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Synthesis and Characterization of Nickel Ferrite Magnetic Nanoparticles

Article  in  Materials Research Bulletin · December 2011

DOI: 10.1016/j.materresbull.2011.09.009

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Materials Research Bulletin 46 (2011) 2208–2211

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Materials Research Bulletin

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Synthesis and characterization of nickel ferrite magnetic nanoparticles

P. Sivakumar a,*, R. Ramesh b, A. Ramanand c, S. Ponnusamy b, C. Muthamizhchelvan b
a
T. S. Srinivasan Centre for Polytechnic College and Advanced Training (CPAT-TVS), Vanagaram, Chennai – 600 095, Tamilnadu, India
b
Center for Materials Science and Nano Devices, Department of Physics, SRM University, Kattankulathur, Kancheepuram – 603 203, Tamilnadu, India
c
Department of Physics, Loyola College, Nungambakkam, Chennai – 600 034, Tamilnadu, India

A R T I C L E I N F O A B S T R A C T

Article history: Nickel ferrite (NiFe2O4) nanoparticles are prepared by a polyvinyl alcohol (PVA) assisted sol–gel auto-
Received 2 May 2011 combustion method. The structure, composition, morphology and magnetic properties of the gel
Received in revised form 6 August 2011 precursor are characterized by powder XRD, FT-IR, TGA, HR-SEM, TEM, HR-TEM and VSM. XRD confirms
Accepted 14 September 2011
the formation of single-phase nickel ferrite with space group of Fd3m and inverse spinel structure. The
Available online 21 September 2011
vibration properties of nanoparticles are analysed by FT-IR spectrum. The thermal decomposition of the
gel precursors is investigated by TGA. HR-SEM and TEM images show that the particles have spherical
Keywords:
shape with particle size in the range of 30 nm and consistent with XRD result. The magnetic properties
A. Composites
A. Nanostructures
of these nanoparticles are studied for confirming the ferromagnetic behaviour at room temperature.
B. Chemical synthesis ß 2011 Elsevier Ltd. All rights reserved.
C. Thermogravimetric analysis (TGA)
D. Magnetic properties

1. Introduction bulk material. The properties of the synthesized materials are

Due to the unique physical and chemical properties, synthesis
and application of nanomaterials is the focus of intense research.
These materials are very attractive in view of both, their scientific
and technological importance. Nanocrystalline spinel ferrites with
the common formula MFe2O4 (M = Ni, Zn, Mn, Co, Mg, etc.) are the
most significant magnetic materials [1]. The spinel structure
belongs to space group Fd3m. The cubic unit cell is formed by 56
atoms, 32 oxygen anions dispersed in a cubic close packed
structure, and 24 cations occupying 8 of the 64 tetrahedral sites (A
sites) and 16 of the 32 octahedral sites (B sites) [2]. Nickel ferrite
powder, one of the very important ferrite materials has been
considered for many applications such as high density magnetic
storage media, MRI contrast agents, colour imaging, ferro-fluids,
high frequency devices, magnetic refrigerators, catalysts and
microwave devices [3–9]. Using a variety of chemical routes, a
specific study has been made to synthesis NiFe2O4 nanoparticles.
The magnetic behaviour of these nanoparticles depends mostly
on their size and synthesis route. The most common feature is
the ferromagnetic behaviour and the value is close to that of
the saturation magnetization in comparison with the related
* Corresponding author at: Department of Basic Engineering, T. S. Srinivasan
Centre for Polytechnic College and Advance Training (CPAT-TVS), Vanagaram,
Chennai – 600 095, Tamilnadu, India. Tel.: +91 9790898204; fax: +91 44 24760808.
E-mail address: p_siva1978@yahoo.co.in (P. Sivakumar).
influenced by the composition and microstructure, which are
sensitive to the preparation methodology used in their synthesis.
Many methods such as citric acid combustion method, sol–gel
auto-combustion method, organic gel-thermal decomposition
method, hydrothermal method, co-precipitation method, gel-
assistant hydrothermal route, thermolysis, wet chemical copreci-
pitation technique, self-propagating and microemulsion [10–21]
have been developed to prepare nanocrystallite nickel ferrite.
We display here the synthesis of nickel ferrite nanoparticles by
sol–gel auto-combustion method which is a unique combination of
the ignition and the chemical gelation processes. This method has
the advantages of simple preparation, cost-effective and gentle
chemistry route resulting in ultra fine and homogeneous powder.
The ability to obtain single-phase nickel ferrite magnetic nanopar-
ticles with controllable particle size and size distribution improves
its adequacy in a wide range of technological applications.
The project describes a simple and cost-effective way of
preparing of NiFe2O4 nanoparticles by sol–gel auto-combustion
method using nickel and ferric nitrates, ethylene glycol and citric
acid via polyvinyl alcohol (PVA). Further it illustrates the
structural, chemical composition, thermal morphology and mag-
netic study of the samples using X-ray diffraction (XRD), Fourier
transform infrared spectroscopy (FT-IR), thermo gravimetric
analysis (TGA), high-resolution scanning electron microscopy
(HR-SEM), transmission electron microscopy (TEM), high-resolu-
tion transmission electron microscopy (HR-TEM) and vibrating
sample magnetometry (VSM) studies.

