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Journal of Magnetism and Magnetic Materials 320 (2008) e869e873 www.elsevier.com/locate/jmmm

Substituted cobalt ferrites for sensors applications

Ovidiu Caltuna,, Ioan Dumitrua, Marcel Federb, Nicoleta Lupuc, Horia Chiriacc
a

Department of Solid State Physics, Faculty of Physics, Blvd Carol I No. 11, 700506 Iasi, Romania b National Institute of Material Physics, P.O. Box MG-7, Bucharest, Romania c National Institute of R&D for Technical Physics, 700050 Iasi, Romania Available online 16 April 2008

Abstract The aim of this work was to study the inuence of the sintering temperature and of the substitution level on the Curie temperature and on the magnetostriction coefcients for four series of cobalt ferrites sintered by conventional ceramic method. The microstructure of the samples was characterized using X-ray diffractometry and scanning surface electron microscopy. Vibrating sample magnetometry and strain gauge measurements were used to characterize the magnetic and magnetostriction properties. The study proves that a small amount of manganese substitution for iron decrease drastically the Curie temperature but in the same time decrease the specic magnetization and magnetostriction coefcient. Despite this drawback, the manganese substituted cobalt ferrites present the largest strain derivative. The maximum of the magnetostriction coefcient is also inuenced by the stoichiometry of the cobalt ferrites. The magnetostriction coefcient of cobalt ferrite can be enhanced by substitution of small fraction of iron or cobalt by silicon or manganese, this implying the modication of the strain derivative as well as magnetostriction at lower magnetic elds. The maximum magnetostriction can be tuned by substitution levels and sintering parameters. r 2008 Elsevier B.V. All rights reserved.
PACS: 75.50.Gg; 75.50y Keywords: Cobalt ferrites; Paralel and perpendicular magnetostriction

1. Introduction Over the last decade, the magnetostrictive materials for smart sensors have attracted a great interest because of their wide range of applications in the automotive industry. Cobalt ferrites are promising materials for stress and noncontact torque sensors. The cobalt ferrites are well known for its highest magnetostrictive coefcient among the oxides-based magnetostrictive materials. There are many studies concerning cobalt ferrites obtained by conventional ceramic technique. Different sintering condition, different sort and level of substitution entail the microstructure of the samples and consequently different maximum values of the magnetostriction coefcient. For specic application of stress sensors, the maximum strain derivative (dl/dH)max, which

Corresponding author. Tel.: +40 232 201176; fax: +40 232 201205.

E-mail address: caltun@uaic.ro (O. Caltun). 0304-8853/$ - see front matter r 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.jmmm.2008.04.067

is related with stress sensitivity, is more important than the maximum value of the magnetostriction. Previous study of cobalt ferrites-based composites [1] reports maximum magnetostriction value of pure sintered CoFe2O4 of 225 106 and a small decrease of the magnetostriction coefcient in the composite samples obtained by addition of small amount of ne metal powders (Ag, Ni, Co) in order to increase the mechanical robustness. A more recent study of Lo et al. [2] was dedicated to the possibility to improve the magnetostriction coefcient of CoFe2O4 samples by air annealing at 300 1C for 36 h. Under hard axis applied elds, the maximum magnetostriction measured along the hard axis at room temperature increased in magnitude from 200 106 to 252 106 after annealing. The (dl/dH)max increased from 1.5 109 to 3.9 109 A1 m1. Recent studies [3,4] report the effect of substitution of Fe by Mn in CoFe2xMnxO4 and showed that the incorporation of Mn leads to a decrease in the magnetostriction and Curie temperature. The maximum magnetostriction

