Professional Documents
Culture Documents
a r t i c l e
i n f o
Article history:
Received 11 January 2013
Received in revised form 15 February 2013
Accepted 24 February 2013
Available online 16 March 2013
Keywords:
Oxide materials
Sol gel process
Spin orbit effect
Magnetically ordered materials
Mossbauer
TEM
a b s t r a c t
Superparamagnetic properties of the cobalt ferrite nanocrystals have been demonstrated. The signicance of the solgel autocombustion method in preparation of cobalt ferrite oxide in the nano range
(3040 nm) has been very well complimented with the structural, dimensional and morphological techniques, such as X-ray diffraction technique, Transmission Electron Microscopy and Scanning Electron
Microscopy. The valence states of the metal ions and single phase formation of the polycrystalline oxide
have been conrmed with the help of X-ray photoelectron spectroscopy and Raman spectroscopy. The
distribution of the Fe3+ ions in the tetrahedral and octahedral lattice sites has been illustrated with the
help of the Mssbauer spectroscopy that shows ve sextets, indicating occupancies of one tetrahedral
and four octahedral sites by Fe3+ ions. Hyperne elds of 51.29, 48.74, 46.78, 43.58 and 48.59 Tesla,
respectively in CoFe2O4 have been found for four octahedral and one tetrahedral site respectively, at
ambient temperature. The magnetic measurements MH and MT demonstrate a change in the magnetic
moment and a superparamagneticferrimagnetic transition at 235 K in the ferrite system.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Magnetic spinel ferrites are of great technological interest and
have grabbed the attention of many researchers due to their fascinating electromagnetic properties. The ease of preparation and the
stability of these materials under various conditions have added lot
of signicance for their use in the industry. The novelty observed in
the physico-chemical and the electromagnetic properties due to
changes in the particle dimension and composition has encouraged
researchers around the globe to synthesize these materials [17].
The exotic magnetic, electronic and magneto-optical properties
of the cobalt ferrite (CoFe2O4) have prioritized them in the manufacturing of magnetic recording devices, magnetic refrigeration,
catalysis, sensors and magnetic uids [8,9]. Magnetic nanocrystals
have been of great interest over the past several years for the fundamental understanding of nanomagnetism and for their technological and biomedical applications [812]. Single phase
magnetic ferrites and their nanocomposites nd tremendous application as antimicrobial agents and vehicle for drug delivery, thus
proving their vitality even in the non-technological eld, thereby
expanding their horizon of application [1315]. The magnetic
properties of nanocrystals vary greatly with changing dimensions
and superparamagnetism is a typical example of such a size-
Corresponding author. Tel.: +91 832 6519315; fax: +91 832 2452889.
E-mail addresses: sal_arun@rediffmail.com, sav@unigoa.ac.in (A.V. Salker).
0925-8388/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.02.163
S.R. Naik et al. / Journal of Alloys and Compounds 566 (2013) 5461
55
eter. Morphology analysis of the compound was carried out on JEOL JSM-6360 LV
Scanning Electron Microscope (SEM). Transmission Electron Microscopy (TEM)
images were recorded on PHILIPS CM 200 Transmission Electron Microscope operating at an accelerating voltage of 200 kV and providing a resolution of 2.4 . Particle size distribution study of the as prepared nanoparticles was carried out by
employing a DELSA NANO S, BECKMAN COULTER, USA. The valence state and binding energies of various chemical species were determined by the X-ray photoelectron spectroscopy (XPS) employing VSW SCIENTIFIC INSTRUMENT with Al Ka as the
incident source having energy of 1486.6 eV with a resolution of 0.9 eV. The vaccum
maintained in the sample analyzer chamber was 1.4 108 Torr. 57Fe Mssbauer
measurements were performed in transmission mode with a 57Co radioactive
source in constant acceleration (triangular wave) mode using a standard PC based
Mssbauer spectrometer (Nucleonix Systems Pvt. Ltd., Hyderabad, India). Velocity
calibration of the spectrometer was done with an enriched a-57Fe metal foil absorber at room temperature and the isomer shift values were given relative to Fe foil.
