Ceramics International 48 (2022) 35719–35732

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Structural, optical, dielectric, and magnetic properties of spinel MFe2O4 (M

= Co and Zn) nanoparticles synthesized by CTAB-assisted
hydrothermal method
Mrinal Saha a, Siddhartha Mukherjee a, Parthasarathi Bera b, **, Md. Motin Seikh c, Arup Gayen d, *
a
Department of Metallurgical & Material Engineering, Jadavpur University, Kolkata 700032, India
b
Surface Engineering Division, CSIR− National Aerospace Laboratories, Bengaluru 560017, India
c
Department of Chemistry, Visva-Bharati, Santiniketan 731235, India
d
Department of Chemistry, Jadavpur University, Kolkata 700032, India

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

Keywords: Nanostructured MFe2O4 (M = Co and Zn) ferrites have been successfully synthesized by hydrothermal method
Nanostructured spinel using cetyltrimethylammonium bromide (CTAB) as a surfactant and ammonium hydroxide (NH4OH) as a
Hydrothermal synthesis precipitating agent at a moderate temperature (~160 ◦ C) for 10 h and subsequent calcination of the precursors at
CTAB-Assisted
400 and 600 ◦ C. These ferrite materials have been characterized by X-ray diffraction (XRD), BET surface area,
Hexagonal CoFe2O4
Spherical ZnFe2O4
scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM), high resolution
Ferromagnetic CoFe2O4 transmission electron microscopy (HRTEM), thermogravimetric analysis− differential scanning calorimetry
Paramagnetic ZnFe2O4 (TGA− DSC), Fourier transformed infrared (FTIR) spectroscopy, Raman spectroscopy, and X-ray photoelectron
spectroscopy (XPS). The CoFe2O4 is found to have both hexagonal and spherical surface morphologies and for
ZnFe2O4 a spherical morphology is obtained at 600 ◦ C. Optical, dielectric, and magnetic properties of these
ferrites have been investigated. CoFe2O4 exhibits ferromagnetism at room temperature. In contrast, ZnFe2O4
shows paramagnetism at room temperature. The Ms and Hc values are observed to increase, respectively, from
74.2 emu g− 1 to 78.9 emu g− 1 and 1221 Oe to 1411 Oe for CoFe2O4 as the calcination temperature increases
from 400 ◦ C to 600 ◦ C. This is related to better crystallinity because of calcination at higher temperature.
Dielectric properties of the ferrite materials are also enhanced with the increase in the calcination temperature.

1. Introduction physical properties of the nanomaterials that include mechanical, opti­

In recent years, the spinel ferrites have drawn considerable attention
of the researchers due to their multifaceted applications in various fields
such as high frequency magnetic materials, catalysts, energy materials,
gas sensors, microwave absorbing materials, antibacterial materials,
biomedical materials, water decontaminants, refractory materials, and
electrical devices [1–18]. There are two major factors that contribute
significant differences in the chemical and physical properties of nano­
ferrite materials from the bulk materials. First, the surface effects which
changes the properties due to the large fraction of atoms at the surface;
and second, the quantum confinement effects where electrons are
spatially confined affecting the electronic energy states in lower
dimension [19]. These factors highly affect the chemical activity and
cal, electrical, and magnetic properties.
Common formula of spinel ferrites is AB2O4. The unit cell of AB2O4
contains 32 oxygen atoms in cubic close packing with 8 tetrahedral (A
atoms) and 16 octahedral (B atoms) occupied sites. Magnetic property of
ferrite materials arises due to differences in the magnetic moments of the
cations distributed at the A and B sites. It also depends on the super­
exchange interactions through oxygen, JAB (A− O–B), JAA(A− O− A) and
JBB (B–O–B). The ferrimagnetism occurs due to the strong interaction of
JAB [4]. Magnetocrystalline anisotropy, spin canting effect, and dipolar
interactions between the moments on the surface of the nanoparticles
also influence the magnetic property.
Nanosized spinel ferrite materials for the wide range of applications
have been developed by various synthesis methods, such as mechanical,

* Corresponding author.
** Corresponding author.
E-mail addresses: partho@nal.res.in (P. Bera), agayenju@yahoo.com, arup.gayen@jadavpuruniversity.in (A. Gayen).

https://doi.org/10.1016/j.ceramint.2022.07.058
Received 15 April 2022; Received in revised form 25 June 2022; Accepted 7 July 2022
Available online 11 July 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
M. Saha et al.
sol-gel, sonochemical, microemulsion, coprecipitation, solution com­
bustion, hydrothermal, and complexometry [2,5,14,20–24]. Within this
context, investigation on the modification of shape, size or morphology
of the spinel ferrites and their influence on properties has been an
important topic of research in materials science since several years. The
properties of spinel ferrite can be tuned by changing the synthesis
routes. Among the preparation methods, hydrothermal synthesis is a
simple, flexible, and powerful method for the preparation of high purity
crystalline nanomaterials with different kinds of surface morphologies.
It is probably the most effective process to obtain weakly agglomerated
as well as homogeneous size distribution of nanoparticles. Further,
amidst spinel ferrites, CoFe2O4 and ZnFe2O4 have significant applica­
tions in catalysis, photocatalysis, magnetic storage, electromagnetic
interference shielding, biomedical, gas sensing, etc. [1,5–13,25–29].
The bulk form of CoFe2O4 is strong ferrimagnetic, whereas ZnFe2O4 is
paramagnetic at room temperature. In this regard, there are quite a large
number of reports on the synthesis of MFe2O4 ferrite (M = Co and Zn) via
hydrothermal route with varied degree of material properties [30–55].
Several reports have pointed out the direct achievement of desired fer­
rites [30,31,33,34,36–38,40,43,46,50,54], whereas a significant num­
ber of the reports follow the subsequent heat treatment of the product
obtained from hydrothermal reaction [32,35,39,41,42,44,45,47–49,
51–53,55]. Another feature is that several reports show the presence of
secondary impurity phases such as Fe2O3 and β-FeOOH, which requires
heat treatment to eliminate that impurity [56,57]. It has also been
observed that the ferrites can be synthesized by using hydrothermal
route through varying conditions, such as pH, surfactant, time, and
synthesis temperature, subsequent heat treatment, etc. Surfactants such
as cetyltrimethylammonium bromide (CTAB), polyethylene glycol
(PEG) are used to hinder the goethite formation and has influence on
oxidation state of A-site metal, crystallinity, and morphology [30,31,
39]. Das et al. have studied the influence of CTAB on the size,
morphology, and agglomeration of CoFe2O4 nanoparticles by hydro­
thermal method [39]. However, as a whole, there is no rationality in
shape, size or morphology of the ferrites obtained by changing the re­
action conditions. This provides the unique opportunity to further
explore the synthesis of ferrites through controlling the hydrothermal
route.
In the present work, synthesis of MFe2O4 (M = Co and Zn) ferrites by
CTAB-assisted hydrothermal method has been investigated. The pure
phase products are obtained by calcining the hydrothermal product at
400 and 600 ◦ C. The selection of CoFe2O4 and ZnFe2O4 as well as
heating at two different temperatures has been done purposefully to
explore the evolution of shape, size or morphology of the ferrites and
their influence on optical, dielectric, and magnetic properties. For cobalt
ferrite, hexagonal and spherical shapes depending on calcination tem­
perature have been obtained, whereas morphology of zinc ferrite is
spherical only. It is to be noted that the hexagonal shape of CoFe2O4 is
observed for the first time by hydrothermal synthesis. Furthermore,
annealing has been done to improve the quality of crystallinity of the
nanoparticles. Such calcination is also required to eliminate the un­
wanted organic matter accompanying the desired product. It has been
recently reported by Ghosh and coauthors that CoFe2O4 prepared by
calcination of metal-organic framework precursor shows remarkable
effect on magnetic properties by annealing the sample at the same
temperature for different time spans [58]. The sample annealed for a
longer time gives four times larger magnetization. The observed
magnetization has been ascribed to the influence of annealing time to
cationic distribution in A and B-sites of the CoFe2O4 spinel. Accordingly,
it is anticipated that the similar hydrothermal precursors annealed at
different temperatures may produce different magnetization. In this
study, it is observed that unlike ZnFe2O4 the magnetic property of
CoFe2O4 is sensitive to the annealing temperature. Effect of calcination
temperature has also been noticed in their electrical properties.
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2. Experimental details
2.1. Materials
All chemicals were used in as-purchased condition without further
purification and were of analytical grade. Nitrate salts of Co(II), Zn(II),
and Fe(III) purchased from E-Merck, Germany were used for the syn­
thesis of ferrites. The purity levels of the precursors were >99.9%.
Cetyltrimethylammonium bromide (Merck, purity >99%) was used as
the surfactant. Ammonium hydroxide (Merck, purity >99%) was used as
the precipitating agent. Deionized water was used as the solvent.
2.2. Synthesis of spinels
In a typical synthesis, under stirring condition 0.001 mol of Co(II)
nitrate and 0.002 mol of Fe(III) nitrate were dissolved in 70 mL of
deionized water. To make homogeneous the resulting solution was
stirred for additional 30 min. Then, 1 g of CTAB which is equivalent to
0.0027 mol was added to the homogeneous solution. After that 30%
NH4OH solution was added drop wise until pH of the solution became
10, during which precipitation occurred. The whole reaction mixture
was stirred further for 2 h at room temperature and was subsequently
sealed in a 100 mL teflon-lined autoclave (about 30% of the space
leaving empty) and placed in an oven maintained at 160 ◦ C for 10 h. The
resultant product was filtered, washed with distilled water and ethanol
for several times, and finally dried under vacuum at 100 ◦ C for over­
night. These dried precursors were calcined at 400 and 600 ◦ C (based on
TGA− DSC studies as discussed later) for 4 h to obtain the ferrite
materials.
2.3. Characterization
TGA− DSC studies were carried out employing Diamond Pyris 480,
Perkin Elmer with a N2 flow of 150 mL min− 1 at a heating rate of 15 ◦ C
min− 1 using alpha alumina as the external standard from room tem­
perature to 1000 ◦ C in order to analyze thermal behavior patterns of the
ferrites.
XRD patterns of precursor and calcined ferrite materials were
recorded using an X-ray powder diffractometer (Bruker D8 advance)
with Lynxeye detector (1D mode). Data were collected with CuKα ra­
diation (λ = 1.5406 Å) at 40 kV and 40 mA at a step size of 0.017◦ and a
scan time of 1 s per step. The samples were scanned over 2θ range of
10–80◦ .
BET surface area (SBET) measurements by N2 sorption analysis was
used to investigate the textural properties of the ferrite materials. Fer­
rites calcined at 600 ◦ C were only subjected for the surface area mea­
surements. NovaWin2 (Quantachrome Instruments, USA) was employed
to measure the N2 sorption isotherms at − 195 ◦ C. Ferrite samples were
degassed at 110 ◦ C for about 3 h before each measurement.
The morphological behaviors were checked using SEM (model JEOL
JAX-840A) and FESEM (model S-4800, Hitachi). INC X Oxford was used
to carry out the composition analyses by EDX at an acceleration voltage
of 10 keV.
HRTEM studies were performed on JEOL-JEM-2100 microscope
operated at 200 kV. A minimum amount of (around 1 mg) of solid ferrite
sample was taken in an eppendorf. The sample was dispersed in 1 mL
ethanol and then the solution was sonicated for at least 15 min. After
that using a micropipette approximately two drops (~10 μL) of the
sample solution were drop-casted on a carbon coated copper grid placed
on a small Petri dish. Then the grid was put under NIR lamp for 5–10 min
for drying the sample. Then the grid was kept inside a new eppendorf
and mouth of the eppendorf was covered with aluminum foil. Then few
small holes were made in the aluminum foil to attain vacuum. After that
the eppendorf was placed inside a desiccator and connected with a
vacuum pump. In vacuum condition, the desiccator was closed and kept
it for the experiment.
M. Saha et al. Ceramics International 48 (2022) 35719–35732

