Rare Metal Materials and Engineering Volume 37, Issue 1, January 2008 Online English edition of the Chinese

language journal Cite this article as: Rare Metal Materials and Engineering, 2008, 37(1): 01800184.

ARTICLE

Preparation of Spinel Ferrite CoFe2O4 Fibres by Organic Gel-Thermal Decomposition Process

Zhang Chunye, Shen Xiangqian, Zhou Jianxin, Shen Jiangying
Jiangsu University, Zhenjiang 212013, China

Abstract:

Functional spinel ferrite fibers are attractive for high-tech applications. The spinel CoFe2O4 fibres have been prepared

by the organic gel-thermal decomposition process from starting materials of Co, Fe nitrate salts and citric acid. The gel spinning performance was a major factor for preparation of uniform gel fibrous precursors. It was related to the citrate-metal complex structure, and linear-type structural molecule [(C6H6O7)4CoFe2]n for the gel precursor was formed during the complexation reaction between the citric acid and metal ions at pH 5.5. As a result, the gel composed of these linear-type molecules exhibited a good spinning performance. The composition, structure of the gel precursors and products derived from thermal decomposition of these precursors were characterized by FTIR, XRD and SEM. The thermal decomposition process of the gel precursors was investigated by TG-DSC. The prepared spinel CoFe2O4 fibres having grain sizes of 40~50 nm possess the diameters of about 1m, aspect ratios up to 1106 (length/diameter), a saturation magnetization value of 81.97 Am2/kg and a coercivity value of 1041.4779.6 A/m. Key Words: organic gel-thermal decomposition process; spinel ferrite fibres; CoFe2O4; spinning performance

Mixed metallic oxides, especially spinels with the general formula AB2O4 are very promising materials for technologically important applications. Spinel type ferrites are widely used in many electronic and magnetic devices due to their high magnetic permeability and low magnetic losses. Among spinel ferrites, cobalt ferrite CoFe2O4 have attracted great attention due to their high magnetocrystalline and shape anisotropy, coercivity, magnetostrictive coefficient, chemical stability and hardness[1,2]. Fibrous forms of ceramic materials can be made stronger and often stiffer than the bulk ceramics. The incorporation of a magnetic material in fibrous form and subsequent effects of composite phase geometry on material properties were reviewed[3] and it was showed that short fibers with a high aspect ratio could bring a much high magnetic permeability than the same volume of materials in non-fibrous form[4]. Sol-gel process can provide a mixing of multicomponents at an atomic or a molecular level at low temperatures, resulting in homogenous precursors. Consequently improved sintering rates at lower temperatures could be expected, leading to im-

proved microstructure[5]. The sol-gel method based on hydrolysis of alkoxide compounds has been used for preparation of fine ceramic fibres. Tsai[6] prepared Mg2SiO4 fibres by the sol-gel process using Si(OC2H5)4 and Mg(OCH3)2 as starting reagents and found that the gel spinnability was improved by addition of linear-type molecular citric acid. Pullar and coworkers [7] obtained barium M ferrite, BaFe12O19 fibres and strontium M ferrite, SrFe12O19 fibres with diameter in 36 m. The aqueous organic gel route was originally developed by Pechini and Marcilly and coworkers. The process involved the aqueous reaction of single or multiple metal ions with a polyfunctional acid such as citric acid, to produce stable complexes and prevent precipitation allowing the production of an amorphous gel on drying, which could be subsequently decomposed to the metal oxides by thermal treatment. In comparison with conventional sol-gel process based on alkoxides, the technique requires inexpensive precursors, allows the use of an aqueous based processing system and results in the formation of the oxides on heating. Although organic gel complex processes were previously used to produce various oxide

Received date: March 2, 2007 Foundation item: Projects (50474038, 50674048) Supported by the National Nature Science Foundation of China Corresponding author: Zhang Chunye, Master, School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, P. R. China. Tel: 0086-511-8791964, E-mail: zhangchunye_2001@126.com Copyright 2008, Northwest Institute for Nonferrous Metal Research. Published by Elsevier BV. All rights reserved.

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powders with multiple components[8], magnetic metal fibers[9] and refractory ceramic fibers[10], few works on magnetic ceramic fibers with a spinel structure prepared by this process were previously reported. The aim of this investigation is therefore to determine the feasibility of utilizing such a process route to produce spinel CoFe2O4 fine fibres from raw materials of metal salts and citric acid.