The outer line width of calibration spectrum was 0.29 mm s1. The recorded
Mssbauer spectrum was tted by using the WinNormos t programme. A QUANTUM DESIGN PPMS-VSM magnetometer was used for magnetic characterization of
the pelletized compounds. The variation of the DC-susceptibility of each sample
with temperature was measured from 5 K to 300 K in the ZFC (zero eld cooling)
and FC (eld cooling) modes using a magnetic eld of 10 KOe. The magnetization
with varying magnetic eld of up to 50 KOe was also measured at 5 K and 300 K.
56
S.R. Naik et al. / Journal of Alloys and Compounds 566 (2013) 5461
Fig. 1. (a) X-ray diffraction pattern of cobalt ferrite nanoparticles sintered at 600 C for 6 h, and (b) WilliamsonHall plot of cobalt ferrite.
Fig. 3. Images depicting TEM (a) and (b), and electron diffraction pattern (c) of cobalt ferrite.
S.R. Naik et al. / Journal of Alloys and Compounds 566 (2013) 5461
57
Fig. 4. Graphs representing (a) comparison of the Raman and IR spectra for cobalt ferrite along with the deconvoluted patterns (b), (c) and (d).
at 617 cm1 are the symmetry vibrations of the metal in the tetrahedral site. A peak is observed in the region of 658 cm1 which can
be attributed to cobalt ions residing at defect sites that are probably located near the surface of the nanoparticles [20]. This peak is
pronounced due to the higher surface-to-volume ratio of the nanoparticles in this sample. Fe2O3 is the most common impurity phase
formed during the synthesis of spinel ferrites. It gives two sharp
signals at 240 cm1 and 300 cm1 with high intensity. The
240 cm1 peak is absent in the spectrum and a protrusion is observed at 308 cm1. This is comparatively weaker in intensity
and can therefore be said as the property of CoFe2O4 and not
Fe2O3 [22]. All together there are two different lattices in the spinel
ferrite structure, and an attempt is made over here to assign the
modes for the various signals observed in the spectrum based on
the idea obtained from the literature.
The difference between Raman and IR vibrational modes for
CoFe2O4 in the range 2751000 cm1 is displayed in Fig. 4a. There
are four different modes (m1, m2, m3 and m4) assigned for the tetrahedral lattice. All the four modes are Raman active while only 2 (m3
and m4) are IR active. From the gure, IR stretching modes are evident for the compound at 400 cm1 and 574 cm1, which are the
FeO symmetric and asymmetric stretching vibrations, along with
2 other signals at 279 cm1 and 302 cm1. On the contrary the signal evident at 393 cm1 which is highly intense in the IR region is
absent in the Raman spectrum proving it to be either a m3 or a m4
mode which are strong IR active modes and are weakly observed
in the Raman spectrum. A weakly intense signal in the Raman
spectrum is observed at 574 cm1 (asymmetric FeO stretching)
indicating that m3 and m4 must be strong IR active modes only.
58
S.R. Naik et al. / Journal of Alloys and Compounds 566 (2013) 5461
Fig. 5. Deconvulated XPS spectra showing (a) full scan (b) Fe 2p (c) Co 2p and (d) O 1s of cobalt ferrite.
S.R. Naik et al. / Journal of Alloys and Compounds 566 (2013) 5461
59
Table 1
Mssbauer tting parameters of CoFe2O4 obtained using Win NORMOS tting
programme. Isomer shift (d), quadrupole splitting (D), line width (C), hyperne
magnetic eld (Hhf) and relative areas (RA) are shown in the table. All the results are
relative to Fe metal foil.
Fe sites
Sextet
Sextet
Sextet
Sextet
Sextet
1
2
3
4
5
(tet)
(oct)
(oct)
(oct)
(oct)
d (mm s1)
D (mm s1)
C (mm s1)
Hhf (T)
RA (%)
0.206
0.377
0.331
0.349
0.346
0.019
0.010
0.071
0.061
0.006
0.232
0.391
0.148
0.394
0.192
48.59
51.29
46.78
43.58
48.74
22.63
23.17
12.53
13.54
28.13
Isomer shift values are in the range of 0.900.95 mm s1 for tetrahedral and 1.051.10 mm s1 for octahedral site, respectively for
Fe2+ ions [3234]. So the hyperne structure does not evidence
of the presence of Fe2+ ions. The quadrupole splitting (D) values
are found to be low indicating the overall presence of cubic symmetry at both the sites. The magnetic hyperne eld results conrm the distribution of the Mssbauer nuclei in all the ve
sublattices (four octahedral and one tetrahedral) of the compound.
