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Integrated Ferroelectrics

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Rietveld Analysis of Iron Oxide Nanoparticles

Joshy Josepha; N. Mishraa; D. Guptaa; M. Sharmaa; R. K. Pandeyb a Department of Physics, Barkatullah University, Bhopal, M.P b University Institute of Technology Barkatullah University, Bhopal, M.P Online publication date: 20 November 2010

To cite this Article Joseph, Joshy , Mishra, N. , Gupta, D. , Sharma, M. and Pandey, R. K.(2010) 'Rietveld Analysis of Iron

Oxide Nanoparticles', Integrated Ferroelectrics, 122: 1, 12 15 To link to this Article: DOI: 10.1080/10584587.2010.492286 URL: http://dx.doi.org/10.1080/10584587.2010.492286

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Integrated Ferroelectrics, 122:1215, 2010 Copyright Taylor & Francis Group, LLC ISSN: 1058-4587 print / 1607-8489 online DOI: 10.1080/10584587.2010.492286

Rietveld Analysis of Iron Oxide Nanoparticles

JOSHY JOSEPH,1 N. MISHRA,1 D. GUPTA,1 M. SHARMA,1 AND R. K. PANDEY2,
1 2

Department of Physics, Barkatullah University, Bhopal (M.P) 462026 University Institute of Technology Barkatullah University, Bhopal (M.P) 462026
A room temperature solution process for synthesis of Fe3 O4 nanoparticles demonstrated. It is shown that the particle size can be controlled with low concentration of oleic acid. The structure of as grown particles using X-ray diffraction and Rietveld renement are discussed. Fe3 O4 samples showed reduction in particle size for decreased concentration of oleic acid employed during synthesis. The as grown nanoparticles were found to possess a preferential (311) orientation of the cubic phase. The X-ray diffraction and the Rietveld renement conrm the inverse spinel structure of cubic phase of magnetite.

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Introduction
The crystal chemistry of the spinel magnetite, Fe3 O4 , is of considerable interest to mineralogists and materials scientists because of its applications in pharmaceutics [1], electronic [2] and biomedical devices [3]. When the ferromagnetic particle size is reduced below a threshold value, the magnetic isotropic energy/particle size become comparable to the ambient thermal energy. The thermal uctuation cause random ipping of the magnetic moment of the nanoparticle with time. As a result, the magnetic moment is no longer directed uniquely, so that the nanoparticles become superparamagnetic [4]. Nanoparticles of Fe3 O4 have been prepared using a variety of methods, such as reverse micelle micro emulsion [5], mechanical ball milling [6], thermal decomposition [7], and co precipitation [8]. In this report we have developed a relatively simple, high throughput room temperature process for growth of magnetic nanoparticles. Characterization of the crystal structure of the as synthesized nanoparticles of Fe3 O4 using X-ray diffraction and Rietveld renement was also undertaken. The results are discussed in this report.

Experimental Techniques
Room temperature synthesis of Fe3 O4 nanoparticles was carried out using an aqueous solution of ferrous chloride (0.164M) and ferric chloride (0.328M) in the molar ratio of 1:2. Ammonia was used as the precipitating agent. Briey, mixed and dissolved ferrous chloride and ferric chloride in 100 ml triple distilled water were under vigorous stirring. Aqueous ammonia (0.3 mol L1) was dropped slowly into the mixture solution until the pH value was titrated to 11. It can be observed that the solution became black due
Received December 11, 2009; in nal form April 3, 2010. Corresponding author. E-mail: directorbuit@gmail.com

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Rietveld Analysis of Iron Oxide Nanoparticles

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to the formation of Fe3 O4 particles. The sample was kept reacting in water bath for 5 min under vigorous stirring. In order to investigate the effect of the presence of oleic acid during synthesis, we added predetermined molar concentration in the bath. Four set of samples were synthesized using varying oleic acid concentration viz 0(sample 1), 0.1(sample 2), 0.06(sample 3) and 0.03(sample 4). The nanoparticles were collected using magnetic separation and centrifugation. X-ray diffraction patterns were recorded using Shimadzu XRD-6000 diffractometer in grazing angle mode at an angle of incidence of 0.5 . Wide-angle X-ray spectra were recorded in the 2 range of 28 to 70 with a step size of 0.02 . Rietveld renement was also used to analyse the structural data. Scale factor, background parameters, lattice parameter, the free positional parameter, x, overall atomic displacement parameters, peak shape parameters and prole asymmetry were the parameters rened.