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coefcients decrease drastically by increasing the substitution level from 200 106 to 80 106 [4,5] but the maximum stain derivative at low eld for small amount of substitution increases spectacularly. The effect of substitution of Fe and Co by Mn on the magnetostrictive properties of Co1.2Fe1.8O4 has been also investigated [6]. A strong dependence of magnetostriction on the Mn content is observed in both cases. The substitution of Co by Mn enhances the magnetostriction for small values of substitution in Co1.2xMnxFe1.8O4 whereas magnetostriction decreases continuously with increasing x in Co1.2Fe1.8xMnxO4. A two-fold increase in the initial slope (dl/dH)max with large magnetostriction as compared to that of the unsubstituted compound is observed when small amounts of Co are replaced by Mn [7]. The Curie temperature of CoFe2O4 can be adjusted over a substantial range by the substitution of Si and Co for Fe, and by varying the sintering condition [8,9]. In the last study, the value of the maximum magnetostriction coefcient of pure cobalt ferrite was 94 106 and of the maximum strain derivative was 1 109 A1 m1. In the case of CoSi0.2Fe1.8O4 sample, a small amount of silicon substitution decreased the maximum magnetostriction coefcient to 90 106 and increased the maximum strain derivative to 4.5 109 A1 m1. The aim of this study is to investigate the inuence of the chemical composition and of the sintering conditions on the microstructure, on the magnetic properties and magnetostriction of four series of substituted Co ferrite samples. The chemical composition was, respectively, CoFe2O4, Co0.8Fe2.2O4, CoFe1.8Mn0.2O4 and Co1.3Si0.3 Fe1.4O4 and the sintering temperature was varied in three steps 1250, 1275 and 1300 1C, respectively. One of the objectives of this study was to rene the sintering process in order to make some remarks very useful for large-scale producers of cobalt ferrite. 2. Experimental details Four series of cobalt ferrite samples with chemical compositions: CoFe2O4 (COFS; stoichiometric) Co0.8Fe2.2O4 (COFU; unstoichiometric) CoFe1.8Mn0.2O4 (COFM; Mn substituted for Fe) and Co1.3Si0.3Fe1.4O4 (COFCS; Co and Si substituted for Fe) were synthesized by using standard powder ceramic technique. The raw material was produced by mixing a-Fe2O3, Co3O4, MnO2 and SiO2 powders in the targeted proportions. The powders were mixed, ball milled for 5 h using the ball to powder ratio for sub-micron particles and calcined in air at 950 1C for 5 h. The powder was again re-milled, mixed and granulated using 8% PVA and lubricated by using zinc stearate. The raw discs were annealed at low heating and cooling rates (lower than 50 1C h1) with two intermediary stairs isotherms (100 and 500 1C for 1 h) to evaporate the binder. For each composition, subseries of samples were obtained by varying the sintering temperature in three steps: 1250, 1275 and 1300 1C. The cooling process

was done in the furnace by switching off the furnace after the soaking temperature. Structural characterization of samples was determined by X-ray diffraction analysis and scanning electron microscopy. The magnetic properties were measured using vibrating sample magnetometry and magnetostriction coefcients were measured using tensile strain gauge technique in both parallel and perpendicular direction to the applied eld. 3. Results and discussion The data summarized in Table 1 refer to microstructure and magnetic properties of the four series of cobalt ferrites. In all cases, the densities of the samples increase by increasing the sintering temperature due to the decrease of porosity. This behavior is an expected one and corresponds to the observation made by Bahme and Joy [7]. Each series has its peculiar behavior. For stoichiometric samples denoted by COFS, the maximum magnetization increases with increasing the sintering temperature, while the remanence magnetization and the coercive magnetic eld show a maximum for 1275 1C proving that the magnetic properties are also inuenced by factors other than intrinsic. The data presented in Table 1 suggest the benecial role of small amount of substitution of Co and Si for Fe to the magnetic properties of cobalt ferrite. In the COFCS ferrite case, the lowest porosity and the highest density of all the studied series were observed. This is explained by the difference in microstructure of the COFCS samples from the other series, as is shown in Fig. 1. This difference is explained by the presence of the silicon oxide, which could be responsible for a series of liquid phase reactions with the base powders during the sintering process and promote bridges and low porosity. However, the COFCS samples have the biggest magnetization and the smallest coercive elds of all the samples investigated in this study. One of the explanations is the presence of the residual phase in the case of the COFS samples. The XRD study conrmed 13.1% hematite
Table 1 Sintering temperature Ts (1C), density d (g cm3), porosity P(%), maximum magnetization (emu g1) at the maximum applied eld of 6 kOe, remanence magnetization Mr (emu g1), coercive eld Hc (Oe) Sample COFS-1 COFS-2 COFS-3 COFU-1 COFU-2 COFU-3 COFM-1 COFM-2 COFM-3 COFCS-1 COFCS-2 COFCS-3 Ts 1250 1275 1300 1250 1275 1300 1250 1275 1300 1250 1275 1300 d 4.0 4.2 4.3 4.2 4.3 4.3 4.5 4.6 4.6 4.7 4.7 4.8 P 25.0 20.7 19.0 21.0 18.8 18.4 14.8 13.0 12.8 9.6 9.0 7.7 Mmax 59.8 59.4 57.0 37.4 44.8 42.0 65.9 65.6 63.0 70.0 69.9 60.0 Mr 13.0 12.1 12.7 9.9 12.8 11.6 9.5 8.4 8.3 7.1 5.4 4.2 Hc 918 767 774 773 625 625 442 378 374 200 161 160

