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Physica B 370 (2005) 1421 www.elsevier.com/locate/physb

Synthesis of nanocrystalline spinel CoFe2O4 via a polymer-pyrolysis route

Xian-Ming Liua,b, Shao-Yun Fua,, Hong-Mei Xiaoa,b, Chuan-Jun Huanga
a

Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100080, PR China b Graduate School, Chinese Academy of Sciences, Beijing 100039, PR China Received 7 May 2005; received in revised form 30 August 2005; accepted 30 August 2005

Abstract Nanocrystalline CoFe2O4 spinel ferrites were synthesized via the pyrolysis of polyacrylate salt precursors prepared by in situ polymerization of metal salts and acrylic acid. The pyrolytic behaviors of the polymeric precursors were analyzed by use of simultaneous thermogravimetric and differential thermal analysis (TG-DTA). The structural characteristics of the calcined products were obtained by powder X-ray diffraction (XRD), infrared spectroscopy (IR) and transmission electron microscope (TEM). The results revealed that cobalt ferrites had nano-sized morphology and good crystallinity even if calcined at moderate temperature like 500 1C for 3 h. The average size of nanocrystalline cobalt ferrites ranged from 20 to 30 nm with a narrow size distribution, while the particle size increased with the increase of the calcination temperature. Magnetic properties were obtained at room temperature using a vibrating sample magnetometer. The samples exhibited hysteresis loop typical of magnetic behaviors, indicating that the presence of an ordered magnetic structure could exist in the mixed spinel system. The as-calcined cobalt ferrites at 500 1C exhibited the highest magnetization value of 77.4 emu/g at 10 kOe, while the highest remanence and coercivity of 35.6 emu/g and 1445 Oe, respectively, for those calcined at 700 1C were obtained. r 2005 Elsevier B.V. All rights reserved.
PACS: 75.50.G; 75.50.T; 81.16.B Keywords: Cobalt ferrite; Polyacrylate salt; Pyrolysis; Magnetization; Coercivity

1. Introduction The nanometer-sized ferrite magnetic materials are the subject of intense research because of their potential applications in high-density magnetic recording media [1,2]. Among the family of ferrite materials, cobalt ferrite (CoFe2O4) with a partially

Corresponding author. Tel.: +86 10 62659041;

fax: +86 10 62564049. E-mail address: syfu@cl.cryo.ac.cn (S.-Y. Fu).

0921-4526/$ - see front matter r 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.physb.2005.08.030

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inverse spinel structure, is one of the most important and abundant magnetic materials. As a conventional magnetic material with a Curie temperature (Tc) around 793 K, CoFe2O4 is well known to have large magnetic anisotropy, moderate saturation magnetization, remarkable chemical stability and a mechanical hardness, which make it a good candidate for the recording media. Large-scale applications of ferrites with nanometer size and the tailoring of magnetic properties have prompted the development of several widely used methods, including sonochemical reactions [3], solgel techniques [46], reverse micelles [7], host template [810], coprecipitation [11], microemulsion procedures [1216], precursor techniques [1720], microwave plasma [21], mechanical alloying [2224], hydrothermal method [25], and combustion method [26] for the fabrication of stoichiometric and chemically pure spinel ferrite nanoparticles. The above methods can produce highly crystalline and uniformly sized magnetic nanoparticles. However, these synthetic procedures cannot be applied to large-scale and economic production because they require expensive and often toxic reagents, complicated synthetic steps, and high reaction temperature and long time. Very recently, the precursor route is one of the most used ones, owing to its economics and the high degree of compositional control. In addition, the precursor synthesis requires neither extremely high processing temperature nor sophisticated process. The above precursor method is an economical way to produce ultrane powders. However, coarse particles may form after the decomposition process due to agglomeration. To avoid compromising the purity and properties of spinel ferrite or agglomeration, it would be desirable to prepare them from a single solid precursor which can be prepared in a pure state in which the Co2+ and Fe3+ cations are uniformly distributed on an atomic level. To the best of our knowledge, there is no report on preparation of nanocrystalline cobalt ferrite by in situ polymerization of the mixed aqueous solution of acrylic acid in the presence of metal salts followed by a pyrolysis process. This method has the advantage that it can be readily scaled up in the form of a batch process producing highly homogeneous

nanocrystalline cobalt ferrite with excellent magnetic performance.

