Synthesis and Characterization of Iron Oxide Nanoparticles by ...

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INTRODUCTION. Iron oxide nanoparticles have been widely studied in recent years due to their magnetic, optical and cat alytic properties and applications in ...
ISSN 20702051, Protection of Metals and Physical Chemistry of Surfaces, 2014, Vol. 50, No. 5 pp. 628–631. © Pleiades Publishing, Ltd., 2014.

NANOSCALE AND NANOSTRUCTURED MATERIALS AND COATINGS

Synthesis and Characterization of Iron Oxide Nanoparticles by Solvothermal Method1 Deepti Mishra, Ruma Arora, Swati Lahiri, Sudhir Sitaram Amritphale, and Navin Chandra Council of Scientific and Industrial Research Advanced Materials and Processes Research Institute, Hoshangabad Road, Bhopal (M.P.) 462 064, India email: [email protected] Received August 23, 2013

Abstract—In the present work iron oxide nanoparticles have been synthesized by alkaline solvo thermal method using anhydrous ferric chloride, sodium hydroxide, polyethylene glycol and cetyl trimethyl ammo nium bromide and characterized by Xray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Field Emission Scanning Electron Microscopy (FESEM), Energydispersive Xray Spectroscopy (EDX) and Thermal Gravimetric Analysis (TGA). XRD indicated that the product is a mixture of different phases of iron oxide viz. gammaFe2O3 (maghemite, tetragonal), Fe2O3 (maghemite, cubic), Fe3O4 (magne tite, cubic) and εFe2O3(epsilon iron oxide). FESEM studies indicated that size of the particles is observed in the range of about 19.8 nm to 48 nm. EDX spectral analysis reveals the presence of carbon, oxygen, iron in the synthesized nanoparticles. The FTIR spectra indicated absorption bands due to O–H stretching, C–O bending, N–H stretching and bending, C–H stretching and Fe–O stretching vibrations. TGA curve repre sented weight loss of around 3.0446 % in the sample at temperature of about 180°C due to the elimination of the water molecules absorbed by the nanoparticles from the atmosphere. DOI: 10.1134/S2070205114050128 1

1. INTRODUCTION

Iron oxide nanoparticles have been widely studied in recent years due to their magnetic, optical and cat alytic properties and applications in diverse areas such as magnetic resonance imaging [1], drug delivery [2], ferrofluids [3], catalysis[4] and magnetic nanodevices [5]. Many techniques have been developed for their synthesis including coprecipitation, solgel method, microemulsion technique and hydrothermal tech nique [6]. Their characteristics depend significantly on particle size and shape. However, the control of size is very important as it plays a major role in determining their properties. In the present work iron oxide nano particles have been synthesized by alkaline solvo ther mal method using anhydrous ferric chloride, sodium hydroxide, polyethylene glycol and cetyl trimethyl ammonium bromide as surfactant and characterized by Xray diffraction (XRD), Fourier Transform Infra red Spectroscopy (FTIR), Field Emission Scanning Electron Microscopy (FESEM), Energydispersive Xray Spectroscopy (EDX) and Thermal Gravimetric Analysis (TGA). 1 The article is published in the original.

2. EXPERIMENTAL Anhydrous ferric chloride, sodium hydroxide and cetyl trimethyl ammonium bromide (CTAB) (all of analytical grade) were procured from Rankem, poly ethylene glycol was procured from Merck and used as such without further purification. For synthesis of iron oxide nano particles, an aqueous solution of anhydrous ferric chloride (25 g in 250 mL water), polyethylene glycol (62.5 g), sodium hydroxide (1.5 M in 250 mL water) and CTAB (2.5 g in 10 mL water) were mixed together and refluxed at tempera ture around 198 to 200°C for a period of around 8 h. After reflux, the system was allowed to cool at ambient temperature. The product in the form of reddish coloured gel was collected at the bottom of flask. It was washed extensively with double distilled water and finally with acetone and dried at room temperature. Xray diffraction pattern was obtained using CuKα radiation on D8 advance Xray diffractometer. The Xray diffraction intensity was recorded as a function of Bragg’s 2θ in the angular range of 5°–70°. IR spec tra was recorded between 500–4000 cm–1 using Bruker alpha Fourier Transform Infra Red Spectrom eter. FESEM images and EDX spectra were taken on Field Emission Scanning Electron Microscope (FESEM), model NOVA NANOSEM430 of COM

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SYNTHESIS AND CHARACTERIZATION OF IRON OXIDE NANOPARTICLES

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Fig. 1. XRD pattern of synthesized iron oxide nano particles.

FEI and Energydispersive Xray spectroscopy (EDX), Model XMAX of Oxford. Thermal Gravi metric Analysis (TGA) was performed by heating sample at a heating rate of 10°C from 30°C to 800°C on Tolendo TGA/DSC1 of Mettler company. 3. RESULTS AND DISCUSSION Xray diffraction pattern of synthesized nanoparti cles is shown in Fig. 1. The pattern showed diffraction peaks at 3.664, 3.221, 2.992, 2.724, 2.691, 2.510, 2.383, 2.201, 2.083, 1.838, 1.692, 1.484, 1.451, 1.311, 1.257, 1.226, 1.212 which can be indexed to the mix ture of iron oxides viz. gammaFe2O3 (maghemite, tetragonal), Fe2O3 (maghemite,cubic), Fe3O4 (mag netite, cubic) and εFe2O3(epsilon iron oxide) when

23 .7 nm

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compared with JCPDS data [File Number 251402, 2481, 19629, 16895] [7]. No other phase due to impurity was detected in the sample. FESEM image of synthesized nanoparticles is shown in Fig. 2 and EDX spectra is shown in Fig. 3. Several particles were investigated to determine parti cle size. It can be seen that sample consist of the parti cles which are well dispersed and almost spherical in shape. The size of the particles varies in the range of about 19.8 nm to 48 nm. EDX spectral analysis reveals (а) Spectrum 1

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Fig. 3. EDX spectra of synthesized iron oxide nano parti cles. (a) Selected area, (b) EDX outcomes.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 50 No. 5 2014

TGA curve of iron oxide nano particles is shown in Fig. 5. The TGA curve represented weight loss of around 3.0446 % in the sample at temperature of about 180°C. This weight loss can be due to the elimi nation of the water molecules absorbed by the nano particles from the atmosphere after that sample weight is almost constant [13] which indicates the thermal stability of the sample. 602.26

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Fig. 4. FTIR spectra of synthesized iron oxide nano particles.

the presence of carbon, oxygen and iron in synthesized nanoparticles. The appearance of peak of carbon in EDX spectra is due to presence of organic linkages of ethylene glycol and CTAB. The FTIR spectrum of synthesised nanoparticles shown in Fig. 4 indicated presence of absoption bands at 3354, 2359, 1621, 1033, 920 and 602 cm–1. These observed bands may be due to O–H stretching (3354 cm–1), C–O bending (2359 cm–1), N–H stretching and bending (1621 cm–1), C–H stretch ing (1033 cm–1), vibrations [8, 9] and vibrations of Fe– O bond (602 cm–1) which is in agreement with the lit erature values [10, 11]. The absorption band at 3354 cm–1 appeared due to absorption of moisture by nanoparticles from the envi ronment [12]. This was further supported by the weight loss observed in thermogravimetric analysis.

Iron oxide nano particle were synthesized successfully by a alkaline solvo thermal technique and characterised using various sophisticated complementary techniques. XRD studies confirmed that the product is a mixture of different phases of iron oxide viz. gammaFe2O3 (maghemite, tetragonal), Fe2O3 (maghemite,cubic), Fe3O4 (magnetite, cubic) and εFe2O3(epsilon iron oxide). FESEM studies indicated that size of the particles is in the range of about 19.8 nm to 48 nm. EDX spectral analysis reveals the presence of carbon, oxygen, iron in the synthesized nanoparticles. Further studies on tailor ing of shape and size of nanoparticles for application in radiation shielding are under way. 5. ACKNOWLEDGMENTS Authors are grateful to Director CSIRAMPRI Bhopal for providing necessary institutional facilities and encouragement. We acknowledge thanks to Mr. Anup Khare and Mr. Mohd. Shafique, CSIRAMPRI, Bho pal (M.P.) India for analysis of samples on FESEM and EDX and providing data of thermal analysis and

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Fig. 5. TGA curve of synthesized iron oxide nano particles. PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 50 No. 5 2014

SYNTHESIS AND CHARACTERIZATION OF IRON OXIDE NANOPARTICLES

Xray diffraction pattern of sample. Thanks are also due to Dr. Neelesh Jain, SIRT, Bhopal (M.P.) India for providing IR spectra of sample. 6. REFERENCES 1. Toyota, T., Ohguri, N., Maruyama, K., et al., Anal. Chem., 2012, vol. 84, p. 3952. 2. Chen, Y. and Chen, B.A., Chin J. Cancer., 2010, vol. 29, p. 125. 3. Behdadfar, B., Kermanpur, A., SadeghiAliabadi, H., et al., Solid State Chem., 2012, vol. 187, p. 20. 4. Park, J.Y., Lee, Y.J., Khanna, P.K., et al., J. Molecular Catalysis A, 2010, vol. 323, p. 84. 5. Freund, B., Tromsdorf, U., Bruns, O., et al., ACS Nano, 2012, vol. 6, p. 7318. 6. Kulkarni, L., Group seminars “Synthesis and Character ization of Nanoparticles,” September, 2009.

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7. Powder Diffraction File, Alphabetical Index Inorganic Phases, Pennsylvania: JCPDS Int. Centre For Diffrac tion Data, 1984. 8. Coates, J., Interpretation of Infrared Spectra, A Practical Approach, Encyclopedia of Analytical Chemistry, Mey ers, A., Ed., Chichester: John Wiley & Sons Ltd, 2000, p. 10815. 9. Farmer, V.C., The Infrared Spectra of Minerals, Lon don: Mineralogical Soc., 1974, p. 539. 10. Basavaraja, S., Balaji, D.S., Bedre, M.D., et al., Bull. Mater. Sci., 2011, vol.34, p. 1313. 11. Gadsden, J.A., Infrared Spectra of Minerals and Related Inorganic Compounds, England: Butterworths Publ., 1975. 12. Rahman, M.M., Khan, S.B, Jamal, A., et al., Iron Oxide Nanoparticles, ISBN: 9789533079134, 2011, p. 43, Intech Open access publisher. 13. Li, G.S. and Smith, R.L., Mater. Res. Bull., 2002, vol. 37, p. 949.

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