The surface characterization of ferrites was done with XPS using a

PHI 5000 VersaProbe II scanning spectrometer using AlKα radiation
(1486.6 eV) as an X-ray source operated at 15 kV. All the spectra were
referenced with C 1s peak at 284.5 eV. A pass energy of 58.7 eV was used
to record all individual spectra. The analyzing chamber was at an ultra-
high vacuum of 10− 10 Torr while collecting XPS data.
Molecular signatures of the ferrite samples were assessed by FTIR
(model Prestige 21, Shimadzu) in transmittance mode in the range of
400–4000 cm− 1. For the FTIR experiment, 2 mg of solid sample was
mixed with 200 mg of vacuum-dried IR-grade KBr. The mixture was
dispersed by grinding for 3 min in a vibratory ball mill, placed in a steel
die of 10 mm diameter, and subjected to a pressure of 12 tons to make a
disk. The sample disk was mounted in the holder of the double grating IR
spectrometer.
Raman spectra of the ferrite materials were recorded employing
Alpha 300, Witec spectrometer at room temperature using a laser
excitation source with wavelength of ~532 nm in the spectral range
from 150 to 800 cm− 1.
The optical behaviors of the ferrites were analyzed by UV–Vis
spectroscopy (Perkin Elmer, Lambda 35) in the range of 200–800 nm in
absorption mode. Before the measurement, the sample was sonicated for
30 min in ethanol and the supernatant suspension was poured into the
cuvette for spectral analysis.
The dielectric studies of ferrites were performed using Agilent 4294
A precision impedance analyzer in the frequency range 40 Hz–110 MHz
at room temperature. For the dielectric measurement, the powder
sample was transformed into its pellet form of diameter ~12 mm under
40 kg cm− 2 for 2 min. Copper wire was attached properly to both sides of
the pellet with silver paste to complete the electric circuit. Fig. 1. TGA− DSC curves of (a) cobalt and (b) zinc precursors for the prepa­
Magnetic measurements of the ferrite materials were carried out at ration of CoFe2O4 and ZnFe2O4.
room temperature using superconducting quantum interference device
(SQUID) on MPMS XL, RDK-415 under the external magnetic field
ranging from − 5 T to +5 T. steps which is in agreement with the TGA results. The diffraction peaks
have been indexed to (111), (220), (311), (222), (400), (422), (511),
3. Results and discussion (440), and (533) reflection planes of the cubic lattice of CoFe2O4 (JCPDS
PDF # 22-1086) and ZnFe2O4 (JCPDS PDF # 82-1049). The desired
3.1. TGA− DSC studies crystalline ferrite material is obtained as the only phase without any
impurities at all the calcination temperatures. Although Toledo-Antonio
Fig. 1 displays the TGA− DSC curves of the ferrite precursor mate­ et al. have reported ZnFe2O4 synthesis via a hydrothermal method, but
rials. The green line represents change of mass with reference to the they could not avoid the formation of Fe2O3 as an impurity [59]. Zhao
programmed temperature, and the red line stands for the nature of heat et al. have synthesized CoFe2O4 along with β-FeOOH as an impurity via a
flow. The mass of the precursor is lost in three steps for cobalt and in two hydrothermal process [60]. As expected, the intensity and sharpness of
steps for the zinc precursor. A minor mass reduction (~2%) takes place the diffraction peaks increase for the samples calcined at higher tem­
up to 200 ◦ C for both the precursors due to the removal of volatile perature because of enhanced crystallinity of the nanoparticles. This can
materials and moisture. The major mass reduction of 7% (4% at ~400 ◦ C as well be because of an increase in crystallite size brought about by
followed by another 3% at ~600 ◦ C) for cobalt precursor is due to the coalescence phenomena during calcination. The samples obtained on
decomposition of nitrate salts to form the oxide phase. For the zinc calcination at 600 ◦ C (CoFe6 and ZnFe6) have been chosen for most of
precursor, the reduction of mass beyond 200 ◦ C is comparatively less the following studies except optical and magnetic studies.
(about 3%) and it extends smoothly up to 600 ◦ C. The endothermic peak The crystallite sizes of the ferrites have been estimated using the
at around 100 ◦ C is due to the removal of volatile materials. The broad Scherrer’s equation as given below:
nature of the exothermic peaks centered at ~480 ◦ C (for cobalt) and
0.94 λ
~460 ◦ C (for zinc) indicates the onset of ferrite phase formation around D= (1)
βcosθ
400 ◦ C. The plateau formed beyond 600 ◦ C suggests the formation of
stable ferrite phase. On the basis of TGA− DSC analyses, two calcination
where D is the average crystallite size, λ is the wavelength of X-ray in
temperatures, namely, 400 ◦ C and 600 ◦ C, and the heating rate of 5 ◦ C
nm, β is the full-width-at-half-maximum (FWHM) of the diffraction peak
min− 1 for 4 h have been chosen to obtain the desired ferrite materials,
in radian and θ is the Bragg angle. The crystallite sizes of CoFe2O4 and
named, respectively, as MFe4 and MFe6.
ZnFe2O4 fall in the ranges of 30–33 nm and 17–28 nm, respectively,
depending on the calcination temperature.
3.2. XRD studies

Fig. 2 represents the XRD patterns of the ferrite materials obtained on
calcination of the respective precursors at 400 and 600 ◦ C together with
the XRD patterns of the precursors. As can be seen the ferrite phase starts
to form during the hydrothermal treatment and is associated with the
formation of Fe2O3 (JCPDS PDF # 86-0550) as an impurity phase. The
pure phase ferrite is formed as the exclusive one after the calcination
3.3. SBET studies
The BET specific surface areas of the ferrites are observed to be
moderate. The CoFe6 exhibits a higher surface area of 47 m2 g− 1,
whereas the ZnFe6 sample shows a lower surface area of 23 m2 g− 1. This
observation indicates that the specific surface areas of the ferrite

