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J Clust Sci (2012) 23:1003–1010

DOI 10.1007/s10876-012-0486-7

ORIGINAL PAPER

Synthesis and Characterization of Copper Ferrite
Nanocrystals via Coprecipitation

Masoud Salavati-Niasari • Tahmineh Mahmoudi •
Mohammad Sabet • S. Mostafa Hosseinpour-Mashkani •

Faezeh Soofivand • Farnosh Tavakoli

Received: 22 February 2012 / Published online: 10 May 2012
Ó Springer Science+Business Media, LLC 2012

Abstract Nanocrystalline CuFe2O4 powder was prepared by a coprecipitation
method from iron chloride and copper chloride in the presence of octanoic acid
(C8H16O2) as surfactant. The as-prepared samples were characterized by XRD,
TEM, SEM, FT-IR and VSM. SEM and TEM indicated that the particles were quasi
spherical with the particle sizes in the range of 23±7 nm. The magnetic properties
of the sample were measured by using a vibration sample magnetometer (VSM),
which showed that the sample exhibited a typical ferromagnetic behavior at room
temperature, while present finite coercivity of 245.5 Oe at 300 K.

Keywords Magnetic nanoparticles  Copper ferrite  Spinel  Chemical method 
Octanoic acid

Introduction

Spinel ferrites and their related structures have been investigated for nearly four
decades, due to their theoretical and technological relevance. A great number of
methods have been successfully employed to synthesize such materials with
improved properties for specific applications, such as magnetic powders for massive
storage devices [1] and gas-sensing applications.

M. Salavati-Niasari (&)  T. Mahmoudi  F. Soofivand  F. Tavakoli
Institute of Nano Science and Nano Technology, University of Kashan, Kashan,
P.O. Box 87317–51167, Islamic Republic of Iran
e-mail: salavati@kashanu.ac.ir

M. Sabet
Young Researchers Club, Kashan Branch, Islamic Azad University, Kashan, Iran

S. M. Hosseinpour-Mashkani
Center for Nanoscience and Technology, IST, Jawaharlal Nehru Technological University
Hyderabad, Hyderabad 500 085, Andhra Pradesh, India

123

Copper ferrite has been synthesized by the thermal decomposition of acetate precursors by Kheder and coworkers [5]. FeCl36H2O (Merck). and octanoic acid (C8H16O2) of HPLC grade as surfactant. CuCl22H2O (Merck). The TEM images were obtained on a Philips EM208 transmission electron microscope with an accelerating voltage of 100 kV. Experimental Section Materials The nanoparticles of copper ferrite were synthesized by chemical coprecipitation reaction using analytical grade iron chloride. Qi et al. using reverse micelle and hydrothermal methods [7]. Copper ferrite. Characterization Scanning electron microscopy (SEM) images were obtained on Philips XL-30E- SEM equipped with an energy dispersive X-ray spectroscopy. CuFe2O4. where d is the inversion parameter and d = 0 and 1 stand for the inverse and normal cases. The structural and magnetic properties of the materials were investigated through different techniques. Combustion synthesis is a method for the preparation of CuFe2O4 [4]. deionized water was used as a solvent. BHV-55. These sites have tetrahedral and octahedral oxygen coordination (A and B sites respectively). The magnetic measurement was carried out in a vibrating sample magnetometer (VSM. In this work. The nanocrystalline CuFe2O4 samples have been prepared by coprecipitating hydroxides of copper and iron from the respective metal nitrate solutions with ammonium hydroxide in a polymer matrix [8].1004 M. which plays a key role for the shape control of the particle. Riken. we present a study of CuFe2O4 nanocrystals obtained by coprecipitation from simple materials such as FeCl36H2O and CuCl22H2O. All the materials were reagent grade and used without further purification. 123 . Fourier transform infrared (FTIR) spectra were recorded on Shimadzu Varian 4300 spectrophotometer in KBr pellets. In addition. so the resulting local symmetries of the two sites are different. with Cu2? and Fe3? ions at two different crystallographic sites [2]. Manipulations and reactions were carried out in air without the protection of nitrogen or inert gas. reported the preparation of CuFe2O4 nanowalls using electrochemical methods [6] and Du et al. Tang and coworkers prepared CuFe2O4 particles with different shape via a one- step solution-phase route at the presence of ethylene glycol ligands. Double distilled. The cation distribution in this kind of structure may be represented by (CudFe1-d)A[Cu1-dFe1?d]BO4. Japan) at room temperature. copper chloride. reported the preparation of CuFe2O4 nanorods and nanodisks. can be described as a cubic close-packed arrangement of oxygen ions. Salavati-Niasari et al. CuFe2O4 nanoparticles have been prepared by coprecipitation method [9] mechanical milling sol–gel method. respectively [3].

