Materials Chemistry and Physics 143 (2013) 203e208

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Materials Chemistry and Physics

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

Synthesis, structural characterization, and magnetic property

of nanostructured ferrite spinel oxides (AFe2O4, A ¼ Co, Ni and Zn)
Chuleeporn Luadthong a, Vorranutch Itthibenchapong a, Nawin Viriya-empikul a,
Kajornsak Faungnawakij a, *, Prasert Pavasant b, Wiwut Tanthapanichakoon b, c
a
Nanomaterials for Energy and Catalysis Laboratory, National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency
(NSTDA), 111 Thailand Science Park, Paholyothin Rd., Klong Laung, Pathumthani 12120, Thailand
b
Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
c
Department of Chemical Engineering, Graduate School of Science & Engineering, Tokyo Institute of Technology, Tokyo 152-8550, Japan

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Mesoporous ferrite spinels AFe2O4

(A ¼ Co, Ni, Zn) from an acid
complexation
 High crystallinity in single spinel
phase at calcination temperature of
500e900  C.
 The controllable pore size in a range
of 3 nm up to a hundred nm.
 The maximum BET surface area at 201
(Co), 315 (Ni), and 273 (Zn) m2 g1
 Ferromagnetism in CoFe2O4, super-
paramagnetismeferromagnetism in
NiFe2O4.

a r t i c l e i n f o a b s t r a c t

Article history: Nanostructured ferrite spinels AFe2O4 (A ¼ Co, Ni, Zn) were successfully synthesized via a co-
Received 26 January 2013 precipitation method using oxalate salt as a precursor in an anionic surfactant system in combination
Received in revised form with a simple calcination process. High crystallinity samples of nanoparticle spinels in a grain size range
6 July 2013
of 15e100 nm were obtained by varying the calcination temperature (300e700  C) and time (1e5 h).
Accepted 30 August 2013
Their pore sizes were controlled in a range of 3 nm up to a hundred nm by tailoring the calcination
conditions. Raising the calcination temperature was found to decrease the BrunauereEmmetteTeller
Keywords:
(BET) surface area, and broaden the pore structure due to enhanced crystal growth and agglomeration of
Nanostructures
Magnetic materials
interparticles of spinels. Transmission electron microscopy (TEM) images of ferrite spinels calcined at
Precipitation 300  C showed mesoporous structures with narrow pore size distribution, and the maximum BET surface
Heat treatment area of CoFe2O4, NiFe2O4 and ZnFe2O4 were found at 201 (Co), 315 (Ni), and 273 (Zn) m2 g1, respectively.
Electron microscopy The magnetic hysteresis loops of the ferrite spinels at room temperature demonstrated ferromagnetism
in CoFe2O4, superparamagnetismeferromagnetism in NiFe2O4, and paramagnetism in ZnFe2O4. The
highest saturation magnetization (Ms), remanent magnetization (Mr), and coercivity (Hc) were obtained
from high crystallinity spinels calcined at 700  C. Nanostructured AFe2O4 with high surface area and
mesoporosity promises potentials as novel magnetic catalysts.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction

* Corresponding author. Tel.: þ66 2 564 7100x6638; fax: þ66 2 564 6981. Ferrite spinels (AFe2O4), cubic or tetragonal spinel type struc-
E-mail addresses: kajornsak@nanotec.or.th, jiw037@yahoo.com (K. Faungnawakij). tures, have been extensively employed in a variety of applications