Result and Discussion

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Figure 1 depicts the powder X-ray diffraction (XRD) patterns of the as-prepared Fe3 O4 nanoparticles (sample 1 to 4) grown by varying the concentration of oleic acid. Normally oleic acid has been used as surfactant in high temperature reaction. But we have examined possibilities of its use in a close to room temperature process. The position and relative intensity of all diffraction peaks match well with a cubic spinel structure of magnetite. The Fe3 O4 nanoparticles display several relatively strong reection peaks in the 2 region of 3065 . All the peaks are well matched with the standard JCPDS, (190629) [9]. Moreover one peak at 32.77 due to the contribution from Fe2 O3 was also observed. The ratio of the integral intensity from all the diffraction peaks of Fe2 O3 to that of Fe3 O4 is very small, revealing that Fe3 O4 is the major product and the proportion Fe2 O3 is very low in the whole sample. Fe3 O4 sample 2 to 4 implied a concomitant reduction in particle size for decreased concentration of oleic acid employed during synthesis. Interestingly, for higher oleic acid concentration, the particle size was larger than for lower concentrations. The

Sample 1

Intensity (A.U)

Sample 2

Sample 3

Sample 4
30 40 50 60 70

Figure 1. X-ray diffraction pattern of Fe3 O4 nanoparticles synthesized by 0M(sample 1), 0.1M(sample 2), 0.06(sample 3) and 0.03(sample 4) concentration of Oleic acid.

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Figure 2. (a) Representation of a typical Rietveld rened pattern of Fe3 04 Sample 1 (Fig 2a), nanoparticles. The experimental data are represented by dotted pattern (grey colour) while the solid curve corresponds to the Rietveld t. The difference between the expected and tted patterns has also been shown in the lower curve; (b) Representation of a typical Rietveld rened pattern of Fe3 04 Sample3 (Fig 2b) nanoparticles. The experimental data are represented by dotted pattern (grey colour) while the solid curve corresponds to the Rietveld t. The difference between the expected and tted patterns has also been shown in the lower curve. (c) Representation of a typical Rietveld rened pattern of Fe3 04 sample4 (Fig 2c) nanoparticles. The experimental data are represented by dotted pattern (grey colour) while the solid curve corresponds to the Rietveld t. The difference between the expected and tted patterns has also been shown in the lower curve.

average diameter of the Fe3 O4 nanoparticles calculated from Scherrers equations were 9, 6.4, 6 and 5.6nm for sample 1, sample 2, sample 3 and sample 4 respectively. The XRD pattern cannot provide enough evidence to conrm the formation of Fe3 O4 , since there is a little difference between the XRD patterns of Fe3 O4 and that of -Fe2 O3 . The black colour of the as prepared sample suggested the formation of Fe3 O4 and not of -Fe2 O3 . Rietveld analysis was, therefore, used to examine the phase of the sample. The results are shown in Figure 2(ac). All the experimental data could be matched with the theoretical data indicating a good t. The difference between the two data was a straight

Rietveld Analysis of Iron Oxide Nanoparticles Table 1 The Rietveld parameters obtained for sample 1,3 and 4. Sample Name Sample 1 Sample 3 Sample 4 R. Factor 4.33 8.00 9.06 Chi2 Factor 1.48 1.86 2.08

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G. of Fitting 1.2 1.4 1.4

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line as shown in the Fig. 2(ac). The nal values of structural parameters, agreement factors R.F and goodness of t (GoF) are listed in Table 1. The goodness of t for all samples was in between 1 and 1.5 indicating a reasonable tting. In general, the rened parameters were consistent with experimental data reported in the literature. Our results thus clearly established that the as synthesized nanoparticle belongs to the magnetite phase.

Summarry and Conclussion

The crystallographic structure and size of the crystallites was studied by X-ray diffraction and Rietveld renement. The effect of oleic acid as surfactant in a close to room temperature process have been investigated. The as grown nanoparticles were found to possess a preferential (311) orientation of the cubic phase. The X-ray diffraction and the Rietveld renement conrm the inverse spinel structure of cubic phase of magnetite.

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