FTIR and VSM techniques. 1 Hysteresis loops for CuFe2O4 (calcined at 600 °C) nanocrystals at room temperature at maximum applied field of 15 kOe 123 . The supernatant liquid was then decanted. To get free particles from Na? and Cl– compounds. 0. Results and Discussion The magnetic property of the CuFe2O4 nanoparticles (calcined at 600 °C for 4 h) has been investigated by magnetization hysteresis curve measurements at room temperature. TEM. which was then removed by heating at 600 °C for 4 h.Synthesis and Characterization of Copper Ferrite Nanocrystals 1005 Synthesis of CuFe2O4 Nanocrystals In a typically synthesized. the beaker contents were then centrifuged for 15 min at 3.4 M (25 mL) solution of FeCl36H2O and a 0. The acquired substance was then grinded into a fine powder. deionized water. Deionized distilled water was used as solvent in order to avoid the production of impurities in the final product.2 M (25 mL) of CuCl22H2O solutions were mixed in double distilled. and then centrifuged until only thick black precipitate remained. The reactants were constantly stirred using a magnetic stirrer until a pH level of 7–8 was reached. the precipitate was then washed twice with distilled water and then with ethanol to remove the excess surfactant from the solution. The final samples were characterized by XRD. Then the final products were obtained after being slowly cooled to room temperature. The liquid precipitate was then brought to a reaction temperature of 80 °C and stirred for 1 h. The obtained products were dried at 100 °C for 8 h.000 rpm.5 M (25 mL) solution of NaOH was prepared and slowly added to the salt solution dropwise. Figure 1 shows magnetization hysteresis curves measured at 300 K for 10 Relative magnetization (emu/g) 0 -10 -10000 -5000 0 5000 10000 Applied Field (Oe) Fig. The product was then cooled to room temperature. A specified amount of octanoic acid (C8H16O2) was added to the solution as a surfactant and coating material. To isolate the supernatant liquid. At this stage the product (CuFe2O4) contains some associated water (up to 10 wt%). The pH of the solution was constantly monitored as the NaOH solution was added. 1. SEM.

06–0545). The XRD patterns of the sample are shown in Fig.11–47.34–45. All of the main peaks are indexed as the CuFe2O4 in the standard data (JCPD No. With the increase of the calcining temperature. the precursor calcined at 400 °C already showed CuO phase (see Fig. JCPD No.4 380–830 [13] 123 . Figure 3 shows representative SEM image of the products.5 Oe and 7. the CuFe2O4. a second phase of CuO (2h& 36. The morphology of the products is examined by SEM and TEM. which is milder. Figure 5 shows the FTIR spectra of the CuFe2O4 nanocrystals. It is seen that coercive force Hc and remanent magnetization Ms at room temperature are 245. crystallinity increased and particles size also increased subsequently. 2d). m2.1006 M. 17. In addition.5°. Table 1 is shown a comparing the VSM data with other methods. 500. All of the main peaks are indexed as the CuO JCPDS No (41–0254). as common of all spinel compounds.56 [10] Electrospinning 17. Figure 4 shows TEM image of CuFe2O4 nanocrystals (with average size of 23±7 nm as estimated by Debye-Sherrers formula).8 [12] High-energy ball milling in an open container 31. K is the so-called shape factor.8–37. Calcination temperature plays a key role in the crystalline type and particle size of the copper ferrite.00 18.73–23.13–252. However. The spectra shows two main absorption bands m1. It can be seen that the coercivity of our product is higher than many of mentioned methods. and more environmental method than other methods. and 600 °C. and k is the wavelength of X-ray source used in XRD and were found to be 13. The average crystallite sizes of CuFe2O4 samples were calculated from Scherrer’s equation [15–23]: Kk Dc ¼ b cos h where b is the breadth of the observed diffraction line at its half-intensity maximum. in this work magnetic CuFe2O4 nanoparticles were synthesized via a coprecipitation method. We only changed the calcination temperature from 400 to 600 °C and the other preparation parameters did not change. more practical. which usually takes a value of about 0. 2c).98 299–625 [11] Mill scale fines via conventional oxide ceramic process.9. Calcination is a necessary step in the preparation of ferrite by chemical coprecipitation [14]. Though. Salavati-Niasari et al. 26. the powders calcined at 600 °C showed pure CuFe2O4 phase (Fig. a little CuO and Fe2O3 phase existed in powders calcined below 600 °C (see Fig. clearly showing that CuFe2O4 possesses a spherical structure.23 6. According to JCPDS (41–0254) values. The precursor showed that there was other oxide phase. 2. simpler. 20 nm for the samples of CuFe2O4 nanocrystals calcined at 400. in Table 1 Comparing the VSM data with other methods Method Ms(emu/g) Hc(Oe) Reference Self flash combustion of a homogeneous mixture 39. Figure 2 shows different XRD patterns for precursor calcined at different temperature. 2b).35 emu/g.85–85. Figure 2a shows the obtained product after precipitation. respectively. 41–0254) was also found in the calcined samples.

Synthesis and Characterization of Copper Ferrite Nanocrystals 1007 Fig. The ferrite can be considered as continuously bonded crystals. covalent or Vander Walls forces. The spectra indicate the presence of two absorption bands m1 at 123 . In ferrite the metal ions are situated in two different sub-lattices. to the nearest neighbors. via ionic. namely tetrahedral and octahedral according to the geometrical configuration of the oxygen nearest neighbors [4]. 2 XRD patterns of (a) precursor and copper ferrite nanocrystals calcined at (b) 400 °C (c) 500 °C and (d) 600 °C accordance to Waldron [16].