0025-5408/$ – see front matter ß 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2011.09.009
 Author's personal copy

P. Sivakumar et al. / Materials Research Bulletin 46 (2011) 2208–2211 2209

2. Materials and methods
2.1. Materials
All the reagents are of analytical grade and are used as received,
without further purification. Nickel nitrate [Ni(NO3)26H2O], ferric
nitrate [Fe(NO3)39H2O], ethylene glycol [C2H6O2], citric acid
[C6H8O7] and polyvinyl alcohol (PVA) [C2H4O]n are purchased
from Sigma–Aldrich chemical reagent Co. (USA).
25 kV, the particle morphological features is imaged by high-
resolution transmission electron microscopy (HR-TEM) (FEI
Quanta FEG200). At room temperature, the magnetic measure-
ments are carried out in a vibrating sample magnetometer (VSM,
JDM – 13).
3. Results and discussion
3.1. XRD analysis

2.2. Methods The room temperature (300 K) of X-ray diffraction (XRD)

The NiFe2O4 ferrite is prepared by the sol–gel auto-combustion
method. The reagents used are nickel nitrate, ferric nitrate and
citric acid. An appropriate amount of metal nitrates and citric acid
are first dissolved in a minimum amount of ethylene glycol. The
molar ratio of nitrates is 1:2 and nitrates to citric acid are 1:1. Then
0.5 g and 0.25 g of polyvinyl alcohol (PVA) is added to the solution.
Here 0.5 g of PVA added to NiFe2O4 is labelled as sample-a and
0.25 g PVA added to NiFe2O4 is labelled as sample-b. The final
solution is magnetically stirred for 4 h at room temperature and
then surplus water is removed in a vacuum rotary evaporator at
60–80 8C until a gel is obtained. For about 10 h, the obtained gel is
dried in a hot air oven at 150 8C. Finally the brown colour nickel
ferrite powder is obtained.
2.3. Characterization
The structure, composition, morphology and magnetic proper-
ties of the gel precursor is characterized. Using PAN alytical X’ pert
and pro X-ray diffractometer with CuKa radiation (1.5406 Å)
source, X-ray diffraction pattern of the sample is recorded. Using a
step scan mode (0.068/s), the intensity data is collected over the
range of 20–808. Fourier transform infrared (FT-IR) spectrum is
recorded on Perkin Elmer 2000 FT-IR spectrometer in KBr pellets.
Using Perkin Elmer, STA 6000 Simultaneous Thermal Analyser, TGA
curve of synthesized product is determined. The rate of heating is
maintained at 10 8C per min and the mass of solid specimen is
40 mg. The measurements are carried out in nitrogen current at the
rate of 50 cm3 per min. Microstructural characteristics such as
morphology, particle size and crystal structure of the sample is
analysed by a high-resolution scanning electron microscope (HR-
SEM) (FEI Quanta FEG200). The TEM micrograph is obtained on a
JEM 3010 (JEOL) transmission electron microscope with an
accelerating voltage of 200 kV. With an accelerating voltage of
patterns of sample-a and nickel ferrite of sample-b are shown in
Fig. 1(a and b). Using powder X-ray diffraction (XRD), the crystal
structure, phase purity and particle size of nanoparticles of the
synthesized product have been investigated. In the X-ray
diffractogram for the product calculated at 150 8C, the most
intense XRD peak at 2u = 35.628 and plane spacing d = 2.494 Å
correspond to the (3 1 1) plane of NiFe2O4 nanoparticles (inverse
spinel structure) [22]. Of crystalline NiFe2O4, the considered
diffraction peaks with 2u values of 30.578, 35.978, 37.378, 43.678,
53.988, 57.628, 63.098, correspond to the crystal planes (2 2 0),
(3 1 1), (2 2 2), (4 0 0), (4 2 2), (5 1 1), (4 4 0), respectively. Accord-
ing to the standard of JCPDS (Card No. 10-0325) [23], it can be
indexed as inverse spinel and face centered cubic (fcc) structure
NiFe2O4. No diffraction peaks of other impurities such as a-Fe2O3,
NiO are observed. Using the broadening reflections of 311 and
Scherrer’s relation [24] X-ray line, the nano-sized nature of the
attained ferrite leads to broadening of the powder XRD peaks. The
crystallite size of NiFe2O4 sample is calculated.
Kl
D¼ (1)
bcosu
where l is the wavelength of the X-ray radiation (1.5406 Å), K is a
constant taken as 0.89, u is the diffraction angle and b is the full
width at half maximum (FWHM) [25], the average crystallite size is
found to be 24 nm and 30 nm in sample-a and sample-b
respectively.
3.2. FT-IR analysis
As shown in Fig. 2, the formation of spinel NiFe2O4 structure in
the synthesized nickel ferrite sample is further supported by FT-IR
spectrum. The bands between 3400 and 3784 cm1 could be
attributed to the O–H stretching vibration of H2O absorbed by the

