ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials 320 (2008) e339e342 www.elsevier.com/locate/jmmm

Magnetic properties of nanocrystalline CoFe2O4 synthesized by modied citrate-gel method

R. Sato Turtellia,, Giap V. Duongb, W. Nunesc, R. Gro ssingera, M. Knobelc
a

Institute of Solid State Physics, Technical University of Vienna, Wiedner Hauptstr. 8-10, A-1040 Vienna, Austria b Faculty of Chemical Engineering, Hanoi University of Technology, No.1 Dai Co Viet, Hanoi, Vietnam c sica, Unversidade Estadual de Campinas, CP 6165, Campinas (SP), Brazil Instituto de F Available online 11 March 2008

Abstract Nanocrystalline CoFe2O4 with an average grain size of about 40 nm was successfully prepared by a modied citrate-gel method. At temperatures of 3 and 300 K, the measured coercive elds are 0.43 and 0.07 T and the magnetizations at 7 T are 89 and 83 emu/g, respectively. At room temperature, the longitudinal and transversal magnetostriction values are 130 and 70 ppm, respectively. The contribution of a disordered magnetic phase was detected by the occurrence of a peak in the ac-susceptibilities curves at around 250 K. The temperature dependence of the eld-cooled and zero eld-cooled low-eld magnetization showed a larger irreversibility below this temperature. This disordered phase behaves like a spin-glass, which is coexisting with the ferrimagnetically ordered main phase r 2008 Elsevier B.V. All rights reserved.
PACS: 75.50.Tt; 75.60.Ej; 75.75.+a; 61.16.Bg Keywords: Cobalt ferrite; Citrate-gel method; Hysteresis loop; Magnetization

1. Introduction CoFe2O4 is a typical ferrimagnetic oxide with a spinel structure. For many years, CoFe2O4 has been the subject of research activities because of fundamental questions as well as potential application. Ferrimagnetic CoFe2O4 exhibits excellent magnetic properties: Curie temperature around 520 1C, large magnetocrystalline anisotropy, high coercivity, Hc, and high saturation magnetization. Additionally, this material exhibits a signicantly higher magnetostriction then metallic Fe or Ni. Recently, we prepared successfully high-quality ultrane particles of Co1xZnxFe2O4 by forced hydrolysis method [1,2]. However, to have a large-scale production by this method is very difcult. Therefore, the search of a simple and economic route, which allows the preparation of a large amount of high-quality nanocrystalline CoFe2O4

is necessary and will benet to practical applications of this interesting material. In this work, we prepared powder of CoFe2O4 using a modied citrate-gel method, a simple, non-grinding, economic and easy production technique, which can be extended for large-scale production. The powder prepared with this method present an average grain size of 40 nm and exhibits excellent magnetic properties. 2. Experiment The precursor salts, Fe(NO3)3 9H2O, Co(NO3)2 6H2O and citric acid, all with analytical purity, were added to 150 ml of deionized water in stoichiometric ratio. The total metal concentration was 1 mol/l. The molar ratio between total metal ions and citric acid was xed to 1. The starting mixture containing the salts, deionized water, and citric acid was stirred to get homogeneous solution and heated to 80 1C with a heating rate of 5 1C/min using a hot plate magnetic stirrer. The pH of the solution was adjusted to 6 by dropping ammonia (NH3 25%). The sol was formed during stirring. Increasing the temperature of the hot plate

Corresponding author. Tel.: +43 1 58801 13150; fax: +43 1 58801 13199. E-mail address: reiko.sato@ifp.tuwien.ac.at (R. Sato Turtelli).

