Synthesis of cobalt ferrite nanoparticles using a combination of the co-precipitation and hydrothermal methods

Sonja Jovanovi1,2, Matja Spreitzer1, Mojca Otoniar1,2, Danilo Suvorov1,2

1 Department

of Advanced Materials, Joef Stefan Institute, Ljubljana, Slovenia 2 Joef Stefan International Postgraduate School, Ljubljana, Slovenia
sonja.jovanovic@ijs.si

Abstract. In this work we have examined the influence of the pH on the structural and magnetic properties of cobalt ferrite (CoFe2O4) nanoparticles obtained by a combination of the co-precipitation and hydrothermal methods. The crystal structures and the particle sizes of the prepared powders were analyzed by the X-ray diffraction and transmission electron microscopy, while the magnetic properties of the cobalt ferrite nanoparticles were measured at room temperature using a vibrating-sample magnetometer. The results showed that an increase of the pH improves both the crystallinity of the CoFe2O4 nanoparticles and their average size. At the same time the pH affects the magnetic properties of the nanoparticles, since the saturation magnetization (MS), remanent magnetization (Mr) and coercivity (HC) increase with the increase of the pH. Keywords: Cobalt ferrite; Nanoparticles; Hydrothermal synthesis; Magnetic properties

1 Introduction
The spinel ferrites are a large group of oxides that were first studied by Nishikawa (1915) and Bragg (1915); they have the structure of the natural spinel MgAl2O4 [1].In recent years, spinel ferrite nanoparticles have been actively investigated because of their magnetic and electrical properties. The general formula of spinel ferrites is MFe2O4, where M is a divalent ion such as Co2+, Ni2+, Zn2+, Mn2+, etc. Cobalt ferrite is a material that possesses an inverse spinel structure. It has a moderate saturation magnetization, a large magnetic anisotropy, a remarkable chemical stability and a mechanical hardness, and because of these properties it can

be used for recording media, spintronics, magnetic refrigeration, ferrofluids, magnetic resonance imaging, the delivery of drugs to specific areas of the body, etc. [2-5]. In order to obtain CoFe2O4 with the appropriate physical and chemical properties, its synthesis via different methods has become an important area of research and development. Several methods for the preparation of cobalt ferrite nanoparticles have been reported, such as the ball milling, co-precipitation, hydrothermal synthesis, sol-gel, and reaction in a micro-emulsion [6-10]. A hydrothermal synthesis offers several advantages over other conventional processes, like the simplicity, cost effectiveness, higher dispersion, higher rate of reaction, better shape control, and lower temperature of operation in the presence of an appropriate solvent, etc [11]. In a recent study, Liu et al. examined the influence of the synthesis time and the concentration of metallic ions on the synthesis of CoFe2O4 nanoparticles [8]. They used sodium dodecyl sulfate (NaDS) during the synthesis, which enabled them to control the morphology of the particles to a certain extent. However, they did not investigate the influence of pH on the morphology and magnetic properties, which is the main purpose of our work.

2 Experimental
As in a typical synthesis, sodium dodecyl sulfate (8.5 mmol) was added to 25 ml of deionized water and stirred for a few minutes at 50oC, and 4.25 mmol of CoCl26H2O was added under stirring to ensure the complete dissolution. Then, 8.5 mmol of FeCl36H2O was added into this solution and stirred until its dissolution. Finally, 25 ml of 2,5 M aqueous solution of NaOH was added and stirred for several minutes. A black precipitate formed in the solution with pH=13.1. A similar sample was treated with 37 % HCl and its pH was adjusted to 8.0. The mixture was transferred into a Teflon-lined, stainless-steel autoclave with a capacity of 75 ml, closed, and kept at 120oC for 8h. The product was sonicated for 30-45 min, and then washed several times with distilled water, ethanol and then centrifuged. The product was dried at 70oC in air over night. The crystal structure of the obtained powders was analyzed by the X-ray diffraction (XRD, Siemens D5000) with the Cu K (=1.5406 ) radiation at room temperature for the 2 range from 20o to 80o (2 step=0.04o with a counting time of 1s per step). The structural characteristics and the particle sizes were examined

using a transmission electron microscope (TEM, JEM-2100, JEOL Ltd., Tokyo, Japan) operated at 200 kV. The magnetic properties of the cobalt ferrite nanoparticles were measured at room temperature using a vibrating-sample magnetometer (VSM, 7307 Lake Shore).