The magnetic hyperne elds for a tetrahedral and four octahedral
sublattices are 48.59, 51.29, 48.74, 46.78, and 43.58 Tesla respectively. The A and B sites were assigned to the sextets based on isomer shift and the magnetic hyperne eld values as reported
[31,35,36]. Since the bond separation between Fe3+O2 is larger
for octahedral ions as compared to that of the tetrahedral ions,
smaller overlapping of the orbitals of Fe3+ ions and oxygen anions
(low s electron density compared to tetrahedral site) and the smaller covalency lead to larger isomer shift at the octahedral site. So
the sextet with a lower isomer shift corresponds to the tetrahedral
site, and the sextet having a higher isomer shift represents the
octahedral sites [35]. The percent distribution of the Fe3+ in the tetrahedral and the octahedral sublattices is calculated from the relative areas of the hyperne sextets. The results display the
distribution to be 22.6% (tetrahedral site) and 77.4% (octahedral
site), respectively showing the degree of inversion to be 0.45 with
the formula (Fe0.45Co0.55)[Co0.45Fe1.55]O4. This proves the possibility of the cation exchange taking place in the nanocrystalline
CoFe2O4 reported herein (CoFe2O4 is an inverse spinel in bulk
form).
Fig. 7. Variation of magnetization with eld cooling (FC) and zero eld cooling
(ZFC) from 5 to 300 K. A magnetic eld of 10 kOe is maintained for the FC
measurement.
60
S.R. Naik et al. / Journal of Alloys and Compounds 566 (2013) 5461
4. Conclusion
Fig. 8. Graphs depicting the variation in the magnetic properties of the cobalt
ferrite nanoparticles at 5 K and 300 K in the magnetic eld of 50 kOe.
the central cation and the cations outside the nearest neighborhood of the central ion. A Co2+ cation with 3d7 electronic conguration at B site in CoFe2O4 has a triplet 4T1g ground state. Even
though the trigonal eld is introduced with the T1g ground state
further splitting into A2 and E states, the Co2+ cation with a degenerated ground state of E is still considered to have a strong LS coupling, and therefore contributes greatly to the magnetic anisotropy
of CoFe2O4 [13]. The strong LS couplings at Co2+ lattice sites generate a large anisotropy constant K and results in much higher
anisotropy energy barrier in CoFe2O4 nanocrystals. Hence, we observe higher blocking temperature for CoFe2O4 nanocrystals.
The coercivity of magnetic nanocrystals is surely related to the
magnetic anisotropy. At a given temperature, the required magnetic eld strength for overcoming anisotropy to ip the magnetic
spin increases with increasing anisotropy energy barrier. Strong L
S couplings in Co2+ cations result in much higher coercivity in
CoFe2O4. The coercivity of nanocrystals also has a contribution
from the surface anisotropy of nanocrystals. Since the compound
under study consist of the particles of varying sizes, it is very difcult to gauge the inuence of the particle size on the resultant
coercivity.
The display of superparamagnetic properties by CoFe2O4 nanocrystals facilitates the fundamental understanding of magnetism at
the nanometer scale. The studies conrm that CoFe2O4 is a better
magnetic material than magnetite. The presence of Co2+ ions in
the octahedral lattice and the contribution of LS coupling towards
the resultant magnetic properties are signicantly higher. The LS
contribution of Fe2+ ions in magnetite is lower than Co2+ in CoFe2O4
and therefore CoFe2O4 nanocrystals clearly display better magnetic
characteristics than Fe3O4 nanocrystals. Clearly, the CoFe2O4 nanoparticles are good candidates for technological applications in
terms of magnetic characteristics.