0254-0584/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matchemphys.2013.08.052
204 C. Luadthong et al. / Materials Chemistry and Physics 143 (2013) 203e208
in the past decades such as magnetic materials [1,2], magnetic
biomedicines [3e5], and catalysis [6e8] because of their excellent
features e.g. magnetism, electronic, and catalytic properties.
Moreover, in recent years, researches on the mesoporous spinels
with well-defined pore structure have gained much attention in
heterogeneous catalysis due to the abilities to control pore size and
pore morphology through particular synthesis approaches. Con-
ventional preparation methods of ferrite spinel that generally do
not rely on templating include solegel auto-combustion [9e11], co-
precipitation [12,13], hydrothermal/solvothermal method [14e17],
plasma reaction [18], and solegel method [19]. On the other hand,
nanocasting technique [20,21] is a well-known method of tem-
plating which is capable to create mesoporous spinels by employ-
ing selected templates of mainly mesoporous materials. For
examples, Hill et al. prepared mesoporous Co3O4 spinel using
mesoporous silicas KIT-6 and SBA-16 as hard templates, leading to a
surface area of 92e122 m2 g1 with pore diameter in a range of 4e
9 nm [22]. Similar surface areas and large pore volumes, i.e. 0.35e
0.41 cm3 g1, of mesoporous MCo2O4 (M ¼ Cu, Mn and Ni) [23] and
MAl2O4 (M ¼ Cu, Ni, Fe, Mg) [24] were obtained by the use of
mesoporous silica SBA-15 as a template. Nonetheless, major dis-
advantages of the nanocasting method are multiple steps of syn-
thesis, time consuming and costly production. For these reasons, a
non-conventional template-free approach yielding mesoporous
structure is desirable.
Interestingly, a preparation of NiFe2O4 into a mesoporous ferrite
spinel by a template-free route using sodium dioctylsulfosuccinate
(AOT) as a surfactant [25] yielded high surface area (up to
301.6 m2 g1) with an average pore diameter of 2.5e16.2 nm.
Therefore, this method should be applicable to other divalent cat-
ions in the AFe2O4 spinel structure. Since most ferrites possess in-
verse spinel structure, where Fe3þ cations occupy both octahedral
and tetrahedral sites, and A2þ divalent cations such as Ni2þ, Co2þ
reside at octahedral sites. In contrast, ZnFe2O4 is inverse spinel at
cryogenic temperature, but normal spinel at room temperature. As
a result, variation of the divalent cations influences the magnetic
structure of ferrites, i.e., ferromagnetic, antiferromagnetic, ferri-
magnetic, paramagnetic, and superparamagnetic behaviors [26].
Previously shown, ferrite spinels prepared by suitable methods
demonstrated high surface area with mesoporous structure,
promising great potentials in catalysis, especially selective re-
actants corresponding to pore size of the catalyst. Therefore, in the
present work, the objective is to synthesize ferrite spinels AFe2O4
(A ¼ Co, Ni, Zn) via modification of the co-precipitation method
using oxalate salt precursor combined with an anionic surfactant.
The effect of various synthesis parameters including molar ratio of
the precursor to the surfactant and calcination conditions on spinel
formation are studied. In addition, the effects of the divalent cat-
ions, namely, Co, Ni, Zn, on the crystal structure, porous structure,
and magnetization of the obtained spinel are systematically
investigated and correlated. With the present findings, we can
tailor the pore size from meso to macropore scale and understand
the crystal structure and magnetic property of the developed ferrite
spinels. The synthesized multifunctional materials would not only
have potential applications in various fields such as catalysis and
adsorption but also are easy to separate and recover by applying a
magnetic field.
2. Experimental
2.1. Material preparation
The AFe2O4 spinels (A ¼ Co, Ni, Zn) were prepared by a co-
precipitation method modified from Z. Gao [25]. Corresponding
