Bull. Mater. Sci., Vol. 34, No. 7, December 2011, pp. 1325–1330. © Indian Academy of Sciences.

Synthesis and characterization of zinc ferrite nanoparticles obtained

by self-propagating low-temperature combustion method

P M PRITHVIRAJ SWAMY, S BASAVARAJA1, ARUNKUMAR LAGASHETTY2,

N V SRINIVAS RAO3, R NIJAGUNAPPA4 and A VENKATARAMAN*
Department of Materials Science, Gulbarga University, Gulbarga 585 106, India
1
Present address: Veeco-India Nanotechnology Laboratory,
Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560 064, India
2
Appa Institute of Engineering and Technology, Gulbarga 585 102, India
3
R&D Centre, Premier Explosives Pvt. Ltd., Hyderabad 500 015, India
4
Department of Environmental Sciences, Gulbarga University, Gulbarga 585 106, India

MS received 14 April 2010

Abstract. The self-propagating low-temperature combustion method was used to produce nanocrystalline
particles of zinc ferrite. The products were characterized for chemical and phase composition, morphology
and magnetic properties. The results obtained showed the formation of single-phase zinc ferrite nanoparticles
with an average particle size of about 40 nm. As-synthesized powder displayed good magnetic property. Due
to the simplicity and low cost of this process, it could also become a valuable starting point for the generation
of other mixed and complex ferrites.

Keywords. Zinc ferrite; self-propagating combustion method; magnetic property; X-ray diffraction;
morphology.

1. Introduction iron and metallic alloys is their high electrical resistivity

due to which ferrites perform much better at high fre-
In recent years, nanosized materials have been exten- quencies. High electrical resistivity prevents induction of
sively studied by researchers worldwide because of their eddy currents and the resultant loss of energy. High per-
unique physical properties, such as electrical conductivity, meability and temperature stability are other advantages.
optical bandgap, refractive index and magnetic proper- In addition, ferrites are more economically viable than
ties, and superior mechanical properties such as hardness most of other magnetic materials, and their magnetic and
of nanomaterials and chemical properties compared with mechanical properties can be ‘tailor made’ as per the
their counterpart bulk materials (Martin 1994). As the requirement of application.
research community is gaining a deeper understanding of Zinc ferrite (ZnFe2O4 ) is a commercially important
these unique behaviours and applications of nanostructured material and has been widely used as magnetic materials
materials, a new field of study known as ‘nanotechno- (Tanaka et al 1998; Sousa et al 2001; Grasset et al 2002;
logy’ has emerged (Bhattacharyya et al 2001; Kondic and Kundu et al 2003a; Bid and Pradhan 2003; Ehrhardt et al
Diez 2009). Among various nanomaterials, mainly spinel 2003; Deng et al 2005), gas sensor (Niu et al 2004), cata-
ferrite (MFe2 O4, M = Ni, Co, Mn, Zn, etc.) nanoparticles lysts (Toledo-Antonio et al 2002), photocatalysts (Qiu
have become immensely popular magnetic materials for a et al 2004), absorbent materials (Pineda et al 1997;
wide variety of applications such as electronic ignition Kobayashi et al 2002a, b; Tomás-Alonso and Palacios
systems, generators, vending machines, medical implants, Latasa 2004; Ikenaga et al 2004) and so on. Zinc ferrite
wrist watches, inductor core, transformer circuits, mag- has been reported from high-temperature solid-state reac-
netic sensors and recording equipment, telecommunica- tion, high-energy ball-milling (Bid and Pradhan 2003;
tions, magnetic fluids, microwave absorbers and other Ehrhardt et al 2003; Shenoya et al 2004), sol–gel
high-frequency applications (Snelling 1989; Jiles 1991; (Hamdeh et al 1997), hydrothermal technique (Toledo-
Willard et al 2004; Mathew and Jiang 2007). A distinct Antonio and Palacios Latasa 2002), coprecipitation
merit of ferrites over other magnetic materials such as (Kundu et al 2003b), rapid quenching (Tanaka et al
1998), liquid mix process (Kundu et al 2003a), thermal
plasma (Mohair et al 2001), etc. However, some of these
*Author for correspondence ([email protected]) methods encountered problems such as the formation of