0304-8853/$ - see front matter r 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.jmmm.2008.02.067

ARTICLE IN PRESS
e340 R. Sato Turtelli et al. / Journal of Magnetism and Magnetic Materials 320 (2008) e339e342

up to 200 1C and keep stirring constantly, the water in the solution was evaporated and a viscous gel was formed. Keep heating, the gel is dried and burnt as being ignited to form loose powder. Differently from reported literatures, chelating agent such as ethylene glycol were not used, additionally the gel was not dried but it was forced to auto-combusted by keeping heating after gelating the sol. This makes the process more simple and economic for preparing large amounts of the material. Finally, the powder was pressed into pellets under a pressure of 4.5 ton/ cm2, and then sintered at 1000 1C for 5 h. After naturally cooling down to room temperature, it was cut in pieces of 2 4 6 mm. The crystal structure of the obtained material was studied by X-ray diffraction (XRD) using CoKa radiation. To estimate the crystallite size, the well-known Scherrer equation for the full-width at half-maximum (FWHM) of the strongest reection was employed. The hysteresis loops and temperature dependence of magnetization were measured by means of a commercial superconducting quantum interference device (SQUID) magnetometer (Quantum Design MPMS XL7) in the temperature range of 3300 K with a maximum magnetic eld of 7 T. Linear magnetostriction was measured at room temperature using a strain gauge method with a 50 kHz bridge (HBM Type KWS 85.A1). 3. Results and discussion The XRD pattern of the sample was shown in Fig. 1. The clear and sharp peaks indicate a well-crystallized sample (the broad peak appears within 20301 due to Si-glass substrate used for gluing the powder). All peaks are characteristics for CoFe2O4 in cubic spinel-type structure. The absence of foreign diffraction lines suggests , the phase purity. The determined lattice constant is 8.38 A a typical value for cobalt ferrite. Using Scherrer equation, we obtained an average grain size of about 40 nm, even after sintering at 1000 1C for 5 h. In our powder production method, the ferrite is grown up from the homogeneous

atomic level mixture, therefore the grain size of powders after sintering still remains small. From the magnetostriction measurements at room temperature, we obtained the longitudinal and transversal magnetostrictions values of 130 and 70 ppm, respectively, which are relatively large. The hysteresis loops obtained at different temperatures are shown in Fig. 2. The coercive eld Hc decreases almost linear with increasing temperature up to around 250 K, then Hc changes slightly with T, as shown in Fig. 3. At 3 K, the value of the coercive eld is of 0.43 T and the maximum magnetization (Mm) achieved at a magnetic eld of 7 T is of 89 emu/g. Although in this experience the maximum applied magnetic eld is about 16 times higher than the coercive eld, it was not possible to saturate the sample magnetically, as shown in the upper inset of Fig. 2. However the Mm value is close to the saturation magnetization of pure Coferrite (93.9 emu/g). At 300K, the maximum magnetization and coercive eld measured under the same applied magnetic eld are 82.8 emu/g and 0.07 T, respectively. The values of the maximum magnetizations are higher than those reported in Ref. [3] for nanocrystalline CoFe2O4 with similar grain size, but prepared with another method. The higher values obtained here may be due to the suitability of our preparation method. However, our magnetic data are still smaller than those of pure crystalline Coferrite. This reduction may be related to the contribution of a magnetically disordered phase mixed with ferrimagnetic order. This disordered phase cannot be superparamagnetic because of Coferrites the mean particles size of 40 nm is too big, that is, the threshold for superparamagnetic behavior for CoFe2O4 may be below 12 nm [3]. Additionally, one can really see that the particles do not behave superparamagnetic due to the linear temperature dependence of the coercivity for To250 K (see Fig. 3). The existence of a disordered phase can be conrmed by the presence of shoulders and peaks at Tf in the curves of the temperature dependence of real, w0 , and imaginary

Fig. 1. XRD pattern obtained on nanocrystalline CoFe2O4 using CoKa radiation.

Fig. 2. Central part of hysteresis loops measured with a maximum eld of 7 T, at 3300 K. Inset shows the magnetization behavior up to 7 T for 3 and 300 K.

ARTICLE IN PRESS
R. Sato Turtelli et al. / Journal of Magnetism and Magnetic Materials 320 (2008) e339e342 e341

Fig. 3. Temperature dependence of the coercive eld.

