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Journal of Magnetism and Magnetic Materials 321 (2009) 18381842

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Journal of Magnetism and Magnetic Materials


journal homepage: www.elsevier.com/locate/jmmm

Synthesis and magnetic characterization of nickel ferrite nanoparticles


prepared by co-precipitation route
K. Maaz a,b,, S. Karim a, A. Mumtaz b, S.K. Hasanain b, J. Liu c, J.L. Duan c
a
b
c

PINSTECH, Post Ofce Nilore, Islamabad, Pakistan


Department of Physics, Quaid-i-Azam University, Islamabad, Pakistan
Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou, PR China

a r t i c l e in f o

a b s t r a c t

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

 Corresponding author at: Department of Physics, Quaid-i-Azam University,


Islamabad, Pakistan. Tel.: +92 321 5029820; fax: +92 51 9290275.
E-mail addresses: maaz@impcas.ac.cn, maaz@phys.qau.edu.pk (K. Maaz).

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)

oxygen and also to stop their agglomeration, the particles are


usually coated with some surfactant like sodium dodecyl
sulfate (NaDS) or the oleic acid [21,22] and then dispersed in
some carrier liquid like ethanol, methanol, ammonia, etc.
depending upon the nature of the materials (nanoparticles) to
be dispersed. The advantage of this method over the others is that
the production rate of ferrite nanoparticles, its size and size
distribution is relatively easy and there is no need of extra
mechanical or microwave heat treatments. In this work, nickel
ferrite nanoparticles (NiFe2O4) have been prepared by coprecipitation technique and then they were heat treated
(annealed) at different temperatures (from 600 to 1000 1C) to
synthesize magnetic nanoparticles with different grain sizes.
Various magnetic properties of nickel ferrite nanoparticles
have been explored as a function of particle size and temperature.
Debey Scherrer formula was used for size determination using
the strongest peak in the XRD pattern. The size variation in this
study was carried out from 8 to 28 nm with a distribution of
73 nm. The physical characterization was performed by X-ray
diffractometer (Model: XPert Philips, Holland, with Cu-Ka
l 0.154056 nm) and high-resolution transmission electron
microscope (HRTEM, 300 keV) (Model: JEM-3010, JEOL) while
the magnetic characterization was done by vibrating sample
magnetometer (VSM, Model 7300 Lake Shore, USA) with an
applied eld of 710 kOe.
In this article we have reported three new results that have
not been reported previously, to the best of our knowledge.
Firstly, we have studied the superparamagnetic blocking effects in
detail for the given size (828 nm) of NiFe2O4 nanoparticles
that has not been reported so far, at least for this size range.
Secondly, we have used a theoretical model for calculating the
ratio of critical single-domain radii for bulk Ni- and Co-ferrite.
This ratio has been used to calculate the single-domain limit for
Ni-ferrite nanoparticles using the previously reported values for
Co-ferrite nanoparticles, that comes out to be 10.7 nm (the detail
is given in Section 3). Comparison of the results shows that our
reported value for the single-domain limit (11 nm) is in good
agreement with calculated (theoretical) value for Ni-ferrite
nanoparticles. The third and important point that makes this
work different from the previous reports is that we have
presented a single-domain limit of around 11 nm for NiFe2O4
nanoparticles that has not been reported previously (the detail is
given in Section 3).

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.

Fig. 2. TEM micrograph of NiFe2O4 nanoparticles prepared by co-precipitation


route annealed at 1000 1C for 10 h.

3. Results and discussion


The X-diffraction pattern (Fig. 1) of the sample annealed at
1000 1C prepared by co-precipitation technique shows that the
nal product is cubic NiFe2O4 with average crystallite size of
28 nm (the XRD peaks were compared to the standard PDF card
number 742081 for inverse cubic nickel ferrite). The average sizes
of the particles annealed at 600, 700, 800, 900 and 1000 1C for 10 h
were found to be 8, 11, 18, 24 and 2873 nm. Fig. 2 shows the highresolution TEM images of the same sample annealed at 1000 1C for
10 h. In the TEM image most of the particles appear spherical in
shape, however, some elongated particles are also present in the
images. Some moderately agglomerated particles as well as
separated particles are also present in the sample. The inset of
Fig. 2 shows the selected area electron diffraction (SAED) analysis
of the sample indicating that the nanoparticles prepared are
crystalline. The same has also been conrmed from the XRD peaks