1325
1326 P M Prithviraj Swamy et al

undesirable phase, the requirement of complicated 2.2 Preparation of ZnFe2 O4

equipment or are time consuming due to multiple steps,
etc. It is intriguing to develop an inexpensive, facile and The ferrous oxalate, zinc oxalate precursors were mixed
fast method in the preparation of single phase zinc ferrite. with PEG in a weight ratio 1 : 1 : 5, respectively, and
Self-propagating combustion synthesis is an exother- ground well with a mortar and pestle. The resultant solid
mic redox reaction between metal nitrates (oxidizing was placed in a silica crucible and heated in air. It was
agents) and an appropriate fuel (a reducing agent) and observed that initially PEG melted, then frothed and
had been successfully used in synthesizing nanocrystal- finally ignited to give ZnFe2 O4 as a residue. On cooling
line metal oxides recently (Tao et al 1997). Compared to room temperature, no traces of carbon impurities were
with other methods, the combustion synthesis exhibits the observed in the final residue of ZnFe2O4. As the reaction
following advantages: a good chemical homogeneity, is fast, i.e. going to completion within 10 min, and ignites
simple equipment and preparation process, inexpensive auto-catalytically, the exact temperature of the reaction
raw materials, fast production rate, etc. In this paper, we could not be measured. However, using a thermocouple
report the synthesis of ZnFe2 O4 nanoparticles through a the highest temperature of the reaction was found to
self-propagation low-temperature combustion route em- be around 500°C. The ZnFe2 O4 was then characterized
ploying metal oxalate precursors. In search of a suitable for its structure (employing XRD), morphology (employ-
economic fuel, our use of polyethylene glycol (PEG) has ing SEM), particle size determination (employing TEM),
given promising results in a single step. Some of the pos- etc.
sible reasons for employing PEG in the present study are:
PEG has a sharp melting point (62°C) and decomposition
3.3 Characterization techniques
temperature, and these are widely separated. The car-
boxylate precursors get well dispersed in the molten
Simultaneous thermogravimetric and differential scan-
polyethylene glycol on its melting. PEG is known to be a
ning calorimetry (TG/DSC) traces were obtained from
good surfactant, and a dispersant and hence, ultrafine and
Mettlar Teledo Star instruments (Weinheim, Germany)
nanomaterials are expected to be formed as the final
under a dynamic flow of nitrogen at a flow rate of
products on combustion. PEG has alcoholic groups and
100 ml/min and at a heating rate of 10°C/min. The XRD
it burns in air exothermically with precursors to form
pattern was obtained employing a JEOL JDX-8p spec-
desired metal oxides/ferrites. In our earlier studies we
trometer using CuKα radiation (λ = 1⋅54 Å). The X-ray
have successfully used this fuel for the synthesis of
generator was operated at 30 kV and 20 mA. The scan-
γ-Fe2 O3 and other metal oxides from different precursors
ning range, 2θ, was selected. The FT–IR spectrum of
(Venkataraman et al 2001; Lagashetty et al 2005;
ZnFe2O4 nanoparticles was recorded on a Perkin–Elmer
Basavaraja et al 2007). The structure and morphology of
Spectrum One instrument in the range 4000–400 cm–1 at
the as-prepared nanocrystalline ZnFe2O4 was character-
a resolution of 4 cm–1 by making KBr pellets. The scan-
ized and its magnetic properties were studied. Our results
ning speed of 1°/min and a chart speed of 20 mm/min
show that self-propagating combustion is a fast and con-
were used for the precise determination of the lattice
venient method in the preparation of nanocrystalline
parameters. The morphology of the nanoparticles was
ZnFe2O4 .
characterized using coupling JSM-840A scanning elec-
tron microscope. The electron microscope was operated
2. Experimental at 20 kV. The sample was made conducting by the sput-
tering of gold using a Poloron DC ‘sputtering unit’ oper-
All the chemicals were of AR grade and were used as ated at 1⋅4 kV and 18–20 mA. Sample for TEM was
received. Double-distilled water was used for preparation prepared by placing a drop of the ethanol suspension of
of the required solutions. the nanoparticles on carbon-coated Cu TEM grids and
subsequently drawing off excess solvent. The grids were
examined using a Philips CM 200 transmission electron
2.1 Preparation of metal oxalates
microscope operating at 200 kV. The preliminary mag-
netic measurements of the sample were recorded at room
An equimolar solution of ferrous ammonium sulphate
temperature on a Magneta, magnetic hysteresis loop
heptahydrate/zinc nitrate and oxalic acid were dissolved
tracer.
in minimum quantity of water and was stirred well. The
respective metal oxalate precipitate obtained was filtered
through a sintered glass crucible and was washed with 3. Results and discussion
cold distilled water and alcohol until it was free from
sulphate/nitrate ions and oxalic acid, and the filtrate was Thermal analysis was performed to understand the com-
finally washed with dry acetone and then dried under bustion process used for the synthesis of the zinc ferrite
vacuum. sample. Simultaneous TG/DSC traces of the mixture of
 Synthesis and characterization of zinc ferrite nanoparticles 1327

