Advances in Materials Physics and Chemistry, 2017, 7, 19-27

http://www.scirp.org/journal/ampc
ISSN Online: 2162-5328
ISSN Print: 2162-531X

Effect of Annealing Temperature on the

Structural and Magnetic Properties of
NiFe2O4 Nanoferrites

A. Sangeetha1*, K. Vijaya Kumar2, G. Nanda Kumar3

1
Department of Physics, Indur Institute of Engineering and Technology, Siddipet, India
2
Department of Physics, Jawaharlal Nehru Technological University, Hyderabad College of Engineering, Nachupally
(Kondagattu), Karimnagar-Dist., Telangana, India
3
Department of Geo-Physics, Osmania University, Hyderabad, India

How to cite this paper: Sangeetha, A., Abstract

Kumar, K.V. and Kumar, G.N. (2017) Ef-
fect of Annealing Temperature on the Stru- Nanocrystalline NiFe2O4 spinel ferrites were synthesized by sol-gel method.
ctural and Magnetic Properties of NiFe2O4 The structural and magnetic properties were investigated using X-ray diffrac-
Nanoferrites. Advances in Materials Phys-
tion (XRD), Fourier Transform Infrared (FTIR) spectroscopy, Scanning Elec-
ics and Chemistry, 7, 19-27.
https://doi.org/10.4236/ampc.2017.72003 tron Microscopy (SEM) and Vibrating Sample Magnetometer (VSM). An-
nealing temperature showed prominent effect on the grain size. The average
Received: December 15, 2016 grain size of NiFe2O4 was observed to increase from 31 nm to 54 nm as the
Accepted: February 6, 2017
Published: February 9, 2017
annealing increased from 500˚C to 1000˚C. The IR spectra showed the ab-
sorption bands corresponding to stretching of tetrahedral and octahedral
Copyright © 2017 by authors and bands. The magnetic properties were observed to depend strongly on the an-
Scientific Research Publishing Inc.
nealing temperature.
This work is licensed under the Creative
Commons Attribution International
License (CC BY 4.0). Keywords
http://creativecommons.org/licenses/by/4.0/
Sol-Gel, Nickel Ferrite, Crystallite Size, Structural Properties,
Open Access
Magnetic Properties

1. Introduction
Nickel ferrite (NiFe2O4) is an important member of the spinel family and it is
found to be the most versatile technological material suited for high-frequency
applications due to its high resistivity [1] [2]. In the bulk state, this material pos-
sesses an inverse spinel structure, in which tetrahedral (A) sites are occupied by
Fe3+ ions and octahedral (B) sites by Fe3+ and Ni2+ ions. It is found from litera-
ture that ferromagnetism in NiFe2O4 originates from the antiparallel orientation
of spins at (A) and (B) sites. Recently graphene oxide based inverse spinel nickel

DOI: 10.4236/ampc.2017.72003 February 9, 2017

A. Sangeetha et al.

ferrite nanocomposite was used for uranium, thorium and dipyrone removal [3]
[4]. Nickel ferrite nanoparticles in calcium phosphate nanostructure for organic
modifier followed by rapid thermal processing in biomedical applications [5],
rare earth doped nickel ferrites as fuel [6], Ni ferrite powders are prepared by
plasma arc discharge process [7].
Previously several researchers have worked on NiFe2O4 materials in bulk, na-
no and thin film form and they presented interesting results. Unexpected mag-
netism in some ferrites has been observed due to homogenous mixing [8], with-
out post annealing [9] or with annealing [10]. However, there are only few ar-
ticles which explain the effect of annealing temperature on ferrite nanomaterials
and especially on Nickel ferrites. Therefore, in this present work, we are report-
ing in detail the structural and magnetic properties of NiFe2O4 nanoparticles due
to effect of annealing temperature. The NiFe2O4 nanoferrites were characterized
by using X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) and Scan-
ning Electron Microscopy (SEM) and the magnetic properties were investigated
using Vibrating Sample Magnetometer (VSM) with an applied of 10 kOe at
room temperature.