The temperature dependence of the ZFC magnetization applying a low eld of H 20 Oe shows also a shoulder around 200 K superimposed with the temperature increasing magnetization similar as found in the real component of the ac-susceptibility (see Figs. 4 and 5). In the ZFC and FC conditions the magnetization measurements were performed during the heating applying a magnetic eld. Fig. 5 shows ZFC and FC measured at 20 and 30 kOe. The peak in the ZFC changes to lower T with increasing eld and the irreversibility becomes larger below this temperature conrming thus the existence of SG phase mixed with the ordered ferrimagnetic component exhibiting a Curie temperature far above 300 K. In a SG, magnetic spins experience random interactions with other magnetic spins, resulting in a state that is highly irreversible and metastable. Above the freezing temperature the system is paramagnetic. In our nanocrystalline CoFe2O4 material, the SG may arises from randomly canted moments at the surface of the grains, which lowers the total maximum magnetization, Hc and remanence. However, due to high value of the total magnetization above Tf, the concentration of SG component may be small. The remanence and squareness ratio decrease with increasing temperature (see Fig. 2). At 3 K the squareness ratio is 0.84, however at 250 K it decreases to 0.60. The decrease of squareness is expected due to the contribution of the SG phase, because the remanence is a function of the ferrimagnetic phase only and the maximum magnetization of both ferrimagnetic and SG phase. In conclusion, the saturation magnetization here obtained is among the highest ones ever achieved for nanocrystalline CoFe2O4. The modied citrate-gel method allows to mix the metal ions at atomic scale using stirring and to combine them through metal-citric gel network, leading to a perfect reaction between ions to form CoFe2O4 with reduced local canting and obtaining nanocrystalline CoFe2O4 with an average grain size of 40 nm even after

Fig. 4. Temperature dependence of the ac-susceptibility measured at Hac 3 Oe for different frequencies f. The insets show some examples of the derivative dw0 /dT vs. T and Tf as function of the log f.

component, w00 , respectively, of the ac-susceptibility below the ordering temperature of CoFe2O4 (see Fig. 4). The position of imaginary peaks, which coincides with the position of peaks obtained by temperature derivative of the w0 (dw0 /dT), shifts to higher temperatures with increasing frequency f (see Fig. 4 and insets). The frequency change of the peaks of w0 and/or w00 with Tf has been used to distinguish the different disordered magnetic systems by the value of a parameter a DTf/ (Tf Dlog f) [4]. This varies from 0.005 for canonical spinglass (SG) to 0.28 for superparamagnetic particles [4]. Tf as function of log f is also shown in Fig. 4, in the lower inset. We found a value of a around 0.07, which may correspond to a SG behavior [4]. Thus, the temperature Tf is explained as a freezing temperature of the SG phase.

Fig. 5. Temperature dependence of the magnetization at 20 and 3000 Oe under FC and ZFC conditions.

ARTICLE IN PRESS
e342 R. Sato Turtelli et al. / Journal of Magnetism and Magnetic Materials 320 (2008) e339e342

annealing. This sample shows also a typical coercivity and high magnetostriction, suggesting that this simple, economic and effective method can be used to prepare highquality nanocrystalline CoFe2O4, suitable for a larger scale. Acknowledgments This work is supported by the FWF Proj. No. P16500 AD). N02, and the Austrian Exchange Service (O

References
[1] Giap.V. Duong, R. Sato Turtelli, N. Hanh, D.V. Linh, M. Reissner, H. Michor, J. Fidler, G. Wiesinger, R. Gro ssinger, J. Magn. Magn. Mater 307 (2006) 313. [2] Giap.V. Duong, R. Sato Turtelli, W.C. Nunes, E. Schaer, N. Hanh, R. Gro ssinger, M. Knobel, J. Non-Cryst. Solids 353 (2007) 805. [3] V. Masheva, M. Grigorova, N. Valkov, H.J. Blythe, T. Midlarz, V. Blaskov, J. Geshev, M. Mikhov, J. Magn. Magn. Mater 196 (1999) 128. [4] M.A. Novak, J. Magn. Magn. Mater 272276 (2004) e707.