Fig. 8 represents the dependence of magnetization of CoFe2O4
nanoparticles on magnetic eld at 300 K and 5 K. At 300 K these
nanoparticles exhibit hysteresis loops with coercivity, remanance
and a saturation magnetization of 1326 Oe, 33 emu g1 and
74 emu g1 respectively. At 5 K the saturation magnetization value
increases to 80 emu g1. This increase in the values may be because of the proper ordering of the magnetic moments along the
direction of the eld, which in turn are randomized at elevated
temperatures (at 300 K) due to the thermal vibrations. The coercivity and remanance are found to be 13939 Oe and 68 emu g1
respectively. The squareness ratio (Mr/Ms) is found to increase from
0.44 (300 K) to 0.86 (5 K).
Preparation of the CoFe2O4 nanocrystalline compound was carried out successfully by the solgel autocombustion method. The
structural characterization like XRD proved the monophasic formation and conrmed the nanocrystalline nature of the particles.
Partial migration of the cobalt ions was suspected from the microdistortion calculated using the WilliamsonHall plots. This was
conrmed from the Mssbauer spectrum which showed the degree
of inversion to be 0.45 and the values for isomer shift veried the
existence of iron in the Fe3+ high spin state. XPS conrmed the
presence of the metal ions in the required valence state, which enhanced the overall magnetic moment. Raman spectroscopy effectively demonstrated the formation of the spinel phase only
thereby eliminating the probability of the formation of non-magnetic a-Fe2O3 phase. The LS contribution from Co2+ ions in
enhancing the magnetic properties was effectively demonstrated.
A large variation in the magnetic properties was observed with
varying eld and temperature. An increase in the value of saturation magnetization was observed at 5 K as compared to 300 K, signifying a decrease in the randomization of the magnetic moments
by the thermal vibrations. The acquisition of lattices by the metal
ions due to a probable migration was effectively proved by the
Mssbauer spectroscopy which conrmed the formation of the
random cobalt ferrite, thereby supporting the explanation provided for the magnetic properties exhibited by the material under
study.
Acknowledgement
S.R. Naik and A.V. Salker would like to acknowledge Dr. A.
Banerjee, Dr. V. Sathe, Dr. T. Shripathi and Dr. S. Tripathi (UGCDAE Consortium for Scientic Research, Indore, India) for providing
VSM, Raman and XPS facility. Dr. Rahul Mohan and Ms. Sahina Gazi
(NCAOR, Goa, India) are acknowledged for providing SEM facility.
References
[1] Q. Song, Z.J. Zhang, J. Am. Chem. Soc. 126 (2004) 6164.
[2] L.D. Tung, V. Kolesnichenko, D. Caruntu, N.H. Chou, C.J. OConnor, L. Spinu, J.
Appl. Phys. 93 (2003) 7486.
[3] T. Hyeon, Y. Chung, J. Park, S.S. Lee, Y.-W. Kim, B.H. Park, J. Phys. Chem. B. 106
(2002) 6831.
[4] R.S. Devan, Y.D. Kolekar, B.K. Chougule, J. Phys. Condens. Matter 18 (2006)
9809.
[5] N. Sivakumar, A. Narayanasamy, K. Shinoda, C.N. Chinnasamy, B. Jeyadevan, J.M. Greneche, J. Appl. Phys. 102 (2007) 0139161.
[6] B.X. Gu, Appl. Phys. Lett. 82 (2003) 3708.
[7] F. Cheng, C. Liao, J. Kuang, Z. Xu, C. Yan, L. Chen, H. Zhao, Z. Liu, J. Appl. Phys. 85
(1999) 2782.
[8] M.A.G. Soler, E.C.D. Lima, S.W. da Silva, T.F.O. Melo, A.C.M. Pimenta, J.P.
Sinnecker, R.B. Azevedo, V.K. Garg, A.C. Oliveira, M.A. Novak, P.C. Morais,
Langmuir 23 (2007) 9611.
[9] N. Moumen, M.P. Pileni, Chem. Mater. 8 (1996) 1128.
[10] E. Manova, B. Kunev, D. Paneva, I. Mitov, L. Petrov, C. Estourns, C. DOrlans, J.L. Rehspringer, M. Kurmoo, Chem. Mater. 16 (2004) 5689.
[11] S. Ammar, A. Helfen, N. Jouini, F. Fivet, I. Rosenman, F. Villain, P. Molini, M.
Danot, J. Mater. Chem. 11 (2001) 186.