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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)

Particle size (nm)

30

15

0
-10
-20

10

-30
5
-40
0
500

600

700

800

900

1000

-50
-10000 -7500 -5000 -2500

1100

Tann (C)

indicating the ploycrystalline nature of the prepared sample. Fig. 3


shows the dependence of size of the particles on annealing
temperature (Tann). The size of the particles was observed to be
increasing linearly with annealing temperature. It has been
reported earlier that annealing process generally decreases the
lattice defects and strains; however, it can also cause coalescence
of smaller grains that results in increasing the average grain size
of the nanoparticles [25]. The observed increase in particle size
with annealing temperature is most likely due to the fact that
higher annealing temperature and time enhances the coalescence
process resulting in an increase in the grain size. Thus it appears
that particle size may be controlled either by varying the
annealing temperature of the sample or the annealing time
during the synthesis process.
Magnetic characterization of the particles was performed by
vibrating sample magnetometer (VSM) between the room
temperature (300 K) and 77 K with maximum applied eld upto
10 kOe. Fig. 4 shows the M(H) loops of 28 nm sample both at room
temperature (300 K) and 77 K. The insets of the gure show the
expanded regions around the origin with different eld ranges
(7400 and 71000 Oe) in order to make the coercivities more
visible at these temperatures. For the 28 nm size particles the
coercivity at room temperature as derived from the M(H) loops
was 89 Oe, while at 77 K it has increased to 175 Oe. The
saturation magnetization (MS) obtained at room temperature was
found to be 40.5 emu/g smaller than the bulk value of 56 emu/g
for nickel ferrite, while at 77 K this value has increased to
45 emu/g. The relatively large coercivity and saturation magnetization at 77 K are consistent with the pronounced growth of
magnetic anisotropy inhibiting the alignment of the moment
along the applied eld direction [24,26].
The coercivity of nanoparticles was also studied as a function
of particle size at room temperature (300 K) as shown in Fig. 5.
The gure shows that for smaller sizes (811 nm) the coercivity
increases with size rapidly, attaining a maximum value of 175 Oe
at 11 nm and then decreases with size of the particles, for larger
particles (1228 nm). A ratio of the critical single-domain radii for
Ni-ferrite (dSD)Ni and Co-ferrite (dSD)Co has been calculated using
the relation for critical single-domain radius dSD 36klex;
where k is the magnetic hardness parameter dened by
k (K1/moMS2)1/2 [27]. For very hard magnetic materials kb1,

2500 5000 7500 10000

Fig. 4. Hysteresis loops for 28 nm NiFe2O4 nanoparticles at room temperature


(300 K) and 77 K at maximum applied eld of 10 kOe. The two insets of the gure
show the expanded eld region around the origin for clear visibility of the readers.

180

160
Coercivity (Oe)

Fig. 3. Particle size as a function of annealing temperature for NiFe2O4


nanoparticles. Samples were annealed at 600, 700, 800, 900 and 1000 1C with
average sizes of 8, 11, 18, 24 and 2873 nm, respectively.

0
H (Oe)

140

120

100

80
5

10

15
20
Particle Size (nm)

25

30

Fig. 5. The coercivity (HC) as a function of average particle diameter at room


temperature. The peak of HC at 11 nm is evident in the gure.