100
3784

80
809
Transmittance (%)

488
670
1050

60

40
1625
3400

20
1316
1360

0
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)

Fig. 1. XRD patterns of the (a) sample-a and (b) sample-b of nickel ferrite sample. Fig. 2. FT-IR spectrum of the nickel ferrite sample.

2210
100
90
Weight Loss (%)
80
70
60
50
40
30
200 400 600
Temperature (ºC)
Fig. 3. Thermo gravimetric analysis (TGA) curve of nickel ferrite sample.
sample and the surface O–H or EG. The bands with the peaks at
488, 670 and 809 cm1 are assigned to the deformation vibration
of Fe–OH groups. The two main metal–oxygen bands at 670 cm1
and 488 cm1 are observed in the FT-IR spectrum of the
synthesized NiFe2O4 samples. These two bands are usually
assigned to vibration of ions in the crystal lattices [26]. This
indicates the presence of uniformly distributed ferrite particles.
The band at 670 and 488 cm1 correspond to the intrinsic
stretching vibrations of the metal at the tetrahedral site (Fe $ O)
[26,27]. The C55O stretching vibration characteristic peak located
at 1625 cm1 in the PVA red shifts in the composite [28]. The band
at 1050 cm1 shows the presence of C–O group vibration modes. At
1360 cm1 there is a significant change in the irrelevant peak of –
CH bending band. The 1316 cm1 peak is attributed to the
characteristic –CH3 bending.
3.3. TG analysis
Fig. 3 shows the thermo gravimetric analysis (TGA) trace of
NiFe2O4 sample. The decomposition process consists of three
regions. They are 50–150 8C, 150–480 8C and 480–640 8C. Owing to
the initial breakdown of the complex and spontaneous combus-
tion, the first weight loss region from 50–150 8C indicates the
evaporation of absorbed water. With the liberation of H2O, CO2 and
NOx and the nitrate ions providing an oxidizing environment for
the combustion of the organic components [13], the spontaneous
combustion is caused from the interactions of ethylene glycol,
citrate and nitrate ions in the gel. The second weight loss region
Fig. 4. (a) HR-SEM, (b) TEM and (c) HR-TEM photographs of the nickel ferrite nanoparticles for sample-b.
Author's personal copy
P. Sivakumar et al. / Materials Research Bulletin 46 (2011) 2208–2211
observed between 150 8C and 480 8C is ascribed to dehydration of
OH group in the spinel structure of some constituents such as NO3
and PVA, that lead to two degradation systems involving both inter
and intra-molecular transfer reaction, the oxidation of complexes
and formation of semi-organic carbon metal/metal oxide [29–31].
The third weight loss region in the temperature range of 480–
640 8C is believed to be due to the formation of corresponding
metal oxide and the spinel phase. Above 640 8C there is no weight
loss. From this study, it is seen that the TGA curve is steady,
demonstrating the absolute volatility of water, organic compound,
nitrates in the composites, the completion of crystallization route
and the immediate formation of pure nickel ferrite.
3.4. HR-SEM, TEM and HR-TEM analysis
Fig. 4(a–c) of sample-b shows that the size and morphology of
800 1000 the synthesized nanoparticles are characterized by HR-SEM, TEM
and HR-TEM. HR-SEM image shows that the nanoparticles have
uniform, almost spherical structural morphology with narrow size
distribution but with agglomeration to some extent. The sizes of
the particles, determined from the HR-SEM micrograph is of the
order of 30 nm. The TEM image of sample-b shows that the average