2. Experimental Procedure
NiFe2O4 nanoferrites were prepared by using sol-gel method [11]. The a.r. grade
citric acid (C6H8O7·H2O), nickel nitrate (Ni(NO3)2·6H2O), ferric nitrate
(Fe(NO3)3·9H2O) from SD fine chemicals were used as starting materials. The
synthesis technique is described in detail elsewhere [11]. The obtained raw
powders were annealed separately at different temperatures ranging from 500˚C,
600˚C, 700˚C, 800˚C, 900˚C and 1000˚C for 5 hours.
XRD analysis was measured using Philips PW 3020 Bragg-Brentano dif-frac-
tometer using Cu Kα radiation (wave length λ = 1.54 Å). The morphology of
powder was observed using scanning electron microscopy (SEM) from Carl
Zeiss. The structural changes were observed using ABB Bomem MB 102 infrared
spectrometer. The samples were mixed with KBr and made in the form of pellets
and recorded at 4 cm−1 resolution giving the spectra in the 4000 - 200 cm−1
range. Room temperature magnetization was measured using ADE magnetics
DMS 4 Vibrating Sample Magnetometer (VSM) Ltd.

3. Results and Discussions

Figure 1 shows the XRD patterns of NiFeO4 nanoferrite samples annealed from
500˚C, 600˚C, 700˚C, 800˚C, 900˚C and 1000˚C for 5 hours. The XRD peaks
correspond to the formation of NiFeO4 ferrite structure. A close examination of
XRD peaks reveals that the peaks became narrower and sharper. This might be
due to the increase in the grain size. The crystallite sizes for all the samples were
measured by considering the most intense (311) peak of XRD using the Debye-
Scherrer Formula (1).
0.9λ
D= (1)
β cos θ

20
 A. Sangeetha et al.

Figure 1. XRD patterns of NiFe2O4 nanoferrites annealed at different tem-

peratures.

where, D is the crystallite size, λ is the wavelength, β is the full width at half
maxima (FWHM) and θ is the Bragg’s angle.
With the increase in the annealing temperature from 500˚C to 1000˚C, the
grain size was observed to increase from 31 to 54 nm as shown in Table 1.
The annealing temperature showed the significant effect on the NiFe2O4 grain
size. This might be directly related to the crystallization of the nanoparticles. A
straight line of ln(d) against 1/T (Figure 2) is plotted according with the Scott
Equation (1) under the homogeneous growth rate conditions of nanocrystallites
[12] [13]. The Scott equation describes the growth rate of nanocrystallites as a
result of thermal treatment of amorphous compounds.
=d C exp ( − E RT ) (2)

where, d is the grain size calculated from XRD, C is a constant, E is the activa-
tion energy for grain growth, R is the ideal gas constant and T is the absolute
temperature.
There exists a good linear relationship between lnd and 1/T. E values could be
calculated from the slope of the straight line, presented in Figure 2. As E = 11.4
kJ/mol, it can be considered that the grain grows primarily due to the interfacial
reaction. Therefore, it can be confirmed that NiFe2O4 nano crystals are easily af-
fected with the annealing temperature as shown in Figure 2. In our NiFe2O4
samples, we observed the activation energy of 11.4 kJ/mol compared with 18.5
kJ/mol for ball milled NiFe2O4 samples [13].
The IR spectra of NiFe2O4 nanoparticles annealed at different temperatures
are presented in Figure 3. NiFe2O4 gives rise to two main absorption bands,
consisting of metal-oxygen stretching bands v1 and v2, in the range 600 - 540
cm−1 and 400 - 380 cm−1, respectively. Considering the inverse spinel structure of

21
A. Sangeetha et al.

Table 1. Dependence of grain size D, saturation magnetization MS and coercive field HC

on different temperatures.

Temperature ˚C D (nm) MS (emu/g) HC (Oe)

500 31 29.7 199
600 35 31.8 151
700 42 35.9 129
800 46 40.9 121
900 49 44.2 69
1000 54 34.9 54

Figure 2. Plot of ln(d) against 1/T. Line presents a linear fit for
ln(d) vs. 1/T dependence.

Figure 3. IR spectra of NiFe2O4 nanoferrites annealed at dif-

ferent temperatures.