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

coercivity of nickel ferrite shows a non-monotonic behavior


with particle size, i.e. for small sizes the coercivity rst increases,
goes through peaks (at around 11 nm) and afterwards it decreases
for larger particles (1228 nm), above the peak. The initial
increase of coercivity for smaller particles, below the peak, with
increasing size may be assigned to the departure from the
superparamagnetic state i.e., from unblocked to blocked state.
This occurs for small particles when the thermal energy
dominates the volume-dependent anisotropy energy (EA KeffV).
Hence in the lower d region (811 nm) the coercivity may
increase with increasing sizes as the larger-sized particles
would tend to show a blocked moment. The decline in HC with
increasing d, above the peak, can occur due to the two different
mechanisms. Firstly, it may occur as the particle sizes become
large enough to sustain a domain wall. In this situation the
magnetization reversal would occur via domain wall motion and
consequently a lower coercivity would be observed. In NiFe2O4,
however, this crossover is expected at much higher than 11 nm
where we observed the peak in our samples. Secondly, it may be
due to the varying role of the surface and the observed bulk
anisotropies as the size is diminished. Starting from larger sizes,
with decreasing size of particles (from 28 nm), the role of the
surface and its associated anisotropy energy is increased. It
has been shown by Bodker et al. [28] that the effective anisotropy constant increases with decreasing particle sizes according
to phenomenological expression (Keff KV+(6/d)KS) for the effective anisotropy of spherical particles. Several other works
including simulation and experimental have also supported this
expression [29]. If we assume similar behavior in NiFe2O4
nanoparticles i.e. an increase in the effective anisotropy constant
with reducing particle sizes (from 28 nm), this would tend to
increase the coercivity of the nanoparticles within the StonerWohlfarth picture (HC 2K/MS) consistent with the behavior of
HC above the peak (2811 nm) as shown in Fig. 5. This increase
will, however, not continue indenitely and as the particle
size decreases to a small enough value (dSD), the thermal effects
will take over. For particles below the critical size (say dSD11 nm)
the thermal energy becomes sufcient to overcome the
overall anisotropy energy enabling the easier reversal of the
moments leading to the lower critical elds for these small sizes
[30]. This leads to the lowering of coercivity in the small size
regime (811 nm).

Fig. 6 shows the blocking temperature (Tb) as a function of


particle size, derived from the M(T) curves of the samples. The
inset of the gure shows a typical zero-eld cooled (ZFC) M(T)
curve for one of the representative samples (with average size of
28 nm). For a single particle, at nite temperature, the ferromagnetically aligned magnetic moments uctuate between their two
energetically degenerate ground states on a time scale given by
the relation [31]

t to exp



K eff V p
kB T

where t is the relaxation time and Keff VP the effective anisotropy


energy (EA) of the particles. The blocking temperature Tb of a
particle is the temperature at which t tm, the measurement
time of the instrument. For a nite temperature T4Tb the particle
behaves like a superparamagnet (unblocked state). On the other
hand, for ToTb the particle is said to be in the blocked state, i.e.
behaves like a ferromagnet. Referring back to our data of (Tbd)
curve for nickel ferrite (Fig. 6), we see that there is a clear increase
in the blocking temperature with size of the particles. The larger
particles seem to be blocked at high temperatures as compared to
the smaller particles. For larger particles, the larger volume causes
increased anisotropy energy, which decreases the probability of a
jump across the anisotropy barrier and hence the blocking is
shifted to higher temperatures. Fig. 7 shows the dependence of
saturation magnetization on particle size. The MS values obtained
for our samples varied between 9 and 40.5 emu/g for the sizes
from 8 to 28 nm. The saturation magnetization increases consistently with size of the nanoparticles. A similar trend has also
been reported for NiFe2O4 nanoparticles earlier [32,33]. The
decrease in MS at smaller sizes is attributed to the pronounced
surface effects in these nanoparticles. The surface of the
nanoparticles is considered to be composed of some canted or
disordered spins that prevent the core spins to align along the
eld direction resultantly decreasing the saturation magnetization of the nanoparticles for smaller sizes [3436]. The surface
may also behaves like a dead or inert layer that has negligible
magnetization [24,37,38]. This effect becomes more pronounced
for smaller particles; due to the increased number of surface to
volume atoms that resultantly decreasing the saturation magnetization for the smaller-sized NiFe2O4 nanoparticles.

45
Linear fit to expt. data points

Linear fit to the 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

Fig. 6. The dependence of superparamagnetic blocking temperature (TB) on


particle size for NiFe2O4 nanoparticles. The inset of the gure shows the
temperature dependence of zero-eld cooled (ZFC) magnetization.

10

15

20

25

30

Particle Size (nm)


Fig. 7. Saturation magnetization (MS) as function of particle size for NiFe2O4
nanoparticles. The observed values of MS lie much below the bulk value of
56 emu/g for NiFe2O4.

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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.
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