size is 30 nm. As seen in the HR-SEM image, the agglomeration is
not observed here. Fig. 4(c), indicating the growth direction,
exhibits the high-resolution transmission electron microscopy
lattice fringes of {3 1 1} planes with the lattice spacing of
0.2494 nm between the adjacent planes. As the grain growth
inhibitor, supporting the role of PVA, these structural studies
clearly illustrate the formation of large amount of distinct uniform
nanoparticles of NiFe2O4. Using Scherrer’s formula, it is estimated
from HR-SEM and TEM photographs that the particle size obtained
from XRD are consonant.
3.5. VSM analysis
Magnetic properties are measured by a vibrating sample
magnetometer. Fig. 5(a and b) of the NiFe2O4 samples (300 K) show
the magnetic hysteresis curves recorded at room temperature. It also
exhibits the ferromagnetic behaviour. The saturation magnetization
(Ms) and coercivity (Hc) of sample-b is 51.3 emu g1 and 250.8 Oe,
whereas Ms and Hc of sample-a is 47.23 emu g1 and 153.62 Oe. The
Ms of the NiFe2O4 nanocrystals is close to that of the corresponding
bulk material (about 50 emu g1) [32]. This is mainly due to the
substitution of a part of Ni2+ in octahedral sites by Fe2+ with a higher
magnetic moment (4.9 mB) [33]. Saturation magnetization of
sample-b is higher than sample-a, which is mainly due to the spin
canting effect of smaller crystalline size. It is reported that the
magnetic properties of the materials have been believed to be
dependent on the particles size, shape, magnetization direction,
 Author's personal copy
P. Sivakumar et al. / Materials Research Bulletin 46 (2011) 2208–2211
Fig. 5. Hysteresis curves for (a) sample-a and (b) sample-b of the nickel ferrite sample at room temperature (300 K).
crystallinity, etc. The magnetic behaviour of these materials
indicates a great promise of their use as materials for gas sensing
application.
4. Conclusion
Sol–gel auto-combustion process with the molar ratio of 1:1
and a nitrate–citrate gel synthesized using ethylene glycol from
metal nitrates and citric acid exhibits auto-combustion behav-
iour. The sol–gel auto-combustion method suits well for the
synthesis of nano-sized nickel ferrite. The PVA plays an important
role in the synthesis process of controlling particle size. The
powder XRD analysis reveals the high purity and single phase of
the nickel ferrite sample. The FTIR data support the formation of a
spinel phase and Fe2+ encroachment in octahedral site (B-site).
TGA measurement suggests that the sol–gel auto-combustion
process could take place at a relatively low temperature to form
spinel ferrite. HR-SEM and TEM images confirm that particles have
spherical shape, narrow size and uniform distribution. The
average crystallite size of 30 nm calculated from Scherrer’s
equation agrees well with the HR-SEM and TEM estimated
average particle size of 30 nm. The obtained HR-TEM result is a
good indication of each particle being a single crystal. The
magnetic measurement in sample-a and sample-b shows that the
nickel ferrite nanocrystals obtained in the synthesis have
ferromagnetic property, with a saturation magnetization (Ms)
of 47.23 and 51.3 emu g1. From these results we conclude that
the sol–gel auto-combustion process provides an interesting
synthesis technique with the advantages like low cost and simple
preparation.
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