amounts of FeSO4$7H2O (Ajax, 98%) and Co(NO3)2$6H2O (Wako,
98%), NiCl2$6H2O (Wako, 98%), or Zn(CH3COO)2$2H2O (Ajax, 99.5%)
were mixed at a 2:1 mol ratio together with 0.5 mol of sodium
dioctylsulfosuccinate (AOT, Aldrich, 98%) as the surfactant. Next,
the mixture was dissolved in deionized water, heated and kept at
80  C with continuous stirring overnight. Then the reaction mixture
was combined with 3 mol of 1 M oxalic acid solution (Ajax, 99.5%),
which was added dropwise while being stirred before continuing
stirring for 14 h at 80  C. Obtained precipitates were filtered, rinsed
with deionized water and ethanol several times, and subsequently
dried in an oven at 60  C overnight. The metal-oxalate precursors
were proposed to be AFe2(C2O4)3 (A ¼ Co, Ni, Zn) [25], and the exact
stoichiometric molar ratio of spinel synthesis became A:Fe:oxalic
acid:AOT ¼ 1:2:3:0.5. Finally, a calcination of the as-synthesized
samples was carried out at 300  C (coded as CoFe300, NiFe300,
ZnFe300), 500  C (CoFe500, NiFe500, ZnFe500) and 700  C
(CoFe700, NiFe700, ZnFe700) with a heating rate of 1  C min1, and
held for 1 h. The formation of AFe2O4 spinel oxides occurred via the
decomposition of AFe2(C2O4)3 in the air. The NiFe2O4 (NiFe700)
sample was selected for further study on the effect of oxalic acid on
the synthesis, resulting sample’s property. The ratios of 1:2:1.5:0.5
(non-stoichiometric oxalic acid usage) and 1:2:6:0.5 (excess oxalic
acid usage) were compared to the stoichiometric one. Effect of
calcination time on crystallinity of NiFe700 was also investigated.
2.2. Characterization
Powder X-ray diffraction (XRD) patterns of the samples were
collected on an X-ray diffractometer (D8 ADVANCE, Bruker, Ltd.,
Germany) using Cu Ka radiation. The measurements were made at
40 kV, 40 mA, and intervals of 0.02 s1 with a time step of 0.5 s
over the range of 10 < 2q < 80 . The specific surface areas and pore
volumes were measured with nitrogen adsorptionedesorption
technique (Belsorp-max, Bel Japan, Inc., Japan). Pore size distribu-
tion plots for mesoporosity were obtained by BarretteJoynere
Halenda (BJH) desorption method using the cylindrical pore model.
The morphology of the spinel particles was obtained by a trans-
mission electron microscopy (TEM; JEM-2100 Jeol, Japan). Magnetic
hysteresis loops were recorded at room temperature utilizing a
vibrating sample magnetometry (VSM; LAKESHORE VSM 7404,
Lake Shore Cryotronics, Inc., USA) with a maximum magnetic field
of 10 kG.
3. Results and discussions
3.1. Phase identification
Phase identity and crystallinity of ferrite spinel samples, syn-
thesized with a ratio of 1:2:3:0.5 (A:Fe:oxalic acid:AOT) and sub-
sequently calcined for 1 h at 300e700  C, are revealed through
peak intensity and position of XRD patterns (Fig. 1). The diffraction
peaks of CoFe2O4 (Fig. 1a) at 2q ¼ 19.0 , 30.4 , 35.6 , 37.1, 43.4 ,
54.2 , 57.3 and 62.9 can be attributed to the reflection of (111),
(220), (311), (222), (400), (422), (511), and (440) planes [27]. The
formation of CoFe2O4 spinel (PDF# 01-076-7254) was achieved by
the calcination from 300  C, and the enhancement of peak intensity
was maximized at 700  C, where high crystallinity of samples was
achieved. Similar results were observed in NiFe2O4 (Fig. 1b) and
ZnFe2O4 (Fig. 1c), although their peak positions shifted slightly from
those of CoFe2O4 as follows: in case of NiFe2O4 (PDF#01-076-6120)
2q ¼ 18.5 , 30.4 , 35.7, 37.3 , 43.3 , 53.9 , 57.3 , and 63.1 [25] and
in case of ZnFe2O4 (PDF# 01-077-4101) 2q ¼ 18.3 , 30.0 , 35.3 ,
43.0 , 53.3 , 56.7, and 62.2 [28]. The crystallite sizes of the sam-
ples were, respectively, determined as 14, 9, and 14 nm for
CoFe500, NiFe500, and ZnFe500 and as 36, 18, and 46 nm for
CoFe700, NiFe700, and ZnFe700. The diffractograms of the samples
 C. Luadthong et al. / Materials Chemistry and Physics 143 (2013) 203e208
Fig. 1. XRD patterns of samples synthesized with the stoichiometric molar ratio of
