octahedral complexes, respectively. The band 1 shifts towards the low frequency site while the band 2 remain constant with increasing the Cd ions which can be interpreted on the base of the cation distribution calculated by the Mssbauer spectroscopy. 4. The temperature variation of the electrical conductivity of all the samples except for the CdFe2 O4 sample shows a denite break, which corresponds to ferrimagneticparamagnetic transition. The activation energy in the paramagnetic region is higher than in the ferrimagnetic region. 5. The Curie temperature and the effective magnetic moment were found to decrease with increasing Cd content.

Acknowledgements The authors would like to thank Dr. A.A. El-Bellihi, Chemistry Department, Faculty of Science, King Abdul Aziz University, Jeddah, KSA, for measuring the DTATG experiments. References
[1] A. Goldman, Modern Ferrite Technology, Marcel Dekker, New York, 1993. [2] B.S. Trivedi, N.N. Jani, H.H. Joshi, R.G. Kulkarni, J. Mater. Sci. 35 (2000) 5523. [3] P.N. Vasambekar, C.B. Kolekar, A.S. Vaingankar, J. Mater. Chem. Phys. 601 (1999) 282. [4] A.A. Ghani, A.A. Sattar, J. Pierre, J. Mag. Mag. Mater. 97 (1991) 141. [5] A.K. Nikumbh, A.V. Nagawade, V.B. Tadke, P.P. Bakare, J. Mater. Sci. 36 (2001) 653. [6] M.A. Gabal, J. Phys. Chem. Solids 64 (2003) 1375. [7] G. Grosse, Mos-90, Version 2.2, Oskar-Maria-Graf-Ring, Mnchen, 1992. [8] El.-H.M. Diefallah, M.A. Gabal, A.A. El-Bellihi, N.A. Eissa, Thermochim. Acta 376 (2001) 43. [9] M.A. Gabal, A.A. El-Bellihi, S.S. Ata-Allah, J. Mater. Chem. Phys. 81 (2003) 84. [10] Q.M. Wei, J.B. Li, Y.J. Chen, J. Mater. Sci. 36 (2001) 5115. [11] E. Woleska, E. Riedel, W. Walski, Phys. Status Solidi (a) 132 (1992) 51. [12] J. Smith, H.P.T. Wijin, Ferrites, Wiley, New York, 1959. [13] M.A. Amer, Phys. Status Solidi (a) 65 (1981) 479. [14] M.M. Girgis, A.M. El-Awad, Mater. Chem. Phys. 36 (1993) 48. [15] J.A. Dean, Langes Handbook of Chemistry, McGraw-Hill Book Company, New York, 1979. [16] S.S. Ata-Allah, M.K. Fayek, H.S. Refai, M.F. Moustafa, J. Solid State Chem. 149 (2000) 434. [17] Yu.P. Irkhin, E.A. Turov, Sov. Phys.-JETP 33 (1957) 673. [18] S.R. Mrrison, The Chemistry and Physics of Surface, Plenum Press, New York, 1977. [19] C.C. Wu, S. Kumarkrishanan, T.O. Mason, J. Solid State Chem. 37 (1981) 144. [20] J.B. Goodenoug, Prog. Solid State Chem. 5 (1971) 146.

4. Conclusions 1. Due to the larger ionic radius of Cd compared with that of Co, the replacement of Co with Cd in the investigated system increases the lattice parameter. 2. The cation distribution was estimated using Mssbauer spectroscopy. It was found that the system varied from an inverse to normal spinel structure by the addition of Cd.