Synthesis and Characterization of MnFe2O4 Nanoparticles by Hydrothermal Method

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1 NANO VISION, Vol.5(4-6), , April-June 2015 (An International Research Journal of Nano Science & Technology), ISSN (Print) ISSN (Online) Synthesis and Characterization of MnFe2O4 Nanoparticles by Hydrothermal Method M. Gurumoorthy 1, K. Parasuraman 1, M. Anbarasu 2 and K. Balamurugan 3 1 Department of Physics, Poompuhar College, Melaiyur, Tamilnadu, INDIA. 2 Department of Physics, Annai College of Arts and Science, Kumbakonam, Tamilnadu, INDIA. 3 Department of Physics, Annamalai University, Annamalainagar, Tamilnadu, INDIA. parasu1959@gmail.com. Presented in Second National Conference on Thin Film Science and Nano Technology (SECOND-NCTFSANT-2015) March 2-3, 2015, Rajah Serfoji Govt. College, Thanjavur, T.N. (India). ABSTRACT MnFe 2 O 4 Crystalline oxide nanopowders were synthesized in nanoscale dimensions by a hydrothermal route, using Manganese Chloride, Ferrous Chloride and NH 4 solution (base). Structural characterization by X-ray diffraction (XRD) technique confirmed incorporation of Manganese in Fe 2 O 4 lattice. Scanning Electron Microscopy also reveals growth of large crystallites with 18 nm, and FT-IR shows the presence of functional groups and impurities in the sample. XRD measurements indicate that the obtained nanoparticles are single phase and the particle size increased by increasing the temperature. This spinal structure of prepared MnFe 2 O 4 nanoparticles were used for the memory storage device applications. Keywords: MnFe 2 O 4, nanoparticles, spinal cubic, hydrothermal. 1. INTRODUCTION Magnetic nanoparticles (MNPs) have attracted an enormous attention for their potential use in biomedical applications like controlled drug delivery, cell separation, magnetic resonance imaging and localized hyperthermia therapy of cancer etc 1-4. Iron oxide based magnetic nanoparticles are of particular significance because of their appropriate biocompatibility and lowtoxicity 5,6. Iron oxides are very common compounds and they are widespread in nature and readily synthesized in laboratory. In almost everywhere of the global system atmosphere, biosphere, hydrosphere, and lithosphere, iron oxides present 7. The future of the data storage industry will be worth of wondering by looking at the options available today and the evolution during the time. Due to the capacity, ultra- high density Nano Vision Vol. 5, Issue 4-6, April-June, 2015 Pages (39-168)

2 102 M. Gurumoorthy, et al., Nano Vision, Vol.5 (4-6), (2015) storage, durability over millions of read-write cycles, reliable performance under challenging environments and ever reducing cost to the user in terms of price per bit of stored data, magnetic data storage might eventually predominate over other competing media Manganese ferrite is exceptionally important member of ferrite family with a variety of applications in modern era of science and engineering. Like other ferrites, Manganese ferrite nano-particles have synthesized by various methods like ball milling, reverse micelle synthesis, thermal decomposition, sol-gel method, solid-phase reaction, pulsed laser deposition, and thermally activated solid-state reaction In the present work, ultra-fine, nano-sized, magnetic manganese ferrite powder has prepared by hydrothermal technique using metallic chlorides of Mn and Fe as precursors. One of our aims was to develop a general synthetic method and explore the structural properties of the MnFe 2 O 4 nanoparticles. 2. EXPERIMENTAL METHODS 2.1 Preparation of MnFe 2 O 4 nanoparticles MnFe 2 O 4 nanoparticles were synthesized by the hydrothermal method. All chemical reagents used as starting materials are of analytical grade and purchased without any further purification. In a typical synthesis process, 0.05M of ferrous Chloride (Fe 2 Cl 3 ) and 0.25M of Manganese Chloride (MnCl 2.4H 2 O) powders dissolved in 100 ml aqueous solution under vigorous stirring to form a clear solution, and then 15ml of ammonia (NH 4 ) added to the above solution. Vigorous stirring of the mixture kept at room temperature for 1hrand form a homogeneous solution. Finally, the mixture transferred into a 100 ml Teflon-lined autoclave, which heated at 180 o C for 16 h. After being cooled to room temperature, the black powders were collected and washed several times with distilled water and ethanol to remove the impurities, and finally dried at 80 o C in a vacuum oven for 8 hr Characterization Prepared MnFe 2 O 4 nanoparticles were characterized by various techniques. The structural characterization performed using a Philip X PERT-PRO diffractometer system. CuK α line with wavelength of Å generated with a setting of 30 mill amperes and 40 kv with the electrode used for diffraction with CuKα radiation. The infrared spectra of prepared sample recorded in the vibrational frequency ranging from 4000 to 400 cm -1 using a JASCO 460 plus FTIR spectrometer. Size and shape of the particles were determined using Scanning electron microscopy (SEM JSM-5610) analysis. 3. RESULTS AND DISCUSSION 3.1. X-ray diffraction analysis The XRD pattern of MnFe 2 O 4 nanoparticles prepared at room temperature is shown in Fig.1.The XRD data clearly confirms the crystalline phase of ferrite (MnFe 2 O 4 ) to be very close to the JCPDS No For the preparedmnfe 2 O 4 the most intensive lines (311)