Table 1 Effects of pH value on gel spinning performances pH 3 4 5 5.5 6 7 Spinnability

1
1.1

Experimental procedure
Preparation of CoFe2O4 fibres

The starting reagents used were analytical grade Co(NO3)2.6H2O, Fe(NO3)3.9H2O and citric acid (C6H8O7.H2O). The metal salts and citric acid were dissolved in deionized water and diluted to form 0.2 mol aqueous solutions, respectively. According to the required composition, the two metal salt solutions were gradually added into the citric acid solution under continuous magnetic stirring. The pH of the solution was continually monitored and maintained at a value of 5.5 by addition of the ammonia solution required. The final solution was magnetically stirred for 2024 h at room temperatures and was transferred to a rotary evaporator and evaporated in a vacuum at 6070 C to remove surplus water until a viscous liquid was obtained. The resultant liquid was then poured into an evaporating basin and heated in vacuum at 75 C until a spinnable gel could be used for drawing gel fibers by handling a glass rod. The spinning performance of the gel was estimated from the capability of fiber formation by immerging a glass rod of about 2 mm in diameter into the gel and then pulling it up by hand. The gel fibers were drawn from the spinnable gels and dried in vacuum at 80 C for about 10 h. The dried gel fibers were then put in a quartz crucible and subsequently were calcined in the ambient atmosphere at 700 C for 2 h.

1.2

Characterization

The structure, composition and morphologies of the gel precursors and the products derived from thermal decomposition of the precursors at different temperatures were examined by Fourier Transform Infrared Spectroscopy (FTIR) using a model of Nexu670 spectrometer, X-Ray Diffraction (XRD) using a D/max2500PC diffractometer (RIGAKU), and Scanning Electron Microscopy using a XL-30ESEM instrument (PHILIPS). The decomposition process was investigated by Thermo-Gravimetric (TG) analysis and Differential Scanning Calorimetry (DSC) using a SDT2960 (TA) system. The magnetic properties were measured by the vibrating sample magnetometer(VSM).

Fe3+ and Co2+. The formation of the organometallic complexes and the nature of the resultant gels and their decomposition depend on pH. In aqueous solution, CA can remain as the compound H3Cit or disassociating increasing numbers of protons to form the species H2Cit-, HCit2-, Cit3- with the proportions of these species varying with pH[11] and at the pH range of 5 to 6 specie HCit2- exists mainly. The pH value of 5.5 was determined by calculation of the conditional formation constant to form stable CA-Fe(Co) complexes and in particular, testing spinning performances of the gel obtained. Table 1 shows the gel spinning performances at different pH values with a molar ratio (CA:Fe3+:Co2+) of 4:2:1. It can been seen that at this pH value the gel exhibited the best spinnability and would be anticipated to result in substantial complexation reactions among HCit2- and Fe3+ and Co2+ ions. Fig.1 shows the FTIR spectra for the gel. The bands at 1415 cm-1 and 1623 cm-1 resulted from the C=O stretching vibration were the characteristic absorption peaks for the citrate. Meanwhile the bands occurred at 831 cm-1 and 570 cm-1 could be assigned to the characteristic peaks of Co-O and Fe-O bonds, respectively[12]. It is believed that the CA-Fe-Co complex molecules have been formed and the liganding type can be classified by the value [13](=as, a and s were the symmetry and dissymmetry stretching vibration peak value of RCOO-). According to data from the gel FTIR spectra, the value was 208 cm-1, which was higher than that for citrate-Na (196 cm-1), and a single dentate liganding type among metal ions and species HCit2- took place largely during the complexation and a linear molecular

Transmittance

831 570 1415

1623

2
2.1

Results and discussion

Gel formation and spinning performance
2000 1600 1200 Wavenumbers/cm
-1

800

400

Aqueous organic gel processing routes most commonly utilize citric acid (CA) as the complexing agent. CA is known to form complexes with metal ions in aqueous solution such as

Fig.1 FTIR spectra of the gel precursor for CoFe2O4 fibres

Zhang Chunye et al. / Rare Metal Materials and Engineering, 2008, 37(1): 01800184

structure could be expected. Fig.2 shows XRD patterns of the gel precursor and the products derived from thermal decomposition of this gel precursor at different temperatures. It can be seen that the gel precursor was amorphous and did not contain crystalline inorganic salts (Fig.2a). The phase of CoFe2O4 started to form when the temperature was above 300 C as shown in Fig.2b. At 640 C the XRD pattern indicated that a relatively pure phase CoFe2O4 (JCPDS22-1086) was obtained. According to above analysis, the complexes of citrate-Fe-Co with possible formula [(C6H6O7)4CoFe2]n and a linear molecular structure as shown in Fig.3 can be deduced. The gel precursor consisted of such a linear molecular structure and exhibited high spinning performances.