Figure 1. TG–DSC traces of precursors.

precursor (ferrous oxalate : zinc oxalate 1 : 1 ratio) is 0⋅48–0⋅51 in as synthesized sample, indicating that this
shown in figure 1. The trace showed a multistep weight sample is indeed zinc ferrite with the chemical formula of
loss. The weight loss from room temperature to 100°C is ZnFe2O4 .
attributed to desorption of water molecules present in the The mean particle diameter was calculated from the
sample, which appear on the DSC curve as an endother- XRD pattern according to the line width of the (3 1 1)
mic peak at 60°C. No considerable change in weight loss plane refraction peak using the following Debye–Scherrer
is observed from 100 to 240°C. Thereafter, a continuous equation (Cornell and Schwertmann 1996):
two step weight loss is noticed in the temperature ranging
from 240 to 600°C, showing a maximum weight loss, Kλ
D= .
which also appeared as two broad endothermic peaks, at β1/2 cosθ
273 and 540°C on the DSC trace. This weight loss is at-
tributed to the decomposition of the oxalate precursor. The equation uses the reference peak width at angle θ,
The last broadened exothermic peak with small weight where λ is the X-ray wavelength (1⋅5418 Å), β1/2 is the
loss could be considered as a solid state reaction attrib- width of the XRD peak at half height and K is the shape
uted to the gradual formation of zinc ferrite (Benito et al factor, about 0⋅9 for spherical shaped particles. The aver-
2001). After 850°C, no further distinguishable weight age crystallite size calculated from peak width is about
loss was detected, indicating that all organic constituents 40 nm, which is in accordance with the TEM results dis-
were eliminated. During the combustion, large amounts cussed later.
of gases such as H2 O, CO, CO2 and NO are liberated Fourier transform infrared (FT–IR) studies were per-
(Mali and Ataie 2004). formed to ascertain the metal–oxygen bonding. The FT–
The phase and purity of the as synthesized ZnFe2 O4 IR spectrum of as synthesized ZnFe2 O4 sample is shown
was examined by X-ray diffraction (XRD) pattern and is in figure 3. The ZnFe2 O4 shows the absorption in the re-
shown in figure 2. The intensity and ‘d’ values of the gion 3402, 1620, 630, 555 and 450 cm–1. The peaks at
entire observed diffraction peaks perfectly match with the 630 and 555 cm–1 correspond to the metal–oxygen (Fe–O
single-crystalline cubic spinel form of zinc ferrite stretching vibrations) vibrational modes and corroborat-
(JCPDS Card No. 82-1049) having lattice constant ing the spinel structure characteristics of zinc ferrite (Rao
a = 8⋅440 Å with space group Fd3m (227). Absence of et al 1970). This result is also in agreement with that of
any peak from ZnO, Fe2 O3 or any other oxide phases con- Waldron (Waldron 1955), assigned the high-frequency
firmed the formation of phase pure zinc ferrite. Accord- bands to the tetrahedral group (630 and 555 cm–1 region)
ing to the cubic crystal structure of spinel phase, the and the low-frequency bands to octahedral group
values of lattice parameter a determined from the most (450 cm–1 ). The peak at 3402 and 1620 cm–1 corresponds
intense (3 1 1) reflection of XRD patterns using the for- to water of hydration (Rao 1963). This was further
2
mula (1/dhkl = (h2 + k2 + l2 )/a2, h k l = 3 1 1) are 8⋅435 Å, supported by the weight loss measurements of thermo-
respectively, well consistent with that of bulk ZnFe2 O4. gravimetric analysis. The peak at 1095 cm–1 is due to
Elemental analysis by ICP-ES gives Zn/Fe atomic ratio of overtones.
1328 P M Prithviraj Swamy et al

Figure 2. XRD pattern of ZnFe2O4.