3 M. Gurumoorthy, et al., Nano Vision, Vol.5 (4-6), (2015) 103 and (440) are observed the diffraction peak indicated at 2θ= and The XRD pattern shows the prepared nanoparticles are in a cubic structure of MnFe 2 O 4. It can be seen that, the sites and intensity of the diffraction peaks are consistent with the standard pattern for JCPDS Card No The sample show very broad peaks, indicating the ultra-fine nature and small crystallite size of the particles. Cubic single-phase nano sized MnFe 2 O 4 powder has been obtained. The observed peaks and structure are good agreement with the reported values of Hironori Iida et al., (2007). The crystallite size of the MnFe 2 O 4 product is determined by using Debye Scherrer s formula 20. D = k / β Cosθ Where, K=0.89 is the shape factor, λ is the X-ray wavelength of CuKα radiation, β is the full width at half maximum (FWHM) of the peaks and θ is the glancing angle and the average crystallite size is 18 nm for (311) plane. Fig.1: X-ray diffraction pattern of MnFe2O4 nanoparticles synthesized by hydrothermal method Fig. 2: Fourier Transform - Infrared (FTIR) spectrum of MnFe2O4 nanoparticles 3.2 Fourier Transform Infrared (FT-IR) spectral Analysis The vibrational frequencies of the various chemical bonds in the MnFe 2 O 4 nanoparticles can assigned from FT-IR spectra of which recorded in the region cm -1. The molecule could identify by the assignments of stretching and bending modes of vibrational frequencies that divided in three regions. In Fig.2 clearly shows an absorption

4 104 M. Gurumoorthy, et al., Nano Vision, Vol.5 (4-6), (2015) bands around cm 1, which are characteristic stretching vibration of hydroxyl functional group (H-O-H) on the surface of nanoparticles or adsorbed water in the sample. The absorption band at 1721 cm 1 corresponds to stretching vibration of carbonyl group (C-O). The stretching vibration of the carboxylate group (C=O) is observed around cm 1. The bending vibration of H-O-H group also localized at cm 1. The absorption band around cm 1 is assigned the stretching vibration of C-C-C group. The above observed FTIR spectra confirm the presence of organic impurities in the sample due to the preparation conditions. In addition, two absorption bands at 584 cm 1 and cm 1 are the vibrations of (Fe-O), which are indicative of formation of spinel ferrite structure. As can be seen from the spectra, the normal mode of vibration of tetrahedral cluster (584.05cm 1 ) is higher than that of octahedral cluster (442.03cm 1 ). 3.3 Surface morphology Analysis Fig.3 shows the SEM micrographs clearly show the surface features, by which it highlight that MnFe 2 O 4 nanoparticle was successfully prepared. It is cleared that the microstructure of the grains of the sample is ultra-small. Most of the grains containing a large number of atoms are very small in dimensions, having an average grain size of 19 nm. The nanoparticles were agglomerated from few µm to a few tens of µm. The prepared crystallites are nearly spherical in shape and uniform distribution. 4. CONCLUSION Fig. 3: SEM images of MnFe2O4 nanoparticles MnFe 2 O 4 nanoparticles with cubic structure have been successfully synthesized by hydrothermal method. The XRD data clearly confirm the polycrystalline nature and the cubic structure of MnFe 2 O 4 nanoparticles and the average particle size of the magnetite obtained from the peak broadening was 18 nm. FT-IR study also confirm the presence of functional groups in MnFe 2 O 4 nanoparticles and the bands can be observed at 584 and cm -1, which corresponds to MnFe 2 O 4, and due shoulders that can be assigned to