CH2COOH HO C COO Fe

CH2COO CH2COO HO C COOH

CH2COO CH2COO HO C COOH Co

2.2

Thermal decomposition of gel precursor

HO

CH2COO CH2COO C COO Fe

Fig.4 shows the TG/DSC data for the gel precursor. The thermal decomposition process consists of the following three stages. (1) At temperatures in the range of 50150 C, the TG/DSC analyses indicated a broad endothermic event occurred with a corresponding mass loss of about 12%. This may be attributed to the loss of free water from the gel precursor. (2) At slightly higher temperatures in the range of 150~350 C, a second stage in the decomposition of the gels took place. This was characterized by a large and sharp exothermic event at around 155 C in the DSC analysis, followed by a small endothermic peak at about 210 C. The first event in the range of 150180 C was accompanied by a corresponding mass loss of approximately 20% occurred in the TG, with a more substantial mass loss of 35% over the range 180350 C. Such a behavior was mainly attributed to the spontaneous combustion at around 155 C and breakdown of the complexes at around 210 C, followed by the decomposition and oxidation of the organic materials to form mixed metal oxides and CoFe2O4 as shown in the XRD

CH2COOH Fig.3 Possible linear molecular structure of the citrate-Fe-Co complexes in gel precursor for CoFe2O4 fibres 100 80 Mass Loss/% 3 60 40 20 0 1 5 Heat Flow/mWmg-1

1 50 150 250 350 450 550 650 750 850

Temperature/ Fig.4 TG-DSC curves of the fibre gel precursor

(e)700 C (d)640 C (c)500 C

(b)300 C (a)Precursor 10 20 30 40 50 2/() Fig.2 XRD patterns of the gel precursor and the products derived from calcinations of the gel precursors at different temperatures 60 70 80

pattern in Fig.2b. The spontaneous combustion was caused by interactions of citrate and nitrate ions in the gel with liberation of H2O, CO2 and NOx as the nitrate ions provided an in situ oxidizing environment for the combustion of the organic components [14,15]. (3) At the temperature range of 350700 C and over, the TG analysis shows a mass loss of about 10% and a small endothermic peak was observed at about 640 C. It was believed that the formation and growth of spinel CoFe2O4 took place at this stage. According to the above analysis, the thermal decomposition processing conditions to form spinel CoFe2O4 fibres from the fibrous gel precursors can be determined: 700 C for 2 h at an ambient atmosphere with a heating rate of 5 C /min.

Intensity/a.u.

2.3

Characterization of spinel CoFe2O4 fibres

Zhang Chunye et al. / Rare Metal Materials and Engineering, 2008, 37(1): 01800184

The morphology and microstructure of the CoFe2O4 fibre were affected by the processing parameters. Defects in the fibres such as cracks, cones, bonds and pores as shown in Fig.5 occurred due to improper processing parameters used during the complex formation, dehydration and subsequent thermal treatment processes. In order to avoid these fibre defects, processing parameters such as molar ratio, pH, complexation reaction time, dehydration and heat treatment programmer should be optimized. The SEM morphology and XRD pattern of spinel CoFe2O4 fibres prepared at the optimized conditions were showed in Fig.6 and Fig.2e, respectively. The results show that the diameter of the CoFe2O4 fibres were fine, as thin as about 1 m and the fiber length could be as long as 1 m, with an aspect ratio up to 1106. The grain sizes estimated from the SEM graph as shown in Fig.6a for these CoFe2O4 fibres were approximately 4050 nm and calculated by Scherrer equation from the XRD data in Fig.2e were 38.8 nm.

Saturation Magnetiation/Am2kg-1

100 50 0 50 100 8000

4000

4000
-1

8000

Coercivity/79.6Am

Fig.7 The magnetic hysteresis loop for the CoFe2O4 fibres

Conclusions

2.4

Magnetic properties of CoFe2O4 fibres

Fig.7 shows the hysteresis loop for CoFe2O4 fibers at room temperatures and the values of saturation magnetiation and coercivity were 81.97 Am2/kg and 1041.4779.6 A/m respectively for CoFe2O4 fibers were obtained. The magnetic properties for the CoFe2O4 fibers can be tailored by optimizing diameters, aspect ratios(length/diameter) et al to meet the requirement for advanced electromagnetic wave absorbers and devices.

Bonds

Cones Cracks

1) The organic gel-thermal decomposition process can be used for the preparation of spinel CoFe2O4 fine fibres with a high aspect ratio using citric acid and metal salts as the starting reagents. The gel spinnability was related to the metal-carboxylate complex structure. 2) The linear-type structural molecule [(C6H6O7)4- CoFe2]n for the gel precursor was formed during the complexation reaction between the citric acid and metal ions. As a result, the gel composed of these linear-type molecules exhibited a good spinning performance. The diameter and aspect ratio of the prepared fibres could be less than 1 m and up to 106, respectively. These spinel CoFe2O4 fine fibres consist of nanosized crystalline grains, with saturation magnetiation value of 81.97 Am2/kg and coercivity value of 1041.4779.6 A/m.

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Fig.5 SEM image of the CoFe2O4 fibre with defects a

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