2. Experimental section 2.1. Preparation of materials The chemical reagents used in this work are ferric nitrate (Fe(NO3)3 9H2O), cobalt nitrate (Co(NO3)2 6H2O), ammonium persulfate ((NH4)2 S2O8), and acrylic acid. All reagents are of analytical grade and used without further purication. Manipulations and reactions were carried out in air without the protection of nitrogen or inert gas. In a typical experiment, nanocrystalline spinel ferrites were prepared by a polymer-pyrolysis route using polyacrylate of Co and Fe as precursor compounds. The simultaneously polymeric precursors were made by in situ polymerization of the mixed aqueous solution of acrylic acid in the presence of Co(NO3)2 6H2O and Fe(NO3)3 9H2O, with (NH4)2S2O8 as the initiator. First, cobalt and ferric nitrates were dissolved in 10 g of acrylic acid aqueous solution (acrylic acid: H2O 70 wt%: 30 wt%) under stirring. The molar fraction of Co/Fe was xed at 1:2. Afterwards, a small amount (0.5 g) of 5% (NH4)2S2O8 aqueous solution as the initiator was added to the mixed acrylic acid solution to promote the polymerization. Under heating at 7090 1C for 2 h, the mixed solution was dried to form the well-distributed polyacrylate salt. The obtained polyacrylates were dried at 100 1C for 24 h, and calcined at different temperatures (such as 500, 700, 900 1C) for 3 h in air, then the nal products were obtained after being slowly cooled to room temperature. 2.2. Characterization The decomposition process of the polymeric precursors during heat treatment was characterized by thermogravimetric and differential thermal analysis (TG/DTA) on a model WCT-1A thermobalance (TA-5000 apparatus) at the temperature range of 25900 1C with a heating rate of 10 1C min1 in air. To reveal the crystalline

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structure of CoFe2O4 powders, XRD analysis was carried out on a Regaku D/max2500 diffractometer at a voltage of 40 kV and a current of 200 mA with Cu-Ka radiation (l 1:5406 A), 1 employing a scanning rate 0.021 s in the 2y ranging from 51 to 701. Transmission electron microscope (TEM) images were recorded on a Hitachi-600 TEM at an accelerating voltage of 200 kV. The infrared (IR) spectra were recorded on a Bruker Equinox-55 spectrometer on samples palletized with KBr powders. Magnetic measurements were carried out at room temperature using a vibrating sample magnetometer (VSM, Lakeshore 7307) with a maximum magnetic eld of 10 kOe. The actual stoichiometric compositions of the obtained powders were determined by a Shimadzu ICPS-75000 inductively coupled plasma atomic emission spectrometer (ICP-AES).

3. Results and discussion The co-polymeric precursor compound is schematically represented in Fig. 1. As it is shown, the

cobalt (II) and iron (III) ions are bound by the strong ionic bonds between the metallic ions and carboxylate ions in a polymeric chain or between the polymeric chains. This uniform immobilization of metallic ions in the polymer chains favors the formation of uniformly distributed solid solution of the metallic oxides in the following pyrolysis process. To clarify the chemical reactions of the copolymeric precursors occurring in the pyrolysis process, we measured TG and DTA curves of the co-polymeric CoFe precursors, as shown in Fig. 2. In the TG-DTA curves of Co ferrite precursors (Fig. 2), there are two weight-losing processes present at 25305 1C and 305428 1C with total weight loss of 82.3%. The rst step of weight loss is ca. 27.1% of total weight, corresponding to a small exothermic peak in the DTA curve, possibly due to the decomposition of nitrate. In the second step of weight loss, the weight loss is ca. 55.2% and correspondingly, a high exothermic peak in the DTA curve is observed in the temperature range of 305428 1C, which is likely to arise from the decomposition of

Co O

C O

Fe

C O

O C O O C O C O O C O O

C O O C O

Fig. 1. Schematic representation of polymeric chain of the co-polymeric precursor of CoFe polyacrylates.