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M. Saha et al.
Fig. 2. XRD patterns of the precursor materials (CoFeP and ZnFeP) and the
calcined precursors (CoFe4, CoFe6, ZnFe4, and ZnFe6) of CoFe2O4
and ZnFe2O4.
materials are increased in comparison with some of the literature reports
[61,62].
3.4. SEM and EDX studies
Fig. 3 depicts SEM images of CoFe6 (Fig. 3 (a, b)) and ZnFe6 (Fig. 3
(d, e)) at various resolutions. To confirm the chemical homogeneity and
stoichiometric ratio, EDX analysis of the ferrite samples for wide range
exposure of the electron beam have been carried out. The EDX spectra
(see Fig. 3 (c, f)) of the different samples indicate the presence of Fe, O,
Co, and Zn in the respective samples. There was no detectable trace of
impurity in the samples. The mole ratio of Fe/M (M = Co and Zn) is
found to be around 2 which is very close to the expected value. There­
fore, it may be assumed that the precursors used in the synthesis process
are transformed completely to the product material.
3.5. FESEM studies
To assess the shapes, sizes, and morphologies of the ferrite samples
FESEM analyses have been performed. Fig. 4 represents the FESEM
images of CoFe6 and ZnFe6. The FESEM images of CoFe6 appear to be
hexagonal in shape of the particles (Fig. 4 (a)) that would be
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Ceramics International 48 (2022) 35719–35732
substantiated from TEM analyses. The morphology of ZnFe6 is almost
spherical with uniform size (Fig. 4 (b)). The nanosized grains are about
70 and 40 nm, respectively, for CoFe6 and ZnFe6. The differential
morphology of these spinels prepared under similar synthetic condition
is possibly related to their chemical nature. The cobalt ferrite exhibits
faceted particles, whereas zinc ferrite shows symmetric spherical par­
ticles. The observed morphologies could be related to the higher surface
roughening temperature for cobalt ferrite compared to that of zinc
ferrite of chemical origin. There is a soft agglomeration tendency among
the particles due to sintering effect. Although these small crystallites are
closely packed, there is a clear boundary between two neighboring
crystallites.
3.6. HRTEM studies
Fig. 5 (a) depicts a general view of the CoFe6 particles, having
average particle size of ~40 nm which is in consistent with the Scherrer
size. HRTEM image of an individual particle is included in Fig. 5 (b).
Both hexagonal and nearly spherical particles are identified in the high
resolution images. The distinct lattice spacing of 2.53 Å corresponds to
(311) plane observed in the inset of Fig. 5 (b). In Fig. 5 (d) the micro­
structure of ZnFe6 is displayed. The particles are spherical in nature with
average size of ~16 nm which is close to the size calculated from
Scherrer’s formula. The lattice spacing of 2.98 Å denotes (220) plane for
ZnFe6 which is seen in Fig. 5 (e). The variations in the particle size and
shape of the ferrites depend on the nucleation and slow growth by the
diffusion of the ions from the solution to the surface of the nuclei. The
particle sizes of the ferrite materials of this study are lower when
compared with some of the literature reports. Chandramohan et al. have
synthesized CoFe2O4 via a solid state reaction and a polymer solution
combustion method with particle sizes of 272 and 123 nm, respectively
[63]. Milanova et al. have made spinel ZnFe2O4 material by a spray
pyrolysis deposition method with particle size of 135 nm [64].
The selected area electron diffraction (SAED) displays ring patterns
as shown in Fig. 5 (c, f) that indicate polycrystalline nature of the fer­
rites. The indexed planes correspond only to the ferrite phases. The
spotty nature of the SAED pattern is attributed to the presence of finer
crystallites.
3.7. XPS studies
XPS of ferrite materials has been carried out to understand the
change in metal binding energy because of different coordination en­
vironments with oxygen ions [5]. Generally, in AB2O4 spinel structure, A
is tetrahedrally coordinated (Td) to oxygen in +2 oxidation state,
whereas B is in octahedral coordination (Oh) to oxygen with +3 oxida­
tion state. On the other hand, in inverse spinel structure, A is in
completely octahedral coordination and B is in both tetrahedral and
octahedral coordinations. Therefore, different coordination environ­
ments of B-site metal result in its different binding energies. In this re­
gard, XPS studies of CoFe2O4 and ZnFe2O4 can provide valuable
information about coordination environments of the metals through
their binding energy values.
Fig. 6 (a− d) represents Co 2p3/2, Zn 2p3/2, and Fe 2p3/2 core level
spectra of CoFe6 and ZnFe6. Co 2p3/2 core level spectral envelope in
CoFe6 is observed to be broad in nature confirming the presence of Co
species in different coordination sites in its lattice. Accordingly, the
spectrum is curve-fitted into its component peaks as shown in Fig. 6 (a).
Co 2p3/2 peaks at 780.4 and 781.9 eV with characteristic satellite peak at
788.8 eV in Co 2p core level spectrum of CoFe6 correspond to Co2+
component species in octahedral coordination and tetrahedral coordi­
nation, respectively, in CoFe6 spinel structure [5,65,66] An intense
component peak at 783.7 eV is ascribed to Fe LMM Auger electron peak
of Fe3+ species present in CoFe6 since Co 2p3/2 core level spectral region
overlaps with Fe LMM Auger electron spectral region when AlKα is used
as an X-ray source for data collection. Relative concentrations of Co
M. Saha et al. Ceramics International 48 (2022) 35719–35732

Fig. 3. SEM images of (a, b) CoFe6, (d, e) ZnFe6 and (c, f) their EDX spectra, respectively.

Fig. 4. FESEM images of (a) CoFe6 and (b) ZnFe6.

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Fig. 5. HRTEM images of (a, b) CoFe6, (d, e) ZnFe6 and (c) and (f) the SAED patterns of CoFe6 and ZnFe6, respectively.

Fig. 6. Core level spectra of (a) Co 2p3/2 in CoFe6, (b) Zn 2p in ZnFe6, (c) Fe 2p3/2 in CoFe6, and (d) Fe 2p3/2 in ZnFe6.

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M. Saha et al.
species associated with the tetrahedral and octahedral coordination sites
are estimated from the area under the related curve-fitted peaks. It has
been found that 42% Co2+ is in tetrahedral coordination and 58% Co2+
is in octahedral coordination. Zn 2p3/2 core level spectrum is resolved
into two component peaks which is presented in Fig. 6 (b). Intense
component peak at 1020.8 is related to Zn2+ species in tetrahedral co­
ordination environment, whereas a weak component peak around
1022.1 eV corresponds to Zn2+ species in octahedral coordination
environment [5]. Relative concentrations of Zn2+ species in tetrahedral
and octahedral coordination sites are 87% and 13%, respectively. Broad
Fe 2p3/2 core level spectra in CoFe6 and ZnFe6 indicate the presence of
multiple Fe species with different coordination sites in the ferrites and
they are curve-fitted into component species as shown in Fig. 6 (c) and
(d), respectively. In CoFe6, Fe 2p3/2 peaks observed at 710.4 and 712.6
eV in curve-fitted Fe 2p3/2 core level spectrum along with a character­
istic satellite peak at 718.2 eV are attributed to octahedral and tetra­
hedral Fe3+ species, respectively (Fig. 6 (c)) [5,65,66]. A strong
component peak at 714.8 eV is attributed to Co LMM Auger electron
peak of Co2+ species present in CoFe6. Because, Fe 2p3/2 core level
spectral region overlaps with Co LMM Auger electron spectral region
when Al Kα is used as an X-ray source for data collection. Fe 2p3/2
binding energy peak positions in ZnFe6 are observed to be similar to that
in CoFe6 as displayed in Fig. 6 (d). However, there is no Auger electron
peak in the spectrum as there is no overlapping peak. In CoFe6, the
concentrations of Fe3+ in octahedral and tetrahedral sites are, respec­
tively, 59% and 41%, whereas in ZnFe6 they are 56% and 44%,
respectively. Thus, XPS analyses of ferrite materials in this study
demonstrate that Co2+, Zn2+, and Fe3+ are present in both tetrahedral
and octahedral sites in the spinel structure of CoFe6 and ZnFe6. Binding
energies and relative peak areas of Co2+, Zn2+, and Fe3+ ions and their
cation distributions at tetrahedral and octahedral sites in CoFe6 and
ZnFe6 ferrites evaluated from XPS data are summarized in Table 1.
Further, surface concentration ratios of Co/Fe and Zn/Fe in CoFe6 and
ZnFe6 have been estimated from the respective areas under the Co 2p3/2,
Fe 2p3/2, and Zn 2p3/2 XPS core level peaks, photoionization
cross-sections, and mean escape depths. Estimated surface concentration
ratios of Co/Fe in CoFe6 and Zn/Fe in ZnFe6 are 0.72 and 0.53,
respectively. Higher value of Co/Fe ratio in CoFe6 is due to the presence
of overlapping Fe LMM Auger peak in Co 2p core level spectrum and that
of Co LMM Auger peak in Fe 2p core level spectrum. On the other hand,
observed Zn/Fe ratio in ZnFe6 is close to the expected stoichiometric
value of 0.5.
3.8. FTIR spectroscopy studies
The ferrite can be considered as continuously bonded crystal,
wherein atoms are bonded to all nearest neighbors by ionic forces. In the
ferrite system, the metal ions are distributed among the two sublattices,
namely tetrahedral (A-sites) and octahedral (B-sites). To assess the na­
ture of metal− oxygen bonds and other bonds FTIR studies of the ferrite
materials have been carried out. In spinel ferrites, the formation of single
phase AB2O4 spinel structure is confirmed by the observation of IR bands
below 1000 cm− 1. Due to lattice vibrations of oxide ions against cations
these bands area observed to appear. Band centered at higher wave­
number (ν1) corresponds to metal− oxygen stretching vibration
Table 1
Binding energies of 2p3/2 core level peaks and relative peak areas of Co2+, Zn2+, and Fe3+ ions and their distributions at tetrahedral (Td) and octahedral (Oh) sites in
CoFe6 and ZnFe6 ferrites evaluated from XPS data.
Ferrite Cation Binding energy (eV) of 2p3/2 core level peak
Td Oh
CoFe6 Co2+ 781.9 780.4
Fe3+ 712.6 710.4
ZnFe6 Zn2+ 1020.8 1022.1
Fe3+ 712.7 710.6
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associated with the tetrahedral sites and lower wavenumber band (ν2) is
related to metal− oxygen bending vibration in octahedral sites [5].
Because of shorter metal− oxygen bond length at tetrahedral sites
compared to longer metal− oxygen bond length at octahedral sites, the
vibrations at tetrahedral sites are observed at higher frequencies than
those for octahedral sites. Accordingly, the bands around 550− 610
cm− 1 and 370− 440 cm− 1 corresponds to ν1 and ν2 modes, respectively
[67]. In the present work, a broad intense band in the 550− 610 cm− 1
frequency region is found for all ferrite materials as displayed in Fig. 7.
Due to limitation of FTIR spectrometer to collect IR data beyond 400
cm− 1 actual signature of a weak band around 400 cm− 1 is not distinct
[5]. Broadening of band is generally observed in inverse spinel ferrites
because of the statistical distribution of Co2+, Zn2+, and Fe3+ at A and
B-sites [5]. The observed band at 606.3 cm− 1 in CoFe4 and CoFe6 is
attributed to M↔O bond stretching in tetrahedral site of CoFe2O4 [68,
69] (see Fig. 7 (a, b)). From this study, it may be concluded that CoFe2O4
exhibits an inverse spinel structure. Similarly, the band observed at 563
cm− 1 in ZnFe4 and ZnFe6 is due to the M↔O bond stretching in tetra­
hedral site of ZnFe2O4 [70] (see Fig. 7 (c, d)). Observation of these bands
confirms the formation of spinel cubic structure in these ferrite mate­
rials. It is to be mentioned that ionic radius of Zn2+ (0.60 Å) is larger
than that of Co2+ (0.58 Å with high spin) and Fe3+ (0.49 Å with high
spin) [5]. In this sense, metal− oxygen bond length in tetrahedral sites
increases and consequently, tetrahedral vibrational frequency decreases
in ZnFe6 and ZnFe4 compared to CoFe6 and CoFe4. This observation
indicates that Zn2+ ions preferentially occupy tetrahedral sites and
substantiates the suggested cation distribution evaluated from XPS
studies.
It is well established that cation mass, cation− oxygen bonding force,
cation− oxygen bond length, and cation distribution influence the
vibrational frequencies of spinel ferrites. Generally, the vibrational
Fig. 7. FTIR spectra of (a) CoFe4, (b) CoFe6, (c) ZnFe4, and (d) ZnFe6.
Relative peak area (%) Cation distribution
Td Oh Td (A-site) Oh (B-site)
42 58 (Co2+ 3+
0.42 Fe0.82 ) [Co2+ 3+
0.58 Fe1.18 ]
41 59
87 13 (Zn2+ 3+
0.87 Fe0.88 ) [Zn2+ 3+
0.13 Fe1.12 ]
44 56
M. Saha et al. Ceramics International 48 (2022) 35719–35732