1:2:3:0.5 and calcined for 1 h: (a) CoFe2O4 (b) NiFe2O4 and (c) ZnFe2O4.
calcined at 300  C are too broad for crystallite size determination
due to their low crystallinity.
The XRD patterns of NiFe2O4, shown in Fig. 2a, indicated that a
single phase of NiFe2O4 was formed when the use of either a stoi-
chiometric molar ratio (A:Fe:oxalic acid:AOT ¼ 1:2:3:0.5) or an
excess oxalic acid condition (A:Fe:oxalic acid:AOT ¼ 1:2:6:0.5),
providing similar XRD patterns and high crystallinity. However, NiO
impurity phase is found when the amount of oxalic acid used was
50% less than the stoichiometric molar ratio. NiO peaks overlapped
with those of NiFe2O4 (or Fe3O4), thereby resulting in relative in-
tensity change in NiFe2O4 diffraction pattern compared to that of
single-phase NiFe2O4. This implies that the reaction between oxalic
acid and metal salts yielded a precursor of the A-Fe oxalate complex
that required 3 M ratio of oxalic acid. Conceivably, the use of excess
oxalic acid would enhance the precipitation, but did not affect the
crystallinity and porous structural property of the samples. As
shown in Fig. 2b, the higher XRD peak intensity can be obtained at a
longer calcination time; therefore an increase of calcination time
enhanced the crystallinity. Furthermore, the increase of crystallite
size of the cubic spinel, from 18 nm (1 h) to 19 nm (2 h), and 22 nm
(5 h), suggests crystal growth without any phase separation and
distortion.
3.2. Morphology, pore structures and surface areas
TEM imaging of AFe2O4 (A ¼ Co, Ni, Zn) was collected on the
samples calcined for 1 h at various temperatures. Interestingly, all
AFe2O4 samples obtained with the same calcination temperature
have similar morphology, as seen in Fig. 3. In addition, all spinel
samples calcined at 300  C exhibited uniform mesoporous struc-
tures with average pore size of ca. 2e3 nm (Fig. 3a, d, g), where
each one consisted of uniform small grains with average size of ca.
3e5 nm. The grains were bonded together as a framework, thereby
205
Fig. 2. XRD patterns of NiFe700 prepared with (a) different molar ratios of oxalic acid
and 1 h calcination (b) different calcination times and the stoichiometric molar ratio
(1:2:3:0.5).
leaving pore structures in between them. We considered that pore
structure formation initially proceeded via a slow release of gases
from thermal decomposition of oxalates in the metal-oxalate
complex during calcination. Subsequently, the corresponding
metals formed spinel crystallites which were aggregated into the
nano-sized grains, and consequently the nanopores between grains
were developed. When the calcination temperature increased, the
spinel grains were enlarged by crystal growth and sintering.
Simultaneously, pore enlargement was achieved. Similarly, the
grain sizes of CoFe2O4 and ZnFe2O4 were in a range of 15e20 nm
(calcination at 500  C) and 80e100 nm (calcination at 700  C).
NiFe2O4 samples developed relatively smaller grain size of ca. 10
and 50 nm upon calcination at 500 and 700  C, respectively. It
should be noted that the grain sizes of the samples calcined at
500  C were nearly comparable between TEM observation (10e
20 nm) and XRD analysis (9e14 nm). The results suggest that each
grain would be single-crystalline; although, the grain boundary has
partially aggregated. The grain size of the samples calcined at
700  C or higher was much larger than their corresponding crys-
tallite size, which suggests strong sintering effect along with crystal
growth.
N2 adsorptionedesorption isotherms of AFe2O4 (A ¼ Co, Ni, Zn)
showed type-IV isotherm (Fig. 4), typical feature of mesoporous
structure. As confirmed by TEM images, the porous structure with
206 C. Luadthong et al. / Materials Chemistry and Physics 143 (2013) 203e208
Fig. 3. TEM images of AFe2O4 (A ¼ Co, Ni, Zn) calcined for 1 h at different temperatures: (a) CoFe300, (b) CoFe500, (c) CoFe700, (d) NiFe300, (e) NiFe500, (f) NiFe700, (g) ZnFe300,