The SEM photograph of ZnFe2 O4 sample (figure 4)

reveals that sample exhibit a compact arrangement of
homogeneous nanoparticles with roughly spherical shape.
Most of the particles are aggregated, and so it is difficult
to determine the exact size and shape of the particles.
Hence, the exact size and shape of the ZnFe2 O4 particles
were examined by TEM images.
TEM was employed to visualize the size and shape and
to confirm the nanocrystalline nature of the as synthe-
sized zinc ferrite. Figure 5 shows the typical bright field
TEM image of the as synthesized zinc ferrite nanoparti-
Figure 3. FT–IR spectrum of ZnFe2O4. cles. The TEM image clearly shows dense assembly of
uniformly sized ferrite nanoparticles. The whole surface
of the grid was covered with ferrute nanoparticles as
shown in this image. It can be seen from the TEM image
that the distribution of zinc ferrite nanoaprticles are
polydispersed and are essentially spherical.
A particle size distribution histogram determined from
TEM image is shown in figure 6. It can be seen that the
mean particle size is ca. 45 nm with almost 93% of the
particles are in the range 25–100 nm, with a small
percentage having diameters between 150 and 300 nm.
The particle sizes range from as low as 25 nm to as high
as 300 nm. The particle size distribution is broader and
indicates the polycrystalline nature. The average particle
size from the TEM and histogram is 45 nm, which is also
in accordance with the result calculated by the Scherrer
formula.
Figure 4. SEM image of ZnFe2O4. The selected-area electron diffraction (SAED) pattern
of the zinc ferrite is shown in figure 7. The ED pattern
consists of concentric rings with spots over the rings.
The morphological characteristics of the obtained This feature indicates the samples are crystalline in
ZnFe2O4 were investigated by SEM and TEM analysis. nature (Wang et al 2001; Pawaskar et al 2002).
 Synthesis and characterization of zinc ferrite nanoparticles 1329

Preliminary magnetic measurements were performed for the zinc ferrite nanoparticles measured at room tempe-
on the zinc ferrite nanoparticles with the use of magnetic rature (300 K), in the range H = ± 10 kOe. The saturation
hysteresis loop tracer. Figure 8 shows the hysteresis loop magnetization (Ms) obtained at room temperature was
found to be 78⋅54 emu/g, remanent magnetization (Mr)
was 74⋅97 emu/g and coercivity (Hc) was 1297⋅52 Oe.
The very large coercivity and low saturation magnetiza-
tion at 300 K are consistent with a pronounced growth
of magnetic anisotropy inhibiting the alignment of the
moment in an applied field (Maaz et al 2007).

4. Conclusions

Self-propagating low-temperature synthesis offers a fast,

relatively straightforward, single-step method for the syn-
thesis of nanosized zinc ferrites. The characterization

Figure 5. TEM image of ZnFe2O4.

Figure 7. Particle size histogram of ZnFe2O4 derived from

TEM image.

Figure 6. SAED pattern of ZnFe 2O4. Figure 8. MH spectrum of ZnFe2O4.

1330 P M Prithviraj Swamy et al

results show the formation of zinc ferrite with small Kondic L and Diez J A 2009 Phys. Rev. E79 026302
nanoparticle sizes. The use of PEG as a fuel and as a con- Kundu A, Anand S and Verma H C 2003a Powder Technol. 132
trollable oxidant in the synthesis of zinc ferrite suggests 131
that this combustion route is simple and can be applied Kundu A, Upadhyay C and Verma H C 2003b Phys. Lett. A311
410
for the synthesis of other ferrites and metal oxides.
Lagashetty A, Havanoor V, Basavaraja S and Venkataraman A
Because of the low cost of this process and the 2005 Bull. Mater. Sci. 28 477
starting materials, this synthetic will be of interest to in- Maaz K, Mumtaz Arif, Hasanain S K and Ceylan Abdullah
dustries. 2007 J. Magn. Magn. Mater. 308 289
Mali A and Ataie A 2004 Ceram. Int. 30 1979
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