frequency of a bond is associated with mass of the system and force

constant of the bond. Classically, vibrational frequency (ν) in wave­
number (cm− 1) of a bond is represented by Hooke’s law as written below
[5]:
√̅̅̅
1 k
v= (2)
2πc μ

where k, μ, and c are force constant of the bond corresponding to its

strength, reduced mass of the bond, and velocity of light, respectively.
Reduced mass is given by the relation:
m1 m2
μ= ×u (3)
m1 + m2

where m1 and m2 are masses of atoms involved in the vibration and u is

unit mass (1.6605 × 10− 24 g).
Further, force constant is calculated by reorganizing equation (2) as
given below:

k = 4π 2 c2 ν⋅2 μ. (4)
Therefore, force constants related to the bands with tetrahedral and
octahedral coordinations can be calculated from observed band posi­
tions (ν), c (3 × 1010 cm s− 1), and μ. Here, m1 and m2 are weighted
average of atomic mass of cations residing at A-site (tetrahedral) or B-
site (octahedral) and atomic mass of oxide ion, respectively, for the
calculation of reduced mass. In the present study, tetrahedral force
constants (ktet) have been calculated, because tetrahedral band positions
of the ferrites are clear from the recorded spectral range. Their octahe­
dral force constants (koct) are not evaluated due to unclarity of corre­
sponding band positions. Observed ktet value of CoFe4 and CoFe6 is
around 272.6 N m− 1, whereas value for ZnFe4 and ZnFe6 is around
245.7 N m− 1. Decrease in wavenumber and reduced mass at tetrahedral
site in ZnFe4 and ZnFe6 lowers the force constant in relation to CoFe4
and CoFe6.

Fig. 8. Raman spectra of (a) CoFe6 and (b) ZnFe6.

3.9. Raman spectroscopy studies

Raman spectroscopy is a very sensitive method to understand the Table 2

structural distortion and oxygen motion in spinel structure. The crys­ Raman active modes of CoFe6 and ZnFe6.
talline cubic ferrite materials belong to the space group Fd 3 m (O7h, Peak assignment Raman mode of CoFe6 (cm− 1) Raman mode of ZnFe6 (cm− 1)
Space Group # 227). The complete unit cell contains 56 atoms (Z = 8) T2g(1) 209 229
and the smallest Bravais cell consists of only 14 atoms (Z = 2). From Eg 299 295
group theoretical analysis there are 17 sets of phonon modes at Γ-point Eg(2) – 339
of Brillouin zone in spinel (Γ = A1g + Eg + T1g + 3T2g + 2A2u + 2Eu + T2g(2) 475 491
T2g(3)
5T1u + 2T2u) [71]. Among these vibrational modes, there are 5
– –
A1g(1) 608 655
Raman-active modes (ΓRaman = A1g + Eg + 3T2g). Of the remaining, 4 A1g(2) 684
vibrational modes are infrared-active (ΓIR = 4T1u), 7 modes are silent
(ΓSilent = 2Au + 2Eu + T1g + 2T2u) and 1 mode is acoustic modes
(ΓAcoustic = T1u). atom in Fe/M− O bond at octahedral sites (BO6). Symmetric bending
Fig. 8 depicts the Raman spectra of CoFe6 and ZnFe6 at the lowest motion of oxygen in octahedral site gives rise to T2g(2) Raman active
optical intensity. Such kind of laser power has been used to avoid mode. Symmetric bending of oxygen atom with respect to the metal ion
possible sample degradation. Table 2 represents the assignments of at octahedral sites corresponds to Eg mode. This mode also provides the
different Raman modes in CoFe6 and ZnFe6. At the higher calcination grain size of the sample. The T2g(1) mode corresponds to the trans­
temperature, CoFe2O4 exhibits inverse spinel structure due to redistri­ lational movement of the AO4 tetrahedral units. In the present study, the
bution of metal cations in the crystal lattice. The cation redistribution in Raman active modes are observed at 209, 299, 475, 608, and 684 cm− 1
the tetrahedral and octahedral sites of the crystal lattice alter the sym­ in CoFe6 sample (see Fig. 8 (a)). The frequencies above 600 cm− 1, i.e.,
metry of the crystal structure to I41/amd space group with more number peak maxima at 608 and 684 cm− 1 are due to A1g symmetry. On the
of active vibrational modes in the Raman spectra and this also influences other hand, low frequency modes at 475, 299, and 209 cm− 1 are related
the fundamental as well as technologically important magnetic prop­ to T2g(2), Eg, and T2g(1) symmetries, respectively. In the case of ZnFe6,
erties of the spinel ferrite materials. Lazzeri et al. [72] and Wijs et al. the Raman active modes are noticed around 229, 295, 339, 491, and
[73] have extensively studied the cation distribution and its effect on the 655 cm− 1 that correspond to T2g (1), Eg(1), Eg(2), T2g (2), and A1g
Raman spectrum of MgAl2O4 spinel. The A1g mode is assigned to the symmetries, respectively, as shown in Fig. 8 (b). However, in both the
symmetric stretching of oxygen atoms along Fe–O and M− O (M = Co ferrites, T2g(3) peak around 550 cm− 1 is not observed. Furthermore,
and Zn) bonds in the tetrahedral sites (AO4) of the crystal lattice. The nanodimension of the ferrites with high crystallinity leads to broadening
T2g(3) mode arises because of the asymmetric bending motion of oxygen of the Raman spectra due to lack of long-range order in these materials.

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M. Saha et al.
It is also worth mentioning that doublet-like feature is noticed for A1g
peak in CoFe6 in relation to ZnFe6. CoFe6 shows two A1g peaks at 608
and 684 cm− 1, whereas a broad band at 655 cm− 1 is observed in ZnFe6.
This is because of cation exchange between tetrahedral and octahedral
sites in CoFe6. Due to ionic radii differences of Co2+ and Fe3+ ions, Co–O
and Fe–O bond lengths are redistributed between both the sites leading
to distinct doublet peak. In contrast, as Zn2+ prefers tetrahedral sites,
extent of cation distribution is less in ZnFe6 compared to CoFe6 as
evident from XPS studies resulting in a broad A1g band in Raman spec­
trum of ZnFe6.
3.10. UV–Vis spectroscopy studies
Fig. 9 shows the absorption spectra of CoFe6 and ZnFe6. The ab­
sorption behavior originates due to charge transfer transition, Fe-cation
playing the main role. According to Haart and coworkers the metal to
metal charge transfer transition occurs between Fe3+ and Fe2+ in the
ferrite system. There is other possibility of absorption because of exci­
tation of an electron from the O 2p level to the Fe 3d level.
The direct band gap value of the ferrites is worked out by using the
Tauc’s equation given below:
( )
(αhν)2 = A hν − Eg (5)
where hν is the photon energy, Eg denotes the band gap value, α is the
absorption coefficient, and A is a constant. The absorption coefficient α
may be expressed as:
( )
A dielectric constant for zinc ferrite compared to that of the cobalt ferrite
α = 2.303 b (6)
t
where Ab is the absorbance and t is the thickness of cuvette. Fig. 10
shows the (αhν)2 vs hν plots, from which the band gap of the ferrite
sample is determined by the method of extrapolation. The band gap
values fall in the ranges from 2.23 eV to 1.94 eV and 2.21 eV–1.99 eV for
CoFe6 and ZnFe6, respectively. These values are lower when compared
to some of the earlier literature reports. For instance, Singh et al. have
reported ZnFe2O4 obtained via a hydrothermal method with a band gap
of 2.82 eV [74].
3.11. Dielectric behaviors
Fig. 11 represents the plots of dielectric constant (εʹ) and complex
Fig. 9. UV–Vis spectra of (a) CoFe4, (b) CoFe6, (c) ZnFe4, and (d) ZnFe6.
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Ceramics International 48 (2022) 35719–35732
dielectric constant (ε’’) with respect to the frequency of the ferrite ma­
terials. The dielectric constant of the material is calculated by using the
following relation:
Cp t
(7)
′
ε =
εo A
where Cp is the measured value of capacitance of the sample, t is the
sample thickness, A stands for the surface area, and εo denotes the
dielectric permittivity of air (8.854 × 10− 14 F cm− 1). The loss tangent
(tanδ) and the complex dielectric constant are evaluated from the
following relations (equations (8) and (9)):
1
tanδ = (8)
2πf εo ε′ ρ
where f denotes the frequency and ρ stands for the specific resistance.
′
ε′′ = ε tanδ. (9)
The values of both the ε and ε increase with the calcination tem­
′ ′′
perature (see Fig. 11). The typical values of ε′ and ε′ ′ are ~4500 and
~5700, respectively for CoFe4, while these values are, respectively,
~6400 and ~800 for CoFe6. The Zn-ferrite samples exhibit compara­
tively much higher values of ε′ and ε′′ than the Co-ferrite samples.
Specifically for the ZnFe6 sample, ε′ and ε′′ values are found to be
~11800 and ~450000, respectively. The larger values of the dielectric
constant for high temperature annealed samples may be related to its
denser nature as expected. One should also note that the higher values of
suggest the former to be more insulating in nature. This is expected as in
cobalt ferrite valence fluctuation is possible between cobalt and iron,
whereas zinc fails to participate in valence fluctuation with iron. This
charge delocalization due to valence fluctuation may result in leakage
current. In contrast to our results, there are reports in the literature
which claim that the as-prepared ferrites are magnetic semiconducting
materials [75,76]. The larger values of complex dielectric constant
indicate the leaky nature of the samples. Furthermore, the value of
dielectric constant also increases due to the presence of polarizations
(electronic, ionic and orientation) including space charge. The space
charge polarization dominates at low frequency and high temperature
[77]. The conducting grains in the dielectric structure are separated by
insulating grain boundaries. In the lower frequencies, the electronic
conduction through the grain boundaries is predominated over that
through the grains. The high permittivity is observed due to the high
resistance of the grain boundary. As a result, the electrons reach the
grain boundaries through hopping and pile up. However, as the fre­
quency increases, it is observed that the permittivity decreases due to
the fact that the electrons generally reverse their direction of motion at
the grain boundaries. The probability of electron reaching the grain
boundary thus decreases that is associated with a decrease in
permittivity.
3.12. Magnetic behaviors
Fig. 12 depicts the M− H hysteresis curves recorded at 300 K of
various ferrite materials of this study. The magnetic parameters such as
saturation magnetization (Ms), remanence magnetization (Mr), and
coercivity (Hc) of the materials are evaluated from the hysteresis loops.
Further, the saturation magnetization can be determined from the
following relation:
[ √̅̅̅̅̅̅̅̅̅̅ ]
2K 25kT
Ms = 1− (10)
Hc KV
where, K is the effective anisotropy constant, k is Boltzmann constant, V
denotes the volume of the particle, and T stands for the temperature.
It is noticed that the saturation magnetization increases with the
M. Saha et al. Ceramics International 48 (2022) 35719–35732

Fig. 10. Plot of (αhν)2 vs photon energy for (a) CoFe4, (b) CoFe6, (c) ZnFe4, and (d) ZnFe6.

Fig. 11. Plots of (a, b) εʹ vs log (f) and (c, d) εʹʹ vs log (f) for the various CoFe2O4 and ZnFe2O4 materials.

increase of the calcination temperature, which can be attributed to the
increase in the average size of the grains or the possible change in
cationic distribution between A- and B-sites as reported for cobalt
ferrite, where the increase in magnetization is associated with the
preferential occupancy of Co2+ in octahedral site [58]. Furthermore, one
of the important parameters that determine the Ms values of the ferrite
materials is cation distribution throughout the crystal lattice. The Ms
and Mr values for CoFe4 are 74.2 emu g− 1 and 31 emu g− 1, respectively,
and those for CoFe6 are, respectively, 78.9 emu g− 1 and 33 emu g− 1 as
shown in Fig. 12 (a). This suggests the improvement of magnetization
values for high temperature annealed sample. As expected, the Hc value
varies with the calcination temperature. It is found to be 1221 Oe for
CoFe4 that is increased to 1411 Oe for CoFe6. These values are higher
when compared to some of the earlier literature reports [78,79]. The

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M. Saha et al. Ceramics International 48 (2022) 35719–35732

Fig. 12. M− H curves of (a) CoFe4 and CoFe6 (the inset shows the expanded view for the range from − 2 kOe to +2 kOe) and (b) ZnFe4 and ZnFe6.

higher value of saturation magnetization in CoFe6 could be related to
redistribution of metal cations in the crystal lattice or to the better
crystallinity and larger particle size for higher temperature annealed
sample. The later one results in suppression of magnetic dead layers
[80]. The unquenched orbital moments of Co2+ in the octahedral site
results in strong spin–orbit coupling. This can be attributed to the in­
crease in magnetic moment when Co moves to octahedral sites [58]. In
the present case, the second possibility is the most likely one for the
increased moment in CoFe6. It may be confirmed that at the higher
calcination temperature CoFe2O4 behaves as an inverse spinel. The na­
ture of the curve indicates that CoFe2O4 is a strong ferromagnetic ma­
terial [81].
However, M− H curves of ZnFe2O4 samples at 300 K do not show any
hysteresis loop as displayed in Fig. 12 (b) and magnetization increases
with the increase in applied field without any saturation unlike CoFe2O4.
This is typical behavior of a paramagnetic material. This indicates that
the replacement of Co by non-magnetic Zn, drastically change the
magnetic properties of ferrite spinels. The ferrimagnetic ordering or
Néel temperature of bulk ZnFe2O4 is about 10 K. Thus, ZnFe2O4 prac­
tically remains in paramagnetic state at 300 K. It also shows almost same
magnitude of magnetization (10 emu g− 1) at 5 T for both the samples
annealed at 400 and 600 ◦ C unlike CoFe2O4. This result supports the
unique feature of phase purity of the sample obtained by hydrothermal
route of synthesis. In other word, there is no formation of strong ferri­
magnetic Fe3O4 which is possible in solid state synthesis. It is worth
mentioning that there is a slight nonlinearity in M− H curves near zero
field (Fig. 12 (b)). This may be related to the possible spin clustering or
defects at the surface of the ZnFe2O4 nanoparticles.
Hydrothermal route has been employed to synthesize several oxide
materials with different nanostructures. Parameters for the synthesis
condition are the key factors to obtain different nanostructures such as
rod, flake, flower, broom, needle, cube, octahedral, etc. In the present
study, hexagonal and spherical morphologies of CoFe2O4 and ZnFe2O4
are obtained in the synthesis condition adopted here in presence of
CTAB surfactant. A comprehensive account of literature reports on
synthesis of these ferrite materials with varied nanostructures involving
hydrothermal synthesis is listed in Table 3.
From the above results it may be concluded that our synthesis pro­
cedure leads to the formation of hexagonal cobalt ferrite which is by far
the first such finding following a hydrothermal route and spherical zinc

Table 3
Comparison of MFe2O4 (M = Co and Zn) ferrites prepared via hydrothermal route.
Ferrite Temperature (◦ C) Time (h) Surfactant/Calcination Morphology Reference

CoFe2O4 180 24 PEG Nanosphere 30

160 24 CTAB Nanooctahedra 31
200 5 750 ◦ C for 3 h Nanooctahedra 32
140 0.5 to 2 – Nanosphere 33
1 to 2 – Nanocube
180 24 – Agglomerated 34
90 10 400 ◦ C for 2 h Nanosheet 35
150 7 – Nanosphere 36
180 3 – Nanosphere 37
180 0.17 – Nanosphere 38
200 6 CTAB/800 ◦ C for 2 h Nanocube 39
180 12 – Nanosphere 40
120 12 800 ◦ C 5 h Nanosphere 41
160 6 500 ◦ C for 4 h Flower-like microsphere 42
120 6 – Nanosphere 43
160 10 CTAB/600 ◦ C for 4 h Hexagonal, Nanosphere This work
ZnFe2O4 180 12 – Nanoparticle 44
120 24 400 ◦ C for 2 h Nanorod 44
160 6 400 ◦ C for 5 h Nanoflower 44
190 6 400 ◦ C for 5 h Hollow microsphere 44
180 12 400 ◦ C for 2 h Sheet stacked hollowsphere 45
180 24 – Nanocube 46
160 12 500 ◦ C for 2 h Nanoparticle 49
120 24 – Nanorod 50
180 12 450 ◦ C for 3 h Hollow microsphere 51
180 18 450 ◦ C for 3 h Nanoflower 52
200 6 450 ◦ C for 3 h Coral 53
100 24 – Nanoneedle 54
150 16 Stepwise 300–500 ◦ C for 1 h duration at each temperature Nanorod 55
160 10 CTAB/600 ◦ C for 4 h Nanosphere This work