22
 A. Sangeetha et al.

the NiFe2O4 it is represented by general formula Fe3+[Ni2+Fe3+]O4, where square

brackets represents the octahedral sites [14], v1 band corresponds to intrinsic
stretching vibrations of tetrahedral Fe3+-O, while v2 is assigned to Fe3+-O and
Ni2+-O bond stretching vibrations of octahedral sites [15]. Therefore, IR analysis
clearly showed the formation of the inverse spinel structure of NiFe2O4 and the
band positions were observed to shift their positions with the increase in an-
nealing temperature from 500˚C to 1000˚C.
Figure 4 shows the SEM micrographs of NiFe2O4 samples annealed at 500˚C,
800˚C, 900˚C and 1000˚C. The SEM micrographs show a slight agglomeration
among the particles. These nanoparticles distinctly exhibit narrow particle size
distribution. SEM image of the sample fired at 500˚C, Figure 4(a) shows that the
microstructure has fairly small grain size. As the annealing temperature was in-
creased to 800˚C and 900˚C, Figure 4(b) to Figure 4(c) a clear crystal structure
having homogeneous microstructure with uniform size distribution. With the
further increase of annealing temperature up to 1000˚C, Figure 4(d) a non-
uniform grain growth with the presence of intragranular pores was observed. It
was observed in other ferrite samples that the sample fired at 1300˚C showed
abnormal grain growth and closed pores [16]. Suck kind of pores may be ac-
counted for the poor physico-mechanical properties and decrease in magnetiza-
tion. In the present case, the samples fired at 1000˚C (Figure 4(d)) did not show
any abnormal grain growth and very small amount of pores were observed in
comparison with other ferrite materials [17].

Figure 4. SEM micrographs of NiFe2O4 nanoferrites annealed at temperatures

(a) 500˚C, (b) 800˚C, (c) 900˚C and (d) 1000˚C.

23
A. Sangeetha et al.

The room-temperature magnetization measurements for all the annealed

NiFe2O4 samples from 500˚C to 1000˚C are shown in Figure 5. The derived pa-
rameters are shown in Table 1. The saturation maximum magnetization for
500˚C annealed sample was found to be 29.7 emu/g, which is about 40% smaller
than the saturation magnetization of 50 emu/g of bulk NiFe2O4 samples [17]. As
the annealing temperature was increased to 900˚C, the saturation magnetization
was observed to be 44.2 emu/g, which is equal to the saturation magnetization of
bulk NiFe2O4 ferrite samples [13].
It is clearly observed that the saturation magnetization increased with increase
in the annealing temperature and grain size. Similar kind of magnetization be-
havior was observed for different ferrite systems. In addition, the reduced mag-
netization in nanomaterials also leads to the reduced ordering temperature and
increased anisotropy [18]. Therefore, the reduced magnetization in nanoferrites
is often connected to the existence of a “magnetically dead” layer at the surface
of particles explained in terms of core-shell exchange-coupling [19], where a fer-
rimagnetic core is surrounded by a surface layer of canted spins. However, in the
case of some nanoferrites the core-shell model failed to explain the enhancement
of magnetization [20] [21] [22]. It is observed that the reduction of magnetic
moment is observed only in the case when the effect of spin canting in the shell
dominates over the effect of cation disorder; otherwise an unusual phenomenon
like the magnetization enhancement may be expected [23]. The reduced magne-
tization with the decreasing particle size observed in the present case can be at-
tributed to the prevailing effect of spin non-collinearity in the near-surface layers
of the NiFe2O4 crystals. It is noted that the decrease in the magnetization in the
case of the sample annealed at 1000˚C may be due to the excessive temperature
which quickens the ion diffusion during annealing and the formation of pores.
As a consequence, the domain wall movement becomes difficult, which causes

Figure 5. Hysteresis loops for NiFe2O4 nanoferrites annealed at dif-

ferent temperatures.

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 A. Sangeetha et al.

Figure 6. Variation of magnetization in 10 kOe and coercive field for

NiFe2O4 nanoferrites annealed at different temperatures.

the magnetization to decrease. A similar change in magnetization with the an-

nealing temperature was observed for CuFe2O4 nanoparticles [16]. Further, due
to the formation of pores higher annealed samples has resulted in the decrease of
magnetization.
The coercivity was observed to decrease with increasing annealing tempera-
ture as shown in Figure 6. The coercivity in the case of 500˚C annealed sample
is nearly three times more than that of the bulk NiFe2O4 [24]. With the increase
in annealing temperature the coercivity gradually decreased and attained a
minimum value of 7.2 Oe. The decrease in the coercivity with annealing temper-
ature may also be accounted for the multi domain nature in the samples at high-
er annealing temperatures [25].

4. Conclusion
NiFe2O4 nanoferrites were successfully synthesized using sol-gel method. The
grain size was observed to increase with increasing annealing temperature. The
activation energy was observed to be 11.4 kJ/mol. The annealing temperature
showed significant effect on the grain growth. The IR analysis confirmed the fer-
rite phase formation by showing the bands corresponding to the tetrahedral and
octahedral sites. The saturation magnetization was observed to increase with in-
crease of grain size as a consequence of annealing temperature. Pores were ob-
served to form with higher annealing temperature of 1000˚C due to which mag-
netization decreased. The coercivity decreased with increasing annealing tem-
perature.

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