[12] E.V. Groman, J.C. Bouchard, C.P. Reinhardt, D.E. Vaccaro, Bioconjugate Chem.
18 (2007) 1763.
[13] S. Rana, J. Rawat, M. Sorensson, R.D.K. Misra, Acta Biomater. 2 (2006) 421.
[14] S. Rana, A. Gallo, R.S. Shrivastava, R.D.K. Misra, Acta Biomater. 3 (2007) 233.
[15] J. Rawat, S. Rana, M.M. Sorensson, R.D.K. Misra, Mater. Sci. Technol. 23 (2007)
97.
[16] S.R. Naik, A.V. Salker, J. Mater. Chem. 22 (2012) 2740.
[17] S.R. Naik, A.V. Salker, Phys. Chem. Chem. Phys. 14 (2012) 10032.
[18] G. Ji, S. Tang, B. Xu, B. Gu, Y. Du, Chem. Phys. Lett. 379 (2003) 484.
[19] P. Vaqueiro, M.A. Lpez-Quintela, Chem. Mater. 9 (1997) 2836.
[20] G. Shemer, E. Tirosh, T. Livneh, G. Markovich, J. Phys. Chem. C 111 (2007)
14334.
[21] M.A.G. Solera, T.F.O. Melo, S.W. da Silva, E.C.D. Lima, A.C.M. Pimenta, V.K. Garg,
A.C. Oliveira, P.C. Morais, J. Magn. Magn. Mater. 272276 (2006) 2357.
[22] L.B. Tahar, L.S. Smiri, M. Artus, A.-L. Joudrier, F. Herbst, M.J. Vaulay, S. Ammar,
F. Fivet, Mater. Res. Bull. 42 (2007) 1888.
S.R. Naik et al. / Journal of Alloys and Compounds 566 (2013) 5461
[23] S. Liang, F. Teng, G. Bulgan, R. Zong, Y. Zhu, J. Phys. Chem. C 112 (2008)
5307.
[24] M. Liu, G.J. Zhang, Z.R. Shen, P.C. Sun, D.T. Ding, T.H. Chen, Solid State Sci. 11
(2009) 118.
[25] G.B. Ji, S.L. Tang, S.K. Ren, F.M. Zhang, B.X. Gu, Y.W. Du, J. Cryst. Growth 270
(2004) 156.
[26] H.S.T.C. ONeil, A. Navrotsky, Am. Mineral. 68 (1983) 181.
[27] J.K. Burdett, G.D. Price, S.L. Price, J. Am. Chem. Soc. 104 (1982) 92.
[28] C. Liu, B. Zou, A.J. Rondinone, Z.J. Zhang, J. Am. Chem. Soc. 122 (2000) 6263.
[29] N. Moumen, P. Bonville, M.P. Pileni, J. Phys. Chem. 100 (1996) 14410.
[30] C.R. Vestal, Z.J. Zhang, Nano Lett. 3 (2003) 1739.
61
[31] A.M. Banerjee, M.R. Pai, S.S. Meena, A.K. Tripathi, S.R. Bharadwaj, Int. J.
Hydrogen Energy 36 (2011) 4768.
[32] K. Sharma, S.S. Meena, S. Saxena, S.M. Yusuf, A. Srinivasan, G.P. Kothiyal, Mater.
Chem. Phys. 133 (2012) 144.
[33] K. Sharma, S.S. Meena, C.L. Prajapat, S. Bhattacharya, Jagannath, M.R. Singh,
S.M. Yusuf, G.P. Kothiyal, J. Magn. Magn. Mater. 321 (2009) 3821.
[34] K. Sharma, A. Dixit, S.S. Meena, Jagannath, S. Bhattacharya, C.L. Prajapat, P.K.
Sharma, S.M. Yusuf, A.K. Tyagi, G.P. Kothiyal, Mater. Sci. Eng. C 29 (2009) 2226.
[35] S.S. Shinde, S.S. Meena, S.M. Yusuf, K.Y. Rajpure, J. Phys. Chem. C 115 (2011)
3731.
[36] D.H. Lee, H.S. Kim, C.H. Yo, K. Ahn, K.H. Kim, Mater. Chem. Phys. 57 (1998) 169.