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M. Saha et al.
ferrite of reasonably small size. There is one report on the synthesis of
hexagonal CoFe2O4 nanoparticles of size 16–35 nm by hydrothermal
method (adapting 1:1 vol ratio of H2O:NH3) using PEG as surfactant
additive at 180 ◦ C for 6 h [66]. A moderate synthesis temperature and
time are important from the perspective of energy consumption. But a
pure phase material is formed only on post calcination treatment in air.
We may attribute the material characteristics (high value of dielectric
constant and reasonably low values for band gap and saturation
magnetization) of the ferrites of this study to (i) the high pressure
generated in the reaction medium due to the formation of nitrogen di­
oxide and oxygen from the decomposition of the nitrate salts in addition
to the ammonia gas from the in situ decomposition of NH4OH used in the
synthetic protocol and (ii) the use of the surfactant CTAB (only a few
studies employ this surfactant) assists further by preventing the
agglomeration process.
Ferrites have been paid much attention because of their excellent
chemical stability, good mechanical hardness, good electrical insulation,
and extraordinarily promising applications as magnetic materials, cat­
alysts, photocatalysts, electrocatalysts, gas sensors, etc. It has been
realized that synthetic routes have significant impact on the particle size
and shape of the ferrites, thereby controlling their physical and chemical
properties. Further, the properties get tuned by various chemical mod­
ifications such as doping A or B lattice sites with other metal ions,
modifying the preparation conditions, making composites with different
inorganic and organic matrices, etc. The guest metal ions settle in
different lattice sites, thereby, changing their structural, magnetic,
electrical, catalytic, and electrocatalytic properties. In the present study,
the obtained magnetic data are comparable with the data available in
the literature. In some cases, Ms values calculated in the present work
are found to be higher than the values obtained from similar ferrites
prepared by other methods. More insulating nature of zinc ferrite
studied here is attributed to higher values of dielectric constant for zinc
ferrite samples compared to that of cobalt ferrite. Considering all the
above facts and obtained results some of the foreseeable applications of
these ferrites are briefly discussed below.
In recent years, microwave absorbing materials (MAM) perceive
great applications in the fields of civil applications, wherein electro­
magnetic interference (EMI) shielding is an important factor and mili­
tary applications, wherein attenuation of radar cross section (RCS) of the
target is a prime parameter. Electromagnetic radiation like microwave
(MW) severely interferes with electronic equipments, namely, com­
puters, mobile phones, and communication systems. Further, military
equipments, namely, fighter jets, missiles, naval ships, etc. need debil­
itation of electromagnetic radiation, so that these equipments cannot be
identified by enemy radars. In this sense, MW absorption technology
employing appropriate materials is the simplest route to attenuate the
radiation. In this way, the electromagnetic energy is converted into heat
or other forms of energy. In this sense, ferrites have been found to be a
promising class of materials for MW absorbing applications due to their
high electrical resistivity, high saturation magnetization, high perme­
ability, and moderate permittivity. They have been used in various
forms like sheets, paints, coatings, ceramic tiles, and powders loaded in
matrix composites or mixed with conducting materials. Among all the
ferrites, spinel is most widely used family of ferrite and CoFe2O4 has
been used for the absorption of MW radiation [5,13].
Ferrites have also been the favorite choice of materials for applica­
tions in MW devices such as circulators, isolators, phase shifters, etc. due
to their very high specific resistance, notable tunability in the magnetic
properties, and ease of preparation.
The research and investigation on gas sensors to monitor the toxic
chemicals, pollutants, and combustible gases has been a subject of in­
terest as per environmental pollution and safety requirements, both for
the industrial applications/needs as well as household requirements. In
this regard, in recent times, metal oxides with spinel ferrite structure
attracted much attention for gas sensing applications. CoFe2O4 and
ZnFe2O4 have been used for the application as gas sensors [1,12,29,45,
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Ceramics International 48 (2022) 35719–35732
48–50,52,55].
In addition, another important application of spinel ferrites that has
emerged in recent times is their prospective use as catalysts due to their
chemical stability, ease of synthesis, low cost, and remarkable potenti­
ality of their structure to accommodate a wide range of substituting and
doping metals for catalytic reactions. CoFe2O4-based ferrites have
appeared to be potential catalysts due to their chemical stability and
easy removal from the reaction media as they are magnetically sepa­
rable. They are used in dye degradation, water remediation, methane
combustion, synthesis of organic compounds, hydrogen production from
alcohols, CO oxidation, electrocatalysis, fuel cell catalysis, etc. [1,5,6,8,
9,23,24,44,46,59,61,62].
4. Conclusions
Spinel MFe2O4 (M = Co and Zn) materials have been successfully
synthesized by the hydrothermal synthesis at a moderate temperature of
160 ◦ C for 10 h followed by calcination at 400–600 ◦ C. The crystallite
sizes of the ferrite materials fall in the range 17–33 nm. The mesoporous
ferrite materials exhibit specific surface areas of 47 and 23 m2 g− 1 for
CoFe6 and ZnFe6, respectively. The dielectric and magnetic properties
of the ferrite materials depend on the calcination temperature required
for pure phase formation. All the materials are uniform in size and ho­
mogeneously distributed throughout the surface. For CoFe6 both hex­
agonal as well as spherical morphologies are obtained. However, the
surface morphology of ZnFe6 is spherical. There is an agglomeration
tendency due to the strong magnetic interaction among the nano­
particles and high surface area. CoFe2O4 samples show relatively much
lower values of ε′ and ε′′ in comparison with ZnFe2O4 samples. CoFe2O4
acts as a hard ferromagnetic material, whereas, ZnFe2O4 behaves as a
paramagnetic material. Ms and Hc values increase from 74.2 emu g− 1 to
78.9 emu g− 1 and 1221 Oe to 1411 Oe, respectively, for CoFe2O4 with
increase in the calcination temperature from 400 ◦ C to 600 ◦ C.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
One of the authors (MS) is thankful to UGC for fellowship. The au­
thors would like to thank Department of Metallurgical & Material En­
gineering, Department of Chemistry and School of Material Science &
Nanotechnology, Jadavpur University for providing the instrumental
facilities. Financial support from the Department of Science and Tech­
nology, Government of India by a grant (EMR/2016/001811) to AG is
gratefully acknowledged.
References
[1] T. Dippong, E.A. Levei, O. Cadar, Recent advances in synthesis and applications of
MFe2O4 (M = Co, Cu, Mn, Ni, Zn) nanoparticles, Nanomaterials 11 (2021), 1560.
[2] A. Vedrtnam, K. Kalauni, S. Dubey, A. Kumar, A comprehensive study on structure,
properties, synthesis and characterization of ferrites,, AIMS Mater. Sci. 6 (2021)
800–835.
[3] S.B. Narang, K. Pubby, Nickel spinel ferrites: A review, J. Magn. Magn. Mater. 519
(2021), 167163.
[4] F.G. da Silva, J. Depeyrot, A.F.C. Campos, R. Aquino, D. Fiorani, D. Peddis,
Structural and magnetic properties of spinel ferrite nanoparticles, J. Nanosci.
Nanotechnol. 19 (2019) 4888–4902.
[5] P. Bera, R.V. Lakshmi, B.H. Prakash, K. Tiwari, A. Shukla, A.K. Kundu, K. Biswas,
H.C. Barshilia, Solution combustion synthesis, characterization, magnetic, and