Fig. 4 TEM image of the CuFe2O4 nanocrystals prepared after calcinations at 600 °C 552. 123 .in the octahedral complexes. Salavati-Niasari et al. 3 SEM image of the CuFe2O4 nanocrystals Fig. is attributed to the stretching vibration of Fe3?–O2.in the tetrahedral complexes and the m2 band to that of Cu2? –O2.7 cm-1. m1. The positions of these bands confirm the existence of Cu2? ions entirely in the octahedral sites and the Fe3? ions in tetrahedral ones [14].1008 M.6 cm-1 and m2 at 472. The band.

Liu. B. Huang (2005). in E. D. and R. Compd. H. Pyrolysis 78. 2487. Bull. Compd. G. W. Copper ions located inter the grains and increase affect of grains from each other. Alloys. J. B. 4063. Nanosci. 41. Matter. Salavati-Niasari. Lu. C. 38. M. 13. Mater. Liu. J. Augustin. Z. 9. Bull. and F. L. Davar (2011). 3. 1. 2948. Z. 7. 14. Salavati-Niasari. 7. Chan (2005). Qi. 3097. Goya (1999). S. J. Cryst. 123 . Esmaeili. 12. Solids. and P. Res. M. Du.-Z. We find that for smaller crystals the saturation magnetization had a value that was significantly lower than the bulk value while the larger size crystals have values approaching those of the bulk. J. Stock Elements of X-ray Diffraction (Prentice-Hall. Li. Eng. F. and A. Q. Phys. Ghose (2006). Nanotechnol. J. 134. Mater. Wu. Compd. H. 61. Roy and J. R. 11. Chen. 465. 11. R. In addition. and A. Abdel-Khalek (2007). Z. J. J. In comparison with Fe3O4 this nanoparticles have low coercivity because of nonmagnetic Cu2? ion presence in lattice. P. O. A. L. E. Compd. References 1. Alloys. F. Lv. T. Salavati-Niasari. 13. and Y. 32. J. Chem. Wohlfarth (ed. Davar and M. J. 1982).-Z. 4. Luo. H. M. M. Nano- technology 16. and H. 40. 8. 509. 1727. J. Novak. X. J. Salavati-Niasari (2011). F. Condens. Seyghalkar. 6. Khansari (2011). D. Amsterdam. Waldron (1955). M. B. Ren. Hafner (1968). and N. L. Wang. Hosseinzadeh. 261.-K. Khedr. Zhang (2008). 5. Berchmans. Magn. J. Li. 1573. F. Englewood Cliffs. Coprecipitation is a suitable method for control of nanoparticle size with variation of reaction conditions. Y. 2001). Farghali. 99. 928. Alloys. Mir (2011). 1990. Anal. M. 10. Han. P. 307. 509. 509.). W. J. Rai (2007). A. S. 5 The FTIR spectra of CuFe2O4 nanocrystals prepared after calcinations at 600 °C Summary In summary. Krupicka and P. 2. Davar. A. Commun.-X. Davar. Evans and S.Synthesis and Characterization of Copper Ferrite Nanocrystals 1009 Fig. W. Alloys. Z. Y. Jiang and G. Saraswathi (2003). the magnetic hysteresis measured shows that the nanoparticles obtained display low ferromagnetic properties at room temperature. Banerjee and A. Selvan. 16. R. W. Cullity and S. Appl. Acknowledgments Authors are grateful to the council of Iran National Science Foundation and University of Kashan for their unending effort to provide financial support to undertake this work. J. 15. Magn. Tian. Phys. CuFe2O4 nanocrystals with a spinel structure with octanoic acid (C8H16O2) as surfactant were obtained. Ferromagnetic Materials (North-Holland. Phys. Mater. B. 29. Rev. Res. K.

507. Davar (2011). M. 22. and F. F. and F. Salavati-Niasari. Alloys. Saberyan (2011). Alloys. 23. 503. Compd. Chem. J. M. Salavati-Niasari. Amini Fazl (2010). 77. A. M. Mir. J. 278–285. 21. M. Salavati-Niasari. J. Chem. and F. N. A. Badiei. Bazarganipour. 779–789. J. Compd. Salavati-Niasari et al. Compd. 499.1010 M. Davar (2010). Sobhani. Salavati-Niasari. Alloys. Eng. Salavati-Niasari. 121. 500. Chem. G. and F. 170. J. 134. Eng. Javidi. and A. Davar (2011). and K. J. Mohandes. Hosseinzadeh. 123 . Esmaeili. M. 509. J. M. 18. Salavati-Niasari. E. 19. Salavati-Niasari. 651–658. Compd. Davar (2010). 173. J. F. M. Alloys. Eng. and F. M. Davar (2012). 181–182. Davar. 20. 17.