See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/238962536

Effect of annealing temperature on the

magnetic properties of CoFe2O4nanoparticles
Article in Philosophical Magazine Letters April 2010
DOI: 10.1080/09500831003630732

CITATIONS

READS

12

1 author:
Samaa El-Dek
Beni Suef University
42 PUBLICATIONS 365 CITATIONS
SEE PROFILE

All in-text references underlined in blue are linked to publications on ResearchGate,

letting you access and read them immediately.

Available from: Samaa El-Dek

Retrieved on: 29 August 2016

This article was downloaded by: [Egypt Consortium - EUN - Trial Account]
On: 18 April 2010
Access details: Access Details: [subscription number 916564154]
Publisher Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 3741 Mortimer Street, London W1T 3JH, UK

Philosophical Magazine Letters

Publication details, including instructions for authors and subscription information:

http://www.informaworld.com/smpp/title~content=t713695410

Effect of annealing temperature on the magnetic properties of CoFe2O4

nanoparticles

S. I. El-Dek a
a
Materials Science Laboratory (1), Physics Department, Faculty of Science, Cairo University, Giza,
Egypt
First published on: 12 March 2010

To cite this Article El-Dek, S. I.(2010) 'Effect of annealing temperature on the magnetic properties of CoFe2O4

nanoparticles', Philosophical Magazine Letters, 90: 4, 233 240, First published on: 12 March 2010 (iFirst)
To link to this Article: DOI: 10.1080/09500831003630732
URL: http://dx.doi.org/10.1080/09500831003630732

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.informaworld.com/terms-and-conditions-of-access.pdf
This article may be used for research, teaching and private study purposes. Any substantial or
systematic reproduction, re-distribution, re-selling, loan or sub-licensing, systematic supply or
distribution in any form to anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation that the contents
will be complete or accurate or up to date. The accuracy of any instructions, formulae and drug doses
should be independently verified with primary sources. The publisher shall not be liable for any loss,
actions, claims, proceedings, demand or costs or damages whatsoever or howsoever caused arising directly
or indirectly in connection with or arising out of the use of this material.

Philosophical Magazine Letters

Vol. 90, No. 4, April 2010, 233240

Effect of annealing temperature on the magnetic properties

of CoFe2O4 nanoparticles
S.I. El-Dek*

Downloaded By: [Egypt Consortium - EUN - Trial Account] At: 15:43 18 April 2010

Materials Science Laboratory (1), Physics Department, Faculty of Science,

Cairo University, Giza, Egypt
(Received 28 February 2009; final version received 12 January 2010)
Nanocrystalline CoFe2O4 samples were prepared using the flash technique
and annealed at different temperatures. X-ray diffraction results indicate a
single-phase spinel structure. The saturation and remanent magnetization
of the samples have been determined as a function of the crystallite size. An
exponential decay of the coercive field with crystallite size is observed.
After annealing, one of the samples at 950 C, 40 nm particles were obtained
with a saturation magnetization of 64.36 emu/g, a coercivity of 396 Oe and
the highest density among all the samples.
Keywords: nanostructures; magnetically ordered materials; CoFe2O4; flash
method; saturation magnetization; coercivity

1. Introduction
Magnetic nanoparticles [1] of spinel ferrites are of great interest in fundamental
science, especially for addressing the fundamental relationships between magnetic
properties, and their crystal chemistry and structure. The synthesis and magnetic
structure characterization of spinel metastable nanoferrites have been investigated
intensely [24]. Cobalt ferrite, with a partially inverse spinel structure, is one of the
most important and most abundant magnetic materials. As a conventional magnetic
material, with a Curie temperature TC of about 793 K, CoFe2O4 is well known to
have large magnetic anisotropy, moderate saturation magnetization, remarkable
chemical stability, and a mechanical hardness, which make it a good candidate for
use as a recording media. Recent studies report on the utilization of CoFe2O4
nanocrystals in various applications, such as lithium ion batteries [5], magnetic
catalysis [6], sensors and actuators [7,8], hyperthermia treatment [9], and antitumor
applications [10].
Caltun et al. [11] found that for stoichiometric CoFe2O4 samples prepared using
the standard ceramic method, the density of the samples as well as their saturation
magnetization increase with the sintering temperature, while the remanence
magnetization and the coercive field show a slight decrease. Another series of
cobalt ferrite CoFe2O4 nanopowders was prepared using the citrate autocombustion
method by Xiao et al. [12]. These authors concluded that the saturation
*Email: [email protected]
ISSN 09500839 print/ISSN 13623036 online
2010 Taylor & Francis
DOI: 10.1080/09500831003630732
http://www.informaworld.com

Downloaded By: [Egypt Consortium - EUN - Trial Account] At: 15:43 18 April 2010

234

S.I. El-Dek

magnetization Ms increases with annealing temperature, with a burst increment

occurring between 600 and 800 C, from 38.30 to 63.26 emu/g. A similar evolution
trend is also found in Mr, which increases from 15.12 emu/g at 600 C to 28.70 emu/g
at 800 C. However, the coercive field Hc reaches its maximum of 1373 Oe at 400 C
and then decreases to 870 Oe at 600 C. The drastic drop of Hc for the sample
annealed at 900 C might originate from the transition of a single magnetic domain to
a multi-domain within a particle. Recently, Ai and Jiang [13] prepared CoFe2O4
using the solgel autocombustion method. They found that the saturation
magnetization of as-synthesized cobalt ferrites seems to increase linearly with the
annealing temperature, and the Ms values of the samples are significantly lower than
the bulk value of 90 emu/g. In the past decade, various methods have been reported
on the preparation of CoFe2O4 nanocrystals [1416].
Little research has been conducted concerning the effect of annealing conditions
such as temperature and/or time on the magnetic properties of CoFe2O4 prepared by
the flash method. The main goal of this study is to investigate the effect of annealing
temperature on the lattice parameter as well as some important magnetic properties
of CoFe2O4 ferrite prepared by this method.

2. Experimental
CoFe2O4 was prepared by the flash combustion technique [1719] using high-purity
(BDH) CoCl2  2H2O, Fe(NO3)3  9H2O, and urea. The chemicals were weighed in the
required stoichiometric proportions (Co:Fe 1:2) and mixed together for a few
minutes. One mole of urea was added and the mixture was well ground to achieve
good mixing. The mixture was transferred to a quartz crucible, introduced into an
electric furnace, and presintered at 500 C for 15 min. At this temperature, the
mixture reacts giving off gases; the combustion was completed in 35 min. A foamy
and highly porous precursor mass was thereby obtained which was collected and
then powdered for further processing. Then the ferrite precursor powder was divided
into batches that were annealed at 900, 950, 1000, and 1050 C for 2 h to achieve
better crystallinity.
The prepared powders were characterized by X-ray diffraction using a model
Proker D8 diffractometer with Cu K radiation ( 1.5418 A) over a wide range of
Bragg angles (2080 ) at room temperature. The average particle size t was
calculated from the X-ray line broadening using the (3 1 1) peak and the Debye
Sherrer equation [20]; t 0.89/ cos ; where  is the FWHM and , the wavelength
of the radiation.
The hysteresis and magnetization measurements were performed using a
vibrating sample magnetometer (VSM; 9600-1 LDJ, USA) with a maximum applied
field of 15 kOe at room temperature.

3. Results and discussion

X-ray diffraction patterns for all the samples are shown in Figure 1. They reveal a
single-phase spinel structure with cubic symmetry with no extra lines that would
indicate the formation of other phases. The data were compared and indexed with

235

(311)

Philosophical Magazine Letters

(533)

(620)

(440)

(511)

(422)

(400)

80

1050C

(222)

(220)

160

Counts

20

30

40

50

60

70

80

160

1000C

80
0
20

30

40

50

60

70

80

Downloaded By: [Egypt Consortium - EUN - Trial Account] At: 15:43 18 April 2010

80

950C

40
0
20

30

40

50

60

70

80

50

900C
0
20

30

40

50

60

70

2q

80

Figure 1. X-ray diffraction patterns of CoFe2O4 at different annealing temperatures.

JCPDS no. 79-1744. The calculated lattice parameter and the crystal size are plotted
versus the annealing temperature in Figure 2a and b. It can be seen that the lattice
parameter decreases slightly with increasing annealing temperature while the crystal
size increases up to a maximum value at 1000 C. The enhancement of the
crystallinity in the annealed samples is believed to originate from the increment of
the crystalline volume ratio, as a consequence of the size enlargement of the nuclei
[21]. The variation of the lattice parameter a with the crystal size L is fitted with the
linear empirical relation: a 8.3455.85  106L. The decrease in the lattice
parameter with increasing annealing temperature could be due to a decrease in the
intergranular spacing which results in the enhancement of grain growth as well as
densification. The values of the lattice parameter, crystal size, and theoretical density
are reported in Table 1. The data in the table clarifies the improvement in the
densification as well as the enhancement of the crystal growth with increasing
annealing temperature. Another reason for the slight decrease in the lattice
parameter with increasing annealing temperature could be a statistical redistribution
of the cations among the A and B sites for samples with small crystallite size.
The data in the table clarifies the improvement of the densification as well as the
enhancement of the crystal growth with increasing annealing temperature. While
annealing generally decreases the lattice defects and strains, however, it can also
cause coalescence of crystallites that result in increasing the average size of the
nanoparticles up to a certain extent at which a large increase in the crystal size is
observed.

236

S.I. El-Dek
(a) 8.6

240
200
160

a ( A)

a ( A)
L (nm)

L (nm)

8.4

120
80
40

8.2
900

950

1000

1050
o

Annealing temperature ( C)

Lattice parameter a ( A)

Downloaded By: [Egypt Consortium - EUN - Trial Account] At: 15:43 18 April 2010

(b) 8.8
8.6

a = 8.3455.85x10 L

8.4
8.2
8.0
40

60

80
140
160
Crystal size L (nm)

Figure 2. (a) Dependence of the lattice patameter on the annealing temperature. (b) Relation
between the lattice parameter and the crystal size.

Table 1. Values of the lattice parameter a (A), theoretical density Dx (g/cm3), crystal size L
(nm), coercive field Hc (Oe), remanent, saturation magnetization Mr and Ms (emu/g) and
squareness ratio Mr/Ms for CoFe2O4 samples as a function of the annealing temperature.
Annealing
temperature ( C)
900
950
1000
1050

a (A)
8.37476
8.32402
8.35051
8.32915

Dx (g/cm3) L (nm) Hc (Oe) Mr (emu/g) Ms (emu/g) Mr/Ms

5.3051
5.4027
5.3514
5.3927

38.81
40.01
144.76
80.46

724.8
396.2
297.7
260

16.84
15.98
14.08
13.68

53.38
64.36
69.29
75.35

0.31
0.24
0.20
0.18

Magnetization studies were performed at room temperature on the investigated

samples and are represented in Figure 3. The values of the saturation magnetization
Ms, coercivity Hc, remanence magnetization Mr, and the squareness ratio Mr/Ms are
reported in Table 1. The obtained values of Ms are slightly higher than that obtained
by Goh et al. [22] and Xiao et al. [12], while the coercivity is smaller than where they
reached the high coercivity of 2216 Oe at Ms 73 emu/g [22]. The variations of the
magnetic parameters as a function of heat treatment may be due to the growth of the
grains with increasing temperature. Cation redistribution may also play a significant

237

Philosophical Magazine Letters

M (emu/g)

100
80

1050C
1000C
950C

60

900C

40
20
0
20000

15000

10000

5000

0
20

5000

10000

15000
20000
H (Oe)

Downloaded By: [Egypt Consortium - EUN - Trial Account] At: 15:43 18 April 2010

40
60
80
100

Figure 3. Hysteresis plots of CoFe2O4 at different annealing temperatures.

role in the increase of saturation magnetization. The octahedral site in the spinel
structure has six nearest tetrahedral sites; the six T sites are occupied by six Fe ions in
the full inverse spinel and by 6, 5, 4, or 3 Fe ions in the partially inverse structure [23].
It is certain that the differences in the saturation magnetization are due to the
different degree of inversion in the samples. This is rather believable, since the
samples differ both in their particle size and in their thermal history, which are
the factors usually indicated as responsible for the degree of inversion attained by the
ferritic spinels. It is likely that the different formation mechanism of the samples has
given rise to a different growth rate of the particles and, in addition, has carried the
reagents through a different thermal path, with respect to both the annealing
temperature and the cooling rate [2426].
The saturation magnetization increases with increasing particle size while the
coercivity and the remanence magnetization decreases. This result agrees well with
the relation [27] Hc / Ko Ms 1 , where K is the magnetocrystalline anisotropy
constant. Since the coercivity of a material is a rough measure of its magnetocrystalline anisotropy, the decrease in Mr and Hc with increasing annealing temperature
can be attributed to a lowering of the anisotropic properties of the CoFe2O4
nanoparticles.
The increase of Ms with the annealing temperature is directly related to the
increase of the magnetization of the B sublattice, which may result from the
redistribution of Co2 ions on the A sites at high annealing temperature.
The squareness ratio Mr/Ms decreases from 0.31 to 0.18 with increasing annealing
temperature, i.e., it depends on the crystal size. This seems reasonable because the
increase in Ms cannot be compensated by the decrease in Mr.
Empirical formulae linearly correlating both Mr and Ms with the crystallite
size (Figure 4a and b) can be expressed as follows: Ms 57:44 0:1L and Mr
16:91  0:023L:

238

S.I. El-Dek

Ms (emu/g)

(a) 100

50

0
40

60

80

100

120

140

160

L (nm)

Mr (emu/g)

20
15
10
5
0
40

60

80

100

120

140

160

L (nm)
(c)
800

Hc (Oe)

Downloaded By: [Egypt Consortium - EUN - Trial Account] At: 15:43 18 April 2010

(b)

Hc = 269.03 + 18886e

(L /9.5)

400

40

60

80

100

120

140

160

L (nm)

Figure 4. (a) Dependence of saturation Ms, (b) remanent magnetization Mr, and (c) coercive
field Hc on the crystal size.

The samples annealed at 1000 and 1050 C have a larger magnetization and a
lower remanence and coercivity, which imply that these samples are multi-domain in
nature.
The data for Hc versus crystal size is fitted to the relation Hc 269:03
18886 expL=9:5 as illustrated in Figure 4c. It is clearly seen that Hc decays
exponentially with increasing particle size.
Regarding the coercivity, the fact that it does not have reduced values even at the
smallest particle size (38 nm) indicates that there is no dominant effect of
superparamagnetism. This is in accordance with the report that the critical particle
size at which the sample becomes a single-domain particle in the case of cobalt ferrite
is 70 nm [28]. The squareness ratio being in the range of 0.20.3 suggests that the
particles are predominantly not in the single-domain state, even in the case of
nanoparticles. Stoner and Wohlfarth [29] have reported the ratio R Mr/Ms 0.5
for randomly oriented non-interacting particles that undergo coherent rotation,

Downloaded By: [Egypt Consortium - EUN - Trial Account] At: 15:43 18 April 2010

Philosophical Magazine Letters

239

while for R50.5 the particles interact by magnetostatic interactions. Exchangecoupling exists when R40.5.
It is possible that the nanosized samples consist of pseudo-single-domain particles
[30,31]. The variation of coercivity with particle size is explained on the basis of
domain structure, diameter of the particles, and crystal anisotropy [30,31]. The
saturation magnetization for the nanocrystalline cobalt ferrite is found to be lower
than the materials bulk value, which can be attributed to surface spin canting
[32,33]. The increase of saturation magnetization with increasing annealing temperature points to an increase in the average magnetic domain size of the particles and
the atomic spins becoming more and more aligned with the direction of the applied
magnetic field [34,35]. An increase in crystallite size is observed with the increase of
annealing temperature up to 1000 C, thus improving the crystallinity which in turns
leads to enhancement of the magnetization.

4. Conclusions
The flash method is a successful technique for obtaining single-phase spinel-structure
CoFe2O4 nanocrystals. The lattice parameter decreases slightly with increasing
particle size. The saturation magnetization increases while the remanent magnetization decreases linearly with the crystal size. An exponential decrease of the
coercivity is observed with increasing particle size.

Acknowledgement
The author is grateful to Professor Dr M.A. Ahmed, Materials Science Laboratory (1),
Physics Department, Faculty of Science, Cairo University, Giza, Egypt, for his invaluable help
during the progress of this work.

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]

D.S. Mathew and R. Juang, Chem. Eng. J. 129 (2007) p.51.

Y.I. Kim, D. Kim and C.S. Lee, Phys. B 337 (2003) p.42.
C. Caizer, M. Popovici and C. Savii, Acta Mat. 51 (2003) p.3607.
D.K. Kim, Y. Zhang, W. Voit, K.V. Rao and M. Muhammed, J. Magn. Magn. Mater.
225 (2001) p.30.
Y.Q. Chu, Z.W. Fu and Q.Z. Qin, Electrochim. Acta 49 (2004) p.4915.
W. Fu, H. Yang, M. Li, M. Li, N. Yang and G. Zou, Mater. Lett. 59 (2005) p.3530.
I.H. Gul and A. Maqsood, J. Alloys Comp. 465 (2008) p.227.
M. Pita, J.M. Abad, C. Vaz-Dominguez, C. Briones, E. Mateo-Marti, J.A. Martin-Gago,
M.d.P. Morales and V.M. Fernandez, J. Colloid. Interface. Sci. 321 (2008) p.484.
G. Baldi, D. Bonacchi and C. Innocenti, J. Magn. Magn. Mater. 311 (2007) p.10.
M.S. Incai, D. Ganga, D. Bica and L. Vekas, J. Magn. Magn. Mater. 225 (2001) p.235.
O. Caltun, I. Dumitru, M. Feder, N. Lupu and H. Chiriac, J. Magn. Magn. Mater. 320
(2008) p.e869.
S.H. Xiao, W.F. Jiang, L. Yu Li and X.J. Li, Mater. Chem. Phys. 106 (2007) p.82.
L. Ai and J. Jiang, Curr. Appl. Phys. 10 (2010) p.284.

Downloaded By: [Egypt Consortium - EUN - Trial Account] At: 15:43 18 April 2010

240

S.I. El-Dek

[14] K.S. Martirosyan, L. Chang, J. Rantschler, S. Khizroev, D. Luss and D. Litvinov, IEEE
Trans. Magn. 43 (2007) p.3118.
[15] X. Yang, X. Wang and Z. Zhang, J. Cryst. Growth 277 (2005) p.467.
[16] N. Hanh, O.K. Quy, N.P. Thuy, L.D. Tung and L. Spinu, Phys. B 327 (2003) p.382.
[17] R.V. Mangalaraja, S. Ananthakumar, P. Manohar, F.D. Gnanam and M. Awano, Mater.
Sci. Eng. A 367 (2004) p.301.
[18] M.A. Ahmed, N. Okasha and S.I. El-Dek, Nanotechnol. 19 (2008) p.065603.
[19] M.A. Ahmed, N. Okasha and M.M. El-Sayed, Ceram. Int. 33 (2007) p.49.
[20] B.D. Cullity, Elements of X-ray Diffraction, 2nd ed., Addison-Wesley Publishing
Company, USA, 1978, p.102.
[21] Y.P. Sui, X.F. Huang, Z.Y. Ma, W. Li, F. Qiao, K. Chen and K.J. Chen, J. Phys.:
Condens. Matter 15 (2003) p.5793.
[22] S.C. Goh, C.H. Chia, S. Zakaria, M. Yusoff, C.Y. Haw, Sh. Ahmadi, N.M. Huang and
H.N. Lim, Mater. Chem. Phys. 20 (2010) p.31.
[23] N. Moumen, P. Bonville and M.P. Pileni, J. Phys. Chem. B 100 (1996) p.14410.
[24] T.A. Anhj, B. Bilenberg, B. Thomsen, C.D. Damsgaard, H.K. Rasmussen,
C.S. Jacobsen, J. Mygind and S. Mrup, J. Magn. Magn. Mater. 260 (2003) p.115.
[25] S. Mrup, J. Magn. Magn. Mater. 266 (2003) p.110.
[26] G. Concas, G. Spano, C. Cannas, A. Musinu, D. Peddis and G. Piccaluga, J. Magn.
Magn. Mater. 321 (2009) p.1893.
[27] Y.W. Dou, Ferrites, Jiangsu Technology Publishing Company, Nanjing, 1996, pp.6269
(in Chinese).
[28] F. Bensebaa, F. Zavaliche, P. LEcuyer, R.W. Cochrane and T. Veres, J. Colloid Interface
Sci. 277 (2004) p.104.
[29] Z.L. Wang, Y. Liu and Z. Zhang, Handbook of Nanophase and Nanostructured Materials.
Volume III: Materials Systems and Applications I, Kluwer Academic/Plenum Publishers,
USA, 2003, pp.252259.
[30] B.D. Cullity, Introduction to Magnetic Materials, Addison-Wesely Publishing Company,
Reading, MA, 1972, p.387 and p.617.
[31] S. Chikazumi, Physics of Magnetism, Chapter 11, Wiley, New York, 1959, p.224.
[32] W.S. Chiu, S. Radiman, R. Abd-Shukor, M.H. Abdullah and P.S. Khiew, J. Alloys
Compd. 459 (2008) p.291.
[33] M. Rajendran, R.C. Pullar, A.K. Bhattacharya, D. Das, S.N. Chintalapudi and
C.K. Majumdar, J. Magn. Magn. Mater. 232 (2001) p.71.
[34] B.G. Toksha, S.E. Shirsath, S.M. Patange and K.M. Jadhav, Solid State Comm. 147
(2008) p.479.
[35] R.H. Kodama, J. Magn. Magn. Mater. 200 (1999) p.359.