dielectric properties of CoFe2O4 and Co0.5M0.5Fe2O4 (Mn, Ni, and Zn), Phys. Chem.
Chem. Phys. 22 (2020) 20087–20106.
[6] M. Béjaoui, A. Elmhamdi, L. Pascual, P. Pérez-Bailac, K. Nahdi, A. Martínez-Arias,
Preferential oxidation of CO over CoFe2O4 and M/CoFe2O4 (M = Ce, Co, Cu or Zr)
catalysts, Catalysts 11 (2021), 15.
M. Saha et al.
[7] S. Dey, G.C. Dhal, Catalytic conversion of carbon monoxide into carbon dioxide
over spinel catalysts: An overview, Mater. Sci. Energy Technol. 2 (2019) 575–588.
[8] J. Thomas, N. Thomas, F. Girgsdies, M. Beherns, X. Huang, V.D. Sudheesh,
V. Sebastian, Synthesis of cobalt ferrite nanoparticles by constant pH co-
precipitation and their high catalytic activity in CO oxidation, New J. Chem. 41
(2017) 7356–7363.
[9] B.I. Kharisov, H.V.R. Dias, O.V. Kharissova, Mini-review: Ferrite nanoparticles in
the catalysis, Arab. J. Chem. 12 (2019) 1234–1246.
[10] M. Bohra, V. Alman, R. Arras, Nanostructured ZnFe2O4: An exotic energy material,
Nanomaterials 11 (2021), 1286.
[11] M.M. Vadiyar, S.C. Bhise, S.K. Patil, S.A. Patil, D.K. Pawar, A.V. Ghule, P.S. Patil, S.
S. Kolekar, Mechanochemical growth of a porous ZnFe2O4 nano-flake thin film as
an electrode for supercapacitor application, RSC Adv. 5 (2015) 45935–45942.
[12] S. Joshi, V.B. Kamble, M. Kumar, M. Arun, A.M. Umarji, G. Srivastava, Nickel
substitution induced effects on gas sensing properties of cobalt ferrite
nanoparticles, J. Alloys Compd. 654 (2016) 460–466.
[13] K. Preveena, S. Srinath, Synthesis and characterization of CoFe2O4/polyaniline
nanocomposites for electromagnetic interference applications, J. Nanosci.
Nanotechnol. 14 (2014) 4371–4376.
[14] R.V. Lakshmi, P. Bera, R.P.S. Chakradhar, B. Choudhury, S.P. Pawar, S. Bose, R.
U. Nair, H.C. Barshilia, Enhanced microwave absorption properties of PMMA
modified MnFe2O4–polyaniline nanocomposites, Phys. Chem. Chem. Phys. 21
(2019) 5068–5077.
[15] M.A. Ansari, S. Akhtar, M.A. Rauf, M.N. Alomary, S. AlYahya, S. Alghamdi, M.
A. Almessiere, A. Baykal, F. Khan, S.F. Adil, M. Khan, M.R. Hatshan, Sol− gel
synthesis of Dy-substituted Ni0.4Cu0.2Zn0.4(Fe2− xDyx)O4 nano spinel ferrites and
evaluation of their antibacterial, antifungal, antibiofilm and anticancer
potentialities for biomedical application, Int. J. Nanomed. 16 (2021) 5633–5650.
[16] U. Riaz, S.M. Ashraf, E.S. Aazam, Microwave-assisted catalytic activity of
superparamagnetic spinel ferrites, J. Chem. Technol. Biotechnol. 96 (2021)
2792–2801.
[17] G. Xian, S. Kong, Q. Li, G. Zhang, N. Zhou, H. Du, L. Niu, Synthesis of spinel ferrite
MFe2O4 (M = Co, Cu, Mn, and Zn) for persulfate activation to remove aqueous
organics: Effects of M-site and synthetic methods, Front. Chem. 8 (2020), 177.
[18] T.N. Pham, T.Q. Huy, A.-H. Le, Spinel ferrite (AFe2O4)-based heterostructured
designs for lithium-ion battery, environmental monitoring, and biomedical
applications, RSC Adv. 10 (2020) 31622–31661.
[19] E. Roduner, Size matters: Why nanomaterials are different, Chem. Soc. Rev. 35
(2006) 583–592.
[20] V. Mameli, M.S. Angotzi, C. Cara, C. Cannas, Liquid phase synthesis of
nanostructured spinel ferrites− A Review, J. Nanosci. Nanotechnol. 19 (2019)
4857–4887.
[21] R.M. Borade, S.B. Somvanshi, S.B. Kale, R.P. Pawar, K.M. Jadhav, Spinel zinc
ferrite nanoparticles: An active nanocatalyst for microwave irradiated solvent free
synthesis of chalcones, Mater. Res. Express 7 (2020), 016116.
[22] A. Scano, V. Cabras, M. Pilloni, G. Ennas, Microemulsions: The renaissance of
ferrite nanoparticle synthesis,, J. Nanosci. Nanotechnol. 19 (2019) 4824–4838.
[23] J.-L. Ortiz-Quiñonez, U. Pal, M.S. Villanueva, Structural, magnetic, and catalytic
evaluation of spinel Co, Ni, and Co− Ni ferrite nanoparticles fabricated by low-
temperature solution combustion process, ACS Omega 3 (2018) 14986–15001.
[24] S. Diodati, P. Dolcet, M. Casarin, S. Gross, Pursuing the crystallization of mono-
and polymetallic nanosized crystalline inorganic compounds by low-temperature
wet- chemistry and colloidal routes, Chem. Rev. 115 (2015) 11449–11502.
[25] O.K. Mmelesi, N. Masunga, A. Kuvarega, T.T.I. Nkambule, B.B. Mamba, K.
K. Kefeni, Cobalt ferrite nanoparticles and nanocomposites: Photocatalytic,
antimicrobial activity and toxicity in water treatment, Mater. Sci. Semicond.
Process. 123 (2021), 105523.
[26] R. Haghniaz, A. Rabbani, F. Vajhadin, T. Khan, R. Kousar, A.R. Khan,
H. Montazerian, J. Iqbal, A. Libanori, H.-J. Kim, F. Wahid, Anti-bacterial and
wound healing-promoting effects of zinc ferrite nanoparticles, J. Nanobiotechnol.
19 (2021), 38.
[27] K.K. Kefeni, T.A.M. Msagati, T.T.I. Nkambule, B.B. Mamba, Spinel ferrite
nanoparticles and nanocomposites for biomedical applications and their toxicity,
Mater. Sci. Eng. C 107 (2020), 110314.
[28] N.A. Masmali, Z. Osman, A.K. Arof, Recent developments in zinc-based two-cation
oxide spinels: From synthesis to applications, Ceram. Int. 47 (2021) 2949–2962.
[29] K. Wu, J. Li, C. Zhang, Zinc ferrite based gas sensors: A review, Ceram. Int. 45
(2019) 11143–11157.
[30] M.A.E.A.A. El-Remaily, A.M. Abu-Dief, R.M. El-Khatib, A robust synthesis and
characterization of superparamagnetic CoFe2O4 nanoparticles as an efficient and
reusable catalyst for green synthesis of some heterocyclic rings, Appl. Organomet.
Chem. 30 (2016) 1022–1029.
[31] A.L. Lopes-Moriyama, V. Madigou, C.P. de Souza, C. Leroux, Controlled synthesis
of CoFe2O4 nano-octahdera, Powder Technol. 256 (2014) 482–489.
[32] S. Moosavi, S. Zakaria, C.H. Chia, S. Gan, N.A. Azahari, Hydrothermal synthesis,
magnetic properties and characterization of CoFe2O4 nanocrystals, Ceram. Int. 43
(2017) 7889–7894.
[33] A.L. Gurgel, A.E. Martinelli, O.L. de Aquino Conceição, M.M. Xavier Jr., M.A.
M. Torres, D.M. de Araújo Melo, Microwave-assisted hydrothermal synthesis and
magnetic properties of nanostructured cobalt ferrite, J. Alloys Compd. 799 (2019)
36–42.
[34] H. Zhang, H. Li, Z. Wang, B. Li, X. Cheng, Q. Cheng, Synthesis of magnetic CoFe2O4
nmanoparticles and their efficient degradation of diclofenac by activating
persulfate via formation of sulfate radicals, J. Nanosci. Nanotechnol. 18 (2018)
6942–6948.
35731
Ceramics International 48 (2022) 35719–35732
[35] H. Gao, J. Xiang, Y. Cao, Hierarchically porous CoFe2O4 nanosheets supported on
Ni foam with excellent electrochemical properties for asymmetric supercapacitors,
Appl. Surf. Sci. 413 (2017) 351–359.
[36] T.A. Truc, N.X. Hoan, D.T. Bach, T.T. Thuy, K. Ramadass, C.I. Sathish, N.T. Chinh,
N.D. Trinh, T. Hoang, Hydrothermal synthesis of cobalt doped magnetite
nanoparticles for corrosion protection of epoxy coated reinforced steel, J. Nanosci.
Nanotechnol. 20 (2020) 3519–3526.
[37] P. Arévalo-Cid, J. Isasi, M.A. Palafox, F. Martín-Hernández, Comparative
structural, morphological and magnetic study of MFe2O4 nanopowders prepared by
different synthesis routes, Mater. Res. Bull. 123 (2020), 110726.
[38] S. Mishra, S.S. Sahoo, A.K. Debnath, K.P. Muthe, N. Das, P. Parhi, Cobalt ferrite
nanoparticles prepared by microwave hydrothermal synthesis and adsorption
efficiency for organic dyes: Isotherms, thermodynamics and kinetic studies, Adv.
Powder Technol. 31 (2020) 4552–4562.
[39] S. Das, M. Bououdina, C. Manoharan, The influence of cationic surfactant CTAB on
optical, dielectric and magnetic properties of cobalt ferrite nanoparticles, Ceram.
Int. 46 (2020) 11705–11716.
[40] R.S. Melo, P. Banerjee, A. Franco Jr., Hydrothermal synthesis of nickel doped
cobalt ferrite nanoparticles: Optical and magnetic properties, J. Mater. Sci.: Mater.
Electron. 29 (2018) 14657–14667.
[41] K.V. Siva, S. Sudersan, A. Arockiarajan, Bipolar magnetostriction in CoFe2O4:
Effect of sintering, measurement temperature, and prestress, J. Appl. Phys. 128
(2020), 103904.
[42] Q.Q. Xiong, J.P. Tu, S.J. Shi, X.Y. Liu, X.L. Wang, C.D. Gu, Ascorbic acid-assisted
synthesis of cobalt ferrite (CoFe2O4) hierarchical flower-like microspheres with
enhanced lithium storage properties, J. Power Sources 256 (2014) 153–159.