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25 100 20 Weight loss (%) 80 15 60 40 20 0 200 400 600 Temperature (C) 800 10 5 0 Temperature difference (C)

Fig. 2. TG-DTA curves of cobalt ferrite precursors.

CoFe polyacrylate into metal oxides. It is noted that the weight is almost unchanged above the decomposition temperature, indicating that the nal decomposed products are ferrites. Fig. 3 showed XRD patterns of cobalt ferrite powders prepared by the polymer-pyrolysis route at different temperatures. The diffraction patterns and relative intensities of all diffraction peaks matched well those of JCPDS card 22-1086 for CoFe2O4. The peaks appeared at around 18.51, 30.21, 35.61, 37.21, 43.01, 53.41, 57.11, and 62.51 which were well indexed to the crystal plane of spinel ferrite (1 1 1), (2 2 0), (3 1 1), (2 2 2), (4 0 0), (4 2 2), (5 1 1), and (4 4 0), respectively. The peak intensity of CoFe2O4 increased with the increase of calcination temperature, which indicated that the calcination temperature played a role in the formation of spinel crystal structure and size. All the ferrites showed a single-phase spinel ferrite with no impurities in the XRD patterns. The fullwidth at half-maximum (FWHM) of the peak (3 1 1) decreased with the increase of the calcination temperature. The average size of the crystallites can be estimated from the FWHM of the peak (3 1 1) using the Scherrers equation and the results are listed in Table 1. In addition, the elemental analyses of these nanoparticles using ICP-AES showed that the molar ratios of Co2+/Fe3+ are close to 0.5. The detailed microstructures of the calcined products were characterized by TEM. Fig. 4ac showed the bright eld TEM images of CoFe2O4

nanoparticles. It can be seen that the particles have nanometer-scale morphology at a relatively low calcination temperature and are clearly dispersive apart from each other. Their average particle sizes are 25, 80, and 120 nm for CoFe2O4 calcined at 500, 700, and 900 1C, respectively. Moreover, the solid materials obtained exhibit a very narrow size distribution for cobalt ferrites. The IR spectrum of the co-polymerized CoFe polyacrylate is shown in Fig. 5a. It is found that the CQO stretching vibration ($1702 cm1) of aand b-unsaturated carboxylic acid, the CQC stretching vibration ($1640 cm1) and the QCH vibrations ($1045 and $984 cm1) of acrylic acid, characteristic of the vinylidene group in the acrylic monomers, are absent, suggesting that the polymerization of acrylates took place in the acrylate of Co and Fe. However, the symmetric ($1618 cm1) and asymmetric ($1451 cm1) stretching bands of carboxylate salts appear in the IR spectrum. Compared with the standard spectrum of acrylic acid [27], these two bands are positively shifted, implying an associating interaction between the metallic ions and carboxylate ions. In addition, the IR bands for H2O ($3428 cm1) and NO vibration ($1384 and 3 $839 cm1) are also observable due to the residual H2O and NO , while characteristic bands of other 3 anions with small quantity are overlapped. Fig. 5b exhibits the IR spectrum of cobalt ferrites obtained by pyrolysis of CoFe polyacrylates at 500 1C. It can be seen that the IR spectrum shows

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(c)

8000 (220) 4000 0 9000 (b) 6000 (422) (511) 50 60 (400) (440) 70
Mr (emu/g)

(111)

3000

0 150 120 90 60 30 0 10 20 30 40 2theta (degree) (a)

Fig. 3. XRD patterns of CoFe2O4 calcined at different temperatures (a) 500, (b) 700 and (c) 900 1C. Table 1 Summaries of some properties of CoFe2O4 nanoparticles derived from XRD, TEM, and magnetic measurements Calcination temperature (1C) 500 700 900
a

dXRD (nm) (3 1 1)

dTEM (nm)

(222)

(311)

12000

Magnetization at 10 kOe (emu/g) 77.4 69.3 70.8

Hc (Oe)

22 74 118a

25 80 120

34.8 35.6 17.7

505 1445 453

The present evaluation is inappropriate for the grain size larger than 100 nm due to a large resulted deviation.