(h) ZnFe500, (i) ZnFe700.
good pore uniformity was apparently formed at 300  C calcination.
On the other hand, mesoporosity decreased as the calcination
temperature rose up to 700  C because of increasing particle ag-
gregation and disruption of pore formation between interparticles
of spinels.
Pore structure parameters of AFe2O4 (A ¼ Co, Ni, Zn) are sum-
marized in Table 1. Surprisingly, the observed BET surface areas
were in the range of several hundred m2 g1 at 300  C calcination
for 1 h: CoFe300 (201 m2 g1), NiFe300 (315 m2 g1) and ZnFe300
(273 m2 g1). An increase of calcination temperature (>300  C)
and/or time significantly decreased the surface areas and mesopore
volumes of the samples. For example, the pore size is widened from
the mesoporous range (2e50 nm) to the macroporous range
(>50 nm) by calcination at 700 and 900  C due to crystal growth
and formation of large spinel particles which generate large voids
(pores) via interparticle contacts. The effect of calcination temper-
ature and time on the pore structure was further investigated over
NiFe2O4 samples through the pore size distributions of NiFe2O4
obtained at various calcination temperatures (Fig. 5). The calcina-
tion at 300  C for 1 h yielded pore sizes well within the mesoporous
range, and the size distribution was narrow with a peak at 3.3 nm.
The broadening of pore size distribution occurred at higher calci-
nation temperature, and the pore size was peaked at 9.2 (500  C),
18.5 (600  C), and 37.9 (700  C) nm. The average pore diameter
increased up to 106.1 nm for the sample calcined at 900  C for 1 h
(Table 1). As seen in Fig. 6, the increase of calcination time from 1 to
5 h could enlarge the pore size from meso to macroporous struc-
tures. The pore size of the NiFe700 was peaked at 37.9 (1 h), 44.1
(2 h), and 51.1 (5 h) nm. The pore size distribution of the sample
became broader at longer calcination time. Nonetheless, the spe-
cific surface area of the sample decreased monotonously with
longer calcination time, i.e. 25 (1 h), 23 (2 h), 19 (5 h) m2 g1. With
these results, the controlled pore size of the spinel samples can
range from meso to macroporous scale by adjustment of the
calcination temperature and time.
3.3. Magnetization
Magnetization measurements of ferrite spinels were carried out
at room temperature using a vibrating sample magnetometer
(VSM). The magnetic hysteresis loops of samples with different
calcination temperatures are displayed in Fig. 7. The saturation
magnetization (Ms), remanent magnetization (Mr) and coercivity
(Hc) are listed in Table 2. The magnetization intensity was enhanced
as the crystallinity obtained via high temperature calcination, e.g.,
CoFe700 and NiFe700. The magnetic hysteresis loops of CoFe2O4
calcined in a range of 300e700  C apparently exhibited ferromag-
netic behaviors, especially with hard magnetic feature observed
in CoFe700, due to large Hc value. Therefore large external
fields applied in the opposite direction are required to yield
 C. Luadthong et al. / Materials Chemistry and Physics 143 (2013) 203e208 207

Fig. 5. Pore size distribution of NiFe2O4 calcined at 300e700  C.

Fig. 4. N2 adsorptionedesorption isotherms of AFe2O4 (A ¼ Co, Ni, Zn) calcined at
300e700  C: (a) CoFe2O4, (b) NiFe2O4 and (c) ZnFe2O4.
demagnetization. The magnetic hysteresis loops of ZnFe2O4 sam-
ples calcined at 300e700  C exhibited paramagnetic behavior with
linear-shape magnetic hysteresis loop and very small saturation
magnetization (0.5e1.2 emu g1). Interestingly, NiFe300 was found
to exhibit a superparamagnetic behavior [26] with a small coer-
civity (6.73 G), whereas NiFe500 and NiFe700 which showed soft-
magnetic property with coercivity less than 300 G displayed
ferromagnetic behavior. We postulate that, in contrast to CoFe300
and ZnFe300, the superparamagnetic property of NiFe300 e typical
of nanoparