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Article history:
Received 22 September 2008
Received in revised form
26 November 2008
Available online 7 December 2008
Magnetic nanoparticles of nickel ferrite (NiFe2O4) have been synthesized by co-precipitation route using
stable ferric and nickel salts with sodium hydroxide as the precipitating agent and oleic acid as the
surfactant. X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses conrmed
the formation of single-phase nickel ferrite nanoparticles in the range 828 nm depending upon the
annealing temperature of the samples during the synthesis. The size of the particles (d) was observed to
be increasing linearly with annealing temperature of the sample while the coercivity with particle size
goes through a maximum, peaking at 11 nm and then decreases for larger particles. Typical blocking
effects were observed below 225 K for all the prepared samples. The superparamagnetic blocking
temperature (TB) was found to be increasing with increasing particle size that has been attributed to the
increased effective anisotropy energy of the nanoparticles. The saturation moment of all the samples
was found much below the bulk value of nickel ferrite that has been attributed to the disordered surface
spins or dead/inert layer in these nanoparticles.
& 2008 Elsevier B.V. All rights reserved.
PACS:
73.63b
75.50Gg
75.50Tt
75.70Rf
Keywords:
Magnetic properties
Ferrite nanoparticles
Surface anisotropy
Magnetic materials
1. Introduction
In the recent years much attention has been paid to the
understanding of nanostructured materials (such as multi-layers,
nanowires, nanoparticles, as well as composite materials), that
exhibit interesting optical, electrical, chemical and magnetic
properties [14]. These properties along with their great chemical
and physical stability, that appear them different from their bulk
counterparts, make these materials of great scientic and
technological interests [59]. The magnetic character of the
nanoparticles used in medical, electronic and recording industries
depends crucially on the size, shape, purity and magnetic
stability (e.g. blocked, unblocked state at particular operating
temperature) of these nanoparticles. These particles should be in
single-domain state, of pure phase, having high coercivity (HC)
and moderate magnetization. From the application point of
view, the superparamagnetic blocking temperature (TB) of
the nanoparticles used for recording devices should be well above
the room temperature in order to have a stable data recording in
0304-8853/$ - see front matter & 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2008.11.098
these devices. In biomedical applications the magnetic nanoparticles are used as drug carriers inside the body where conventional drug delivery systems may not work. The nanoparticles
used for this purpose should be magnetically in the superparamagnetic unblocked state with relatively low blocking
temperature. The most signicant properties of magnetic nanoparticles (ferrites), namely magnetic saturation, coercivity,
magnetization and loss, etc. change drastically as the particle size
reduces to the nanometric range [1012]. Among various ferrites,
which form a major constituent of the magnetic ceramic
materials, nano-sized nickel ferrite possesses attractive properties
for the application as soft magnets and low loss materials at high
frequencies [13].
Conventional techniques for preparation of nanoparticles and
nanowires include solgel processing, evaporation condensation,
microemulsion technique, combustion method, spray pyrolysis,
hydrothermal process and template-assisted electrochemical
synthesis [1420]. Generally in most of these methods the precise
control over the size and its distribution is quite difcult [1]. In
order to overcome these difculties, co-precipitation method has
been used for synthesis of these nanoparticles. In this method the
nanometer-sized reactors for the formation of homogeneous
nanoparticles of nickel ferrite have been used. To protect the
oxidation of these nanoparticles in the presence atmospheric
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K. Maaz et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 18381842
2. Synthesis procedure
3 M solution of sodium hydroxide (as the precipitating agent)
was slowly mixed with salt solutions of 0.4 M ferric chloride
(FeCl3 6H2O) and 0.2 M nickel chloride (NiCl2 6H2O). The
pH of the solution was constantly monitored as the NaOH solution
was added dropwise. The reactants were constantly stirred
using a magnetic stirrer until a pH level of 412 was achieved. A
specied amount of oleic acid (23 drops for total reacting
solution of 75 ml) was added to the solution as the surfactant
[23,24]. The liquid precipitate was then brought to a reaction
temperature of 80 1C and stirred for 40 min. The product was
cooled to room temperature and then washed twice with distilled
water and ethanol to remove unwanted impurities and the excess
surfactant from the prepared sample. The sample was centrifuged
for 15 min at 2000 rpm and then dried overnight at above 80 1C.
The acquired substance was then grinded into a ne powder and
then annealed for 10 h at 600 1C. The nal product obtained as
conrmed by the X-ray diffraction and SAED was found to be
magnetic nanoparticles of nickel ferrite (NiFe2O4) with inverse
spinel structure.
(311)
8500
8000
~28 nm NiFe2O4
7500
7000
5000
(511)
(422)
5500
(400)
6000
(440)
6500
(220)
Intensity (a.u)
1839
4500
30
40
50
2 (degree)
60
70
Fig. 1. X-ray diffraction pattern of NiFe2O4 nanoparticles prepared by coprecipitation method annealed at 1000 1C for 10 h with average grain size of
28 m.
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K. Maaz et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 18381842
50
35
Linear fit to data points
40
30
77 K
300K
25
20
20
10
M (emu/g)
30
15
0
-10
-20
10
-30
5
-40
0
500
600
700
800
900
1000
-50
-10000 -7500 -5000 -2500
1100
Tann (C)
180
160
Coercivity (Oe)
0
H (Oe)
140
120
100
80
5
10
15
20
Particle Size (nm)
25
30
while for very soft magnetic materials k51. The exchange length
(lex) is dened by lex (A/moMS2)1/2 representing the length below
which the atomic exchange interactions dominate the typical
magnetostatic elds. For a typical permanent magnet the value of
exchange length (lex) is of the order of 3 nm and A is the called the
exchange constant or the exchange stiffness parameter. The value
of k was calculated by taking the values of K1 and MS for bulk
materials from Skomsky [27], while the value of lex was calculated
by estimating the exchange constant (A) directly proportional to
the respective Tcs of Co- and Ni-ferrite (790 and 865 K for Co- and
Ni-ferrite). The ratio [(dSD)Ni]/[(dSD)Co] was found to be 0.38. For
a single-domain limit of 28 nm for CoFe2O4 as reported in one of
our previous papers [24], this suggests the value of single-domain
limit (dSD) for Ni-ferrite as 10.7 nm. We observed a maximum in
HC-d curve (Fig. 5) for NiFe2O4 at 11 nm. This value is smaller
than the previously reported value of 14 nm for single-domain
limit of NiFe2O4 nanoparticles [12]. We noticed in Fig. 5 that the
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K. Maaz et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 18381842
t to exp
K eff V p
kB T
45
Linear fit to expt. data points
40
220
35
210
30
MS (emu/gm)
TB (K)
230
1841
200
190
25
20
15
180
10
170
5
160
0
5
10
15
20
Particle Size (nm)
25
30
10
15
20
25
30
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K. Maaz et al. / Journal of Magnetism and Magnetic Materials 321 (2009) 18381842
4. Conclusion
In this article we have presented synthesis of NiFe2O4
nanoparticles by co-precipitation route in the range 828 nm.
The size of the particles was measured both by XRD and TEM and
was found in good agreement with each other. The size of the
particles appeared to increase linearly with annealing temperature most probably due to the coalescence that increases with
increasing temperature of annealing. The relatively large coercivity and saturation magnetization at 77 K in comparison with room
temperature appeared to be due to the pronounced growth of
magnetic anisotropy at low temperatures. The coercivity showed a
peak with particle size at a value smaller than the previously
reported value of single-domain limit for NiFe2O4 that has been
attributed to the enhanced role of the surface anisotropy as
compared to the bulk for small sizes. The superparamagnetic
blocking temperature was found to increase linearly with
increasing particle sizes. This was assigned to the increasing
volume of the larger particles that resultantly increasing the
effective anisotropy energy and hence the blocking temperature of
nanoparticles. The smaller value of MS for smaller particles was
attributed to the greater fraction of surface spins in these
nanoparticles that tend to be in a canted, spin glass like or dead
layer like state with a smaller net moment.
Acknowledgments
K. Maaz acknowledges the PCSIR of Pakistan for providing 6
months fellowship titled Establishment of Nano-Tech Lab at PCSIR
and some nancial support from the Material Science Group-II,
Institute of Modern Physics, Chinese Academy of Sciences P.R.
China. J. Liu and J.L. Duan acknowledge the National Natural
Science Foundation of China (No.10775161, 10775162, 10805062)
and the West Light Foundation of Chinese Academy of Sciences for
their nancial support to enable this work.
References
[1] M. Dariel, L.H. Bennett, D.S. Lashmore, P. Lubitz, M. Rubinstein, W.L. Lechter,
M.Z. Harford, J. Appl. Phys. 61 (1987) 4067.