3 Results and Discussion

The XRD patterns of the as-prepared CoFe2O4 nanoparticles are shown in Figure 1. The results show that as the pH increases the diffraction maxima become sharper and more pronounced. This indicates that the crystallinity and the average particle size are increased as the pH increases. The crystal structure of the CoFe2O4 prepared at pH=13.1 has a cubic symmetry and is in accordance with JCPDS card No. 22-1086. The average crystallite size of the cobalt ferrite prepared at pH=13.1, based on the Scherrer formula [12], was estimated to be 15 nm.

Figure 1: XRD patterns of the as-prepared CoFe2O4 nanoparticles: a) coprecipitation, b) pH=8.0 and c) pH=13.1. Figure 2 presents TEM images of the as-prepared cobalt ferrite nanoparticles. The samples prepared at pH=8.0 and by co-precipitation are mainly amorphous, as corroborated by the XRD patterns (Figure 1). The crystallinity and the particle size of the samples increases with the pH. In the case of the highest pH the particles are of a cube-like shape and have a broad size distribution.

Figure 2: TEM images of the CoFe2O4 nanoparticles a) co-precipitation, b) pH=8.0 and c) pH=13.1. The magnetic properties of the CoFe2O4 nanoparticles were investigated using a vibrating-sample magnetometer (VSM). Figure 3 shows the hysteresis loops that were measured at room temperature in a magnetic field of 15 kOe. The values for the saturation magnetization (MS), remanent magnetization (Mr), and the coercivity (HC) are shown in Table 1. Table 1: Magnetic properties of the CoFe2O4 nanoparticles prepared at T=120 oC and pH = 8.0 and 13.1 and by co-precipitation pH Co-precipitation 8.0 13.1 MS, emu/g 3.2 10.9 65.4 Mr, emu/g 0.00 0.01 19.95 HC, Oe 3.9 5.7 775.8

The MS, Mr and HC values increase with increasing pH and for the sample synthesysed at pH=13.1 these values are 65.4 emu/g, 19.95 emu/g and 775.8 Oe,

respectively. As is clear from Figure 3, with the increase of the pH the samples change their magnetic behaviour: they go from paramagnetic to ferromagnetic. We anticipated that an increase in the magnetic properties is related to the higher crystallinity of the sample obtained at pH=13.1. Furthermore, we observed that the values of MS, Mr and HC obtained here (Table 1) are higher than the corresponding values (60.27 emu/g, 15.63 emu/g and 465 Oe, respectively) reported by Liu at al. [8].

Figure 3: Hysteresis loops of the CoFe2O4 nanoparticles

4 Conclusion
The effect of pH on the structural and magnetic properties of the CoFe2O4 nanoparticles prepared by a combination of the co-precipitation and hydrothermal methods was investigated. The results show that the crystallinity and average particle size increase with the increase of the pH. Also, the values of MS, Mr and HC follow this trend. The sample prepared at pH=13.1 has the highest values of MS, Mr and HC (65.4 emu/g, 19.95 emu/g and 775.8 Oe, respectively) and, according to Scherrers equation, the average crystallite size for the sample with pH=13.1 was estimated to be 15 nm.

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For wider interest

Because of its magnetic and electrical properties, cobalt ferrite is an interesting material. It has a moderate saturation magnetization, a large magnetic anisotropy, a remarkable chemical stability and a mechanical hardness. Because of these properties it can be used for recording media, spintronics, magnetic refrigeration, ferrofluids, magnetic resonance imaging, the delivery of drugs to specific areas of the body, etc. The presented results are part of the project aimed to improve the magnetic properties of cobalt ferrite particles along with the control of particle sizes and their stability, which would enhance the applicability of cobalt ferrite.