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Fig. 1. The microstructure of (a) COFS and (b) COFCS samples.

[311] [220] [400] [422] [511] [440] COFCS

Intensity (au)

[220]

[400]

[422] [511] [440] COFM

Hematite [220] [104] [400] [422] [511] [440] COFU

[220] [104]

[400]

[422] [511] [440] COFS

20

30

40

50

60

70

2 Theta (degree)
Fig. 2. The XRD patterns of the representative of each series. Samples are sintered at 1300 1C.

residual phase in COFS samples and 32.9% in COFU samples, and 2.1% in COFM samples. Free of residual phases in our study were COFCS samples. The sintering temperatures have low inuence on the phase content and XRD patterns presented in Fig. 2 remain unchanged in this range of sintering temperatures. This observation is important for the ferrite producer because small variation of the sintering temperature could not imply major change in magnetic properties whereas change in chemical composition certainly leads to important change on magnetic properties. The Curie temperature for the pure and substituted cobalt-ferrite was determined and reported in many study as being inuenced by the sintering conditions and by the nature and the level of the substitution [39]. Paulsen et al.

reported [8], for COFSC samples, a Curie temperature higher then that reported by Smith and Wijn [10], and less tunable by Fe substitution with Co or Si cations in the works done by Rao et al. [9] and, Bahme and Joy [7]. The samples produced in the present study were richer in cobalt as the samples produced by Paulsen et al. [8]. The COFU samples, out of stoichiometric composition CoFe2O4, as shown in Table 1 have smallest magnetization values due to the presence of the residual phase in such a big amount. The SEM micrographs of COFU samples are similar with COFS micrographs showing over that SEM analysis is not useful in comparing or determining the residual phase content. The cobalt ferrite producers should compare XRD patterns and performs EDAX analysis [8] to identify residual phases and possible drawbacks in chemical composition. The micrographs obtained by surface electron microscopy in fracture for COFM samples differ slowly by the COFS and COFU micrographs. In the case of the COFM samples, the microstructure is more uniform and the average grain size is smaller together with an evident growth of the density and decrease of the porosity. Furthermore, differences in thermal preparation, including both temperatures and times, could affect compositional homogeneity and possible presence of secondary phases. The thermal equilibrium during the heating and cooling process could affect the site occupancy of Co, Mn, Si and Fe among the A and B sites, thereby affecting the strength of the exchange interactions. For these reasons, one might expect differences in Curie temperatures and in magnetic properties of cobalt ferrites prepared in different ways or annealed at different temperature in applied magnetic eld [11]. Rather, the improved magnetomechanical properties of magnetically annealed samples may degrade over time or after operation at elevated temperatures, which is undesirable for sensor applications.