5 M. Gurumoorthy, et al., Nano Vision, Vol.5 (4-6), (2015) 105 maghemite. From the SEM results, the microstructure of the grains of the sample is ultrasmall. Most of the grains containing a large number of atoms are very small in dimensions, having an average grain size of 19nm. The size distribution is extraordinarily narrow. The nanoparticles were agglomerated from few µm to a few tens of µm. The agglomeration was reduced with increase in grain growth. ACKNOWLEDGMENT The Corresponding author Dr. K. Parasuraman, would like to express his thanks to the University Grants Commission, South Eastern Region (UGC-SERO), Hyderabad, India, for sanctioning the financial assistance [F. No.6304/15 Dated:] to carry out the present research work. REFERENCES 1. N. Ozer and F.Tepehan, Optical and electrochemical characteristics of sol-gel deposited iron oxide films. Solar Energy Materials and Solar Cells, 56: p (1999). 2. S. Mathur, et al., Phase selective Deposition and microstructure control in iron oxide films obtained by single-source CVD. Chemical Vapor Deposition, 8(6): p (2002). 3. Sousa MH, HasmonayE, DepeyrotJ, Tourinho FA, BacriJC, Dubois E et al. NiFe2O4 nanoparticles in ferrofluids: evidence of spin disorder in the surface layer. Journal of Magnetism and Magnetic Materials. 572: (2002). 4. Kamala BharathiK, MarkandeyuluG and Ramana CV. Structural, magnetic, electrical, and magnetoelectric properties of Sm- and Ho-substituted nickel ferrites. Journal of Physical Chemistry C., 115: (2011). 5. J.D. Desai, et al., Nanocrystalline hematite thin films by chemical solution spray. Semiconductor Science and Technology, 20: p (2005). 6. WangL and Gao L. Morphology transformation of hematite nanoparticles through oriented aggregation. Journal of the American Ceramic Society. 91: (2008). 7. W. Cai, J. Wan. J. Colloid Interface Sci. 305, (2007). 8. N. Agarwal, Characterization of Lithographically Patterned Magnetic Nanostructures, Arizona State University, USA, 2007.M.G. Naseri, E.B. Saion, H.A. Ahangar, M. Hashim, A.H. Shaari, Powder Technol. 212, 80e88 (2011). 9. Lin S, Shen C, Lu D, Wang C and Gao H J, Carbon (2013). 10. T. Prabhakaran, J. Hemalatha, J. Alloys Compd. 509, (2011). 11. Mahmoud MH,Williams CM, Cai J, Siu I, Walker JC. Investigation of Mn-ferrite films produced by pulsed laser deposition. J. Magn. Magn. Mater., 261(3): (2003). 12. Muroi M, Street R, McCormick PG, Amighian J. Magnetic properties of ultrafine MnFe2O4 powders prepared by mechanochemical processing. Physical Review B., 63 (18): (2001).

6 106 M. Gurumoorthy, et al., Nano Vision, Vol.5 (4-6), (2015) 13. Ding J, Street R, McCormick PG. Formation of spinel Mn-ferrite during mechanical alloying. J. Magn. Magn. Mater., 171(3): (1997). 14. Liu C, Zhang ZJ. Size-dependent superparamagnetic properties of Mn spinel ferrite nanoparticles synthesized from reverse micelles. Chem. Mater., 13(6): (2001). 15. Balaji G, Gajbhiye NS, Wilde G, Weissmuller J. Magnetic properties of MnFe2O4 nanoparticles. J. Magn. Magn. Mater., 617(20): (2002). 16. Nemoto N, Schleich DM, Zhang Y. Preparation of some metal ferrite MFe2O4 thin films through a nonaqueous sol method. Mater. Res. Bull., 30(4): (1995). 17. Deraz NM, El-Shobaky GA. Solid-solid interaction between ferric oxide and manganese carbonate as influenced by lithium oxide doping. Thermochimica Acta. 375: (2001). 18. Gajbhiye NS, Balaji G. Synthesis, reactivity, and cations inversion studies of nanocrystalline MnFe2O4 particles. Thermochimica Acta. 385(1-2): (2002). 19. Chen LY, Dai H, ShenYM and Bai JF. Size-controlled synthesis and magnetic properties of NiFe2O4 hollow nanospheres via a gel-assistant hydrothermal route Journal of Alloys and Compounds. 491: L33-L38 (2010). ttp://dx.doi.org/ /j.jallcom W.S. Chiu, S. Radiman, M.H. Abdullah, P.S. Khiew, N.M. Huang, R. Abd-Shukor. One pot synthesis of monodisperse Fe 3 O 4 nanocrystals by pyrolysis reaction of organometallic compound. Mater. Chem. Phys. 106, (2007).