[43] P.T. Phong, P.H. Nam, N.X. Phuc, B.T. Huy, L.T. Lu, D.H. Manh, I.-J. Lee, Effect of
zinc concentration on the structural, optical, and magnetic properties of mixed Co-
Zn ferrites nanoparticles synthesized by low-temperature hydrothermal method,
Metall. Mater. Trans. 50A (2019) 1571–1581.
[44] M. Dhiman, R. Sharma, V. Kumar, S. Singhal, Morphology controlled hydrothermal
synthesis and photocatalytic properties of ZnFe2O4 nanostructures, Ceram. Int. 42
(2016) 12594–12605.
[45] C. Zhang, Q. Wu, B. Zheng, J. You, Y. Luo, Synthesis and acetone gas sensing
properties of Ag activated hollow sphere structured ZnFe2O4, Ceram. Int. 44 (2018)
20700–20707.
[46] Y. Jia, B.W. Lee, C. Liu, Magnetic ZnFe2O4 nanocubes: Synthesis and photocatalytic
activity with visible light/H2O2, IEEE Trans. Magn. 53 (2017), 2800305.
[47] Y. Wang, Y. Jin, R. Zhang, M. Jia, Facile synthesis of ZnFe2O4-graphene aerogels
composites as high-performance anode materials for lithium ion batteries, Appl.
Surf. Sci. 413 (2017) 50–55.
[48] M.I. Nemufulwi, H.C. Swart, W.B. Mdlalose, G.H. Mhlongo, Size-tunable
ferromagnetic ZnFe2O4 nanoparticles and their ethanol detection capabilities,
Appl. Surf. Sci. 508 (2020), 144863.
[49] W. Zhang, Y. Shen, J. Zhang, H. Bi, S. Zhao, P. Zhou, C. Han, D. Wei, N. Cheng,
Low-temperature H2S sensing performance of Cu-doped ZnFe2O4 nanoparticles
with spinel structure, Appl. Surf. Sci. 470 (2019) 581–590.
[50] L. Li, J. Tan, M. Dun, X. Huang, Porous ZnFe2O4 nanorods with net-worked
nanostructure for highly sensor response and fast response acetone gas sensor,
Sens. Actuators B 248 (2017) 85–91.
[51] Z. Fang, L. Zhang, H. Qi, H. Yue, T. Zhang, X. Zhao, G. Chen, Y. Wei, C. Wang,
D. Zhang, Nanosheet assembled hollow ZnFe2O4 microsphere as anode for lithium-
ion batteries, J. Alloys Compd. 762 (2018) 480–487.
[52] R. Sahoo, S. Santra, C. Ray, A. Pal, Y. Negishi, S.K. Ray, T. Pal, Hierarchical growth
of ZnFe2O4 for sensing applications, New J. Chem. 40 (2016) 1861–1871.
[53] M. Amiri, T. Gholami, O. Amiri, A. Pardakhti, M. Ahmadi, A. Akbari,
A. Amanatfard, M. Salavati-Niasari, The magnetic inorganic-organic
nanocomposite based on ZnFe2O4-Imatinib-liposome for biomedical applications,
in vivo and in vitro study, J. Alloys Compd. 849 (2020), 156604.
[54] H.-Y. Xu, B. Li, P. Li, Morphology dependent photocatalytic efficacy of zinc ferrite
probed for methyl orange degradation, J. Serb. Chem. Soc. 83 (2018) 1261–1271.
[55] M.M. Rahman, S.B. Khan, M. Faisal, A.M. Asiri, K.A. Alamry, Highly sensitive
formaldehyde chemical sensor based on hydrothermally prepared spinel ZnFe2O4
nanorods, Sens. Actuators B 171− 172 (2012) 932–937.
[56] C.X. Feng, J. Dongli, G. Yu, Z. Chenmou, Ethanol gas sensor based on CoFe2O4
nano-crystallines prepared by hydrothermal method, Sens. Actuators B 120 (2006)
177–181.
[57] X. Hu, P. Guan, X. Yan, Hydrothermal synthesis of nano-meter microporous zinc
ferrite, China Particuol. 2 (2004) 135–137.
[58] D. Ghosh, D.K. Singha, O.I. Lebedev, Md.M. Seikh, P. Mahata, A remarkable
annealing time effect on the magnetic properties of single-source coordination
polymer precursor-derived CoFe2O4 nanoparticles, New J. Chem. 43 (2019)
19044–19052.
[59] J.A. Toledo-Antonio, N. Nava, M. Martínez, X. Bokhimi, Correlation between the
magnetism of non-stoichiometric zinc ferrites and their catalytic activity for
oxidative dehydrogenation of 1-butene, Appl. Catal. A 234 (2002) 137–144.
[60] L. Zhao, H. Zhang, Y. Xing, S. Song, S. Yu, W. Shi, X. Guo, J. Yang, Y. Lei, F. Cao,
Studies on the magnetism of cobalt ferrite nanocrystals synthesized by
hydrothermal method, J. Solid State Chem. 181 (2008) 245–252.
[61] C.A. Chagas, E.F.D. Souza, M.C.N.A.D. Carvalho, R.L. Martins, M. Schmal, Cobalt
ferrite nanoparticles for the preferential oxidation of CO, Appl. Catal. A 519 (2016)
139–145.
[62] A. Urdă, A. Herraïz, Á. Rédey, I.C. Marcu, Co and Ni ferrospinels as catalysts for
propane total oxidation, Catal. Commun. 10 (2009) 1651–1655.
M. Saha et al.
[63] P. Chandramohan, M.P. Srinivasan, S. Velmurugan, S.V. Narasimhan, Cation
distribution and particle size effect on Raman spectrum of CoFe2O4, J. Solid State
Chem. 184 (2011) 89–96.
[64] M. Milanova, I. Koleva, R. Todorovska, J. Zaharieva, M. Kostadinov,
D. Todorovsky, Polymetallic citric complexes as precursors for spray-pyrolysis
deposition of thin ferrite films, Appl. Surf. Sci. 257 (2011) 7821–7826.
[65] R.S. Yadav, I. Kuřitka, J. Vilcakova, J. Havlica, J. Masilko, L. Kalina, J. Tkacz,
J. Švec, V. Enev, M. Hajdúchová, Impact of grain size and structural changes on
magnetic, dielectric, electrical, impedance and modulus spectroscopic
characteristics of CoFe2O4 nanoparticles synthesized by honey mediated sol-gel
combustion method, Adv. Nat. Sci. 8 (2017), 045002.
[66] P.N. Anantharamaiah, P.A. Joy, Enhancing the strain sensitivity of CoFe2O4 at low
magnetic fields without affecting the magnetostriction coefficient by substitution
of small amounts of Mg for Fe, Phys. Chem. Chem. Phys. 18 (2016) 10516–10527.
[67] R.D. Waldron, Infrared spectra of ferrites, Phys. Rev. 99 (1955) 1727–1735.
[68] L. Avazpour, M.A.Z. Khajeh, M.R. Toroghinejad, H. Shokrollahi, Synthesis of
single-phase cobalt ferrite nanoparticles via a novel EDTA/EG precursor-based
route and their magnetic properties, J. Alloys Compd. 637 (2015) 497–503.
[69] V.S. Kumbhar, A.D. Jagadale, N.M. Shinde, C.D. Lokhande, Chemical synthesis of
spinel cobalt ferrite (CoFe2O4) nano-flakes for supercapacitor application, Appl.
Surf. Sci. 259 (2012) 39–43.
[70] R.K. Sharma, R. Ghose, Synthesis and characterization of nanocrystalline zinc
ferrite spinel powders by homogeneous precipitation method, Ceram. Int. 41
(2015) 14684–14691.
[71] M.D.P. Silva, F.C. Silva, F.S.M. Sinfrônio, A.R. Paschoal, E.N. Silva, C.W.
A. Paschoal, The effect of cobalt substitution in crystal structure and vibrational
modes of CuFe2O4 powders obtained by polymeric precursor method, J. Alloys
Compd. 584 (2014) 573–580.
35732
Ceramics International 48 (2022) 35719–35732
[72] M. Lazzeri, P. Thibaudeau, Ab initio Raman spectrum of the normal and disordered
MgAl2O4 spinel, Phys. Rev. B 74 (2006), 140301.
[73] G.A. de Wijs, C.M. Fang, G. Kresse, G. de With, First-principles calculation of the
phonon spectrum of MgAl2O4 spinel, Phys. Rev. B 65 (2002), 094305.
[74] A. Singh, A. Singh, S. Singh, P. Tandon, B.C. Yadav, R.R. Yadav, Synthesis,
characterization and performance of zinc ferrite nanorods for room temperature
sensing applications, J. Alloys Compd. 618 (2015) 475–483.
[75] S.A. Mazen, S.F. Mansour, E. Dhahri, H.M. Zaki, T.A. Elmosalami, The infrared
absorption and dielectric properties of Li–Ga ferrite, J. Alloys Compd. 470 (2009)
294–300.
[76] S.R. Devan, Y.R. Ma, B.K. Chougule, Effective dielectric and magnetic properties of
(Ni–Co–Cu)ferrite/BTO composites, Mater. Chem. Phys. 115 (2009) 263–268.
[77] M. George, S.S. Nair, K.A. Malini, P.A. Joy, M.R. Antharaman, Finite size effects on
the electrical properties of sol–gel synthesized CoFe2O4 powders: Deviation from
Maxwell− Wagner theory and evidence of surface polarization effects, J. Phys. D:
Appl. Phys. 40 (2007) 1593–1602.
[78] J.B. Silva, C.F. Diniz, J.D. Ardinson, A.I.C. Persiano, N.D.S. Mohallem, Cobalt
ferrite dispersed in a silica matrix prepared by sol–gel process, J. Magn. Magn.
Mater. 272 (2004) 1851–1853.
[79] A. Jabbar, I. Qasim, S.A. Khan, K. Nadeem, M. Waqee-ur-Rehman, M. Mumtaz,
F. Zeb, Highly coercive cobalt ferrite nanoparticles-CuTl-1223 superconductor
composites, J. Magn. Magn. Mater. 377 (2015) 6–11.
[80] J. Curiale, M. Granada, H.E. Troiani, R.D. Sánchez, A.G. Leyva, P. Levy, K. Samwer,
Magnetic dead layer in ferromagnetic manganite nanoparticles, Appl. Phys. Lett.
95 (2009), 043106.
[81] M. Rajendran, R.C. Pullar, A.K. Bhattacharya, D. Das, S.N. Chintalapudi, C.
K. Majumdar, Magnetic properties of nanocrystalline CoFe2O4 powders prepared at
room temperature: Variation with crystallite size, J. Magn. Magn. Mater. 232
(2001) 71–83.