no residual organic compounds and NO ions after 3 calcination, and the peak at about 588 cm1 is assigned to the stretching vibrating mode of MO (MQFe,Co) bands, indicating that the pyrolysis products are inorganic metal oxide species. The hysteresis loops of the samples are shown in Fig. 6. At room temperature, the samples exhibited hysteresis loops typical of magnetic

behaviors, indicating that the presence of an ordered magnetic structure can exist in the spinel system. Magnetization data are listed in Table 1. The magnetization of the samples is much higher and tends to be saturated at a high eld. The value for the sample calcined at 500 1C is close to the saturation magnetization of bulk cobalt ferrite, known as 80 emu g1 [28]. After being calcined at

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Fig. 4. TEM photographs of CoFe2O4 calcined at different temperatures (a) 500, (b) 700 and (c) 900 1C.

(a)

(b)

4000

3200

2400

1600

800

Wavenumber (cm-1)

Fig. 5. IR spectra of the samples (a) CoFe PA and (b) CoFe2O4 calcined at 500 1C.

700 or 900 1C, ordering of the samples takes place and results in lowering of magnetic moments, which leads to lower Ms value and higher coercivity. The increase in coercivity is observed for the sample calcined at 700 1C. This can be expected due to the rise in the size of the particles. However, calcination at 700 1C causes Hc to grow anomalously large, but decreases upon further increase in calcination temperature to 900 1C. If the increase in Hc was only due to the increase in nanocrystallite size, Hc would not decrease upon to the higher temperature which results in addi-

tional nanocrystal growth. One explanation for the observed excessive increase in Hc is an increase in the nanocrystallize average aspect ratio upon raising the calcination temperature as indicated by TEM observations. Very small increase in the aspect ratio can lead to large changes in coercivity. The decline in Hc upon higher calcination temperature could be the result of additional growth of the nanocrystals due to the increased atomic mobility at higher calcination temperature, resulting in an overall decrease in the aspect ratio and giving rise to a rounding of the particles [20].

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500 C 60 700 C 900 C 30 M (emu /g)

-30

-60

-10000

-5000

0 H (Oe)

5000

10000

Fig. 6. Hysteresis loops of the as-calcined CoFe2O4 at room temperature.

Alternatively, it is possible that magnetization pinning defects were incorporated into the nanocrystallites upon onset of signicant crystallite growth at 700 1C, perhaps due to lattice mismatch between the intergrowing nanocrystallites. Calcination at higher temperature would reduce these defects and result in the decrease in Hc observed. The effect of calcination temperature on the remanence (Mr) is similar to that of coercivity. It can be seen that the highest remanence (Mr) is observed in the sample calcined at 700 1C, which indicated that the highest coercivity can be obtained under certain conditions. It can be found that the magnetization of CoFe2O4, produced by a polymer-pyrolysis route had much higher values than those of CoFe2O4 produced by wet chemical methods [36,11,25,26]. This is because the polymer-pyrolysis route possesses several advantages as a single molecular precursor to form spinel ferrites that lead to enhanced saturation magnetization. Use of a molecular precursor with cations randomly distributed with no long order facilitates the synthesis of a homogeneous spinel phase.

nanocrystalline cobalt ferrites by the pyrolysis of CoFe co-polymeric precursors in situ polymerized by reaction of metal salts and acrylic acid. TG-DTA measurements showed that the pyrolysis process could occur at a low temperature to form spinel ferrites. The results from the XRD and TEM measurements revealed that the ferrite powders have good crystallinity with the spinel structure. The as-calcined cobalt ferrites at 500 1C exhibited the highest magnetization value of 77.4 emu/g at 10 kOe, while the highest remanence and coercivity of 35.6 emu/g and 1445 Oe, respectively, for those calcined at 700 1C were obtained. Furthermore, spinel ferrites derived from the CoFe polyacrylates have higher saturation magnetizations than those of the same materials produced by the conventional ceramic and wet chemical routes.

Acknowledgment We appreciate the nancial support of the National High Technical Research and Development Program of China (No. 2003AA305890). References
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4. Conclusions In summary, a simple and novel route has been presented for producing highly homogeneous

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