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To characterize the magnetic properties of the samples, the hysteresis loop at room temperature was measured for all the specimens. The VSM measurement results for the sample series sintered at 1300 1C are shown in Fig. 3. By increasing the sintering temperature usually the magnetization increases because spinel structure should be promoted by residual phase transformation. As shown in Table 1, there are samples breaking this simplest rule proving complex mechanism of magnetization process. Magnetization is the interplay of domain walls movement and spin rotation, a sum of exchange interactions. In the case of the spinel structure, the strength of the exchange interaction depends on the octahedral and tetrahedral sites lling [12,13]. The magnetization at 6 kOe is increased by a small amount with substitution of Co and Si for Fe as shown in Fig. 3. The diminution of the magnetization is reported when Mn is substituted for Fe in CoFe2O4 [3,4,12]. The changes in the magnetization at room temperature of the COFM samples can be due to the difference in the contributions from the magnetic moment of the substituted ion or due to the diminution of the magnetocrystalline anisotropy after substitution of the Co and Fe cations by Mn or Si. An increase of the total magnetic moment is possible when Co2+ is replaced by Mn2+. In the same time it is a well-known inuence of the Mn cations on the COFM total magnetic moment. If the substituted Mn ions are incorporated as Mn2+ in the tetrahedral or octahedral sites, a larger increase in the magnetic moment is expected, whereas if the Mn is present as Mn3+ in the octahedral sites, the increase in the magnetic moment will be smaller. The cobalt ferrite has higher magnetostriction in the parallel direction with negative values as compared to the smaller positive values in the perpendicular directions. The parallel and perpendicular magnetostriction curves

measured at room temperature up to maximum eld strength of 10 kOe are shown in Fig. 4 and the data are summarized in Table 2. The magnitude of magnetostriction shows a strong dependence on the chemical composition and on the nature and the level of the substitutions. The analysis of the dependence of the magnetostriction parameters on the sintering temperature is not conclusive. In the case of the COFS samples increasing the sintering temperature, the maximum of the magnetostriction coefcient decrease while in the case of the COFM samples increase monotonically. The maximum value of the parallel magnetostriction coefcient and of the maximum strain derivative corresponds to the COFM sample sintered at 1300 1C. Small amount of Mn substitution increases the magnetic and magnetostriction properties of cobalt ferrite. At the same time, the study demonstrates the inuence of the Si and Co substitution for Fe on the magnetostriction properties of the COFCS samples. Even though the total magnetic moment decreases and the maximum of the parallel magnetostriction coefcient diminishes in the case
40 0 par, perp (ppm) -40 -80 -120 -160 -200

COFS - par COFS - perp COFU - par COFU - perp COFM - par COFM - perp COFCS - par COFCS - perp -5000 0 5000 10000

80 60 Specific magnetization (emu/gram) 40 20 0 -20 -40 -60 -80 -6000 -4000 -2000 0 2000 4000 6000 Magnetic field strength (Oe)
Fig. 3. The hysterisis loops of the representative of each series. Samples are sintered at 1300 1C.

-10000

Magnetic field strength (Oe) COFS COFU COFM COFSC

Fig. 4. The magnetostriction curves at room temperature. Samples are sintered at 1275 1C. Table 2 Magnetostriction parameters: magnetic eld strength HII (kOe) corresponding to the lII max (ppm); maximum value of the parallel magnetostriction coefcient lII max (ppm); magnetic eld strength H? (kOe) corresponding to the l? max(ppm); maximum perpendicular magnetostriction coefcient l? max (ppm); magnetic eld strength Hder max (kOe) corresponding to the maximum strain derivative (dlII/dH)max; maximum strain derivative value (dlII/dH)max ( 109 Oe1); parallel magnetostriction coefcient lII d (ppm) corresponding to maximum of the strain derivative (dlII/dH)max Sample COFS-2 COFU-2 COFM-2 COFCS-2 HII 9.2 9.4 9.3 4.2 lII
max

H? 9.2 9.4 8.8 6.0

l? 37 17 32 33

max

Hder 5.9 6.6 4.4 1.2

max

dlII
dH max

lII

177 79 198 87

51 16 57 39

98 38 125 48

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of the COFCS, the strain derivative has high value at very low values of the strength of the applied magnetic eld. In special cases, COFCS could be a promising candidate for sensors applications. 4. Conclusions The study demonstrates the importance of the parameters of the sintering process and of the chemical compositions on the magnetostrictive properties of the pure and substituted cobalt ferrites. The control of the sintering condition and of the substitution levels is an important factor in producing magnetostrictive cobalt ferrites for dedicated sensors and actuator applications. The study identied the processes that dene the magnetostrictive properties of substituted Co ferrites and the possibility to tailor this in the production process in order to obtain materials with desirable properties. Acknowledgment This work was supported by Romanian MATNANTECH Program under CEEX MASTRICH and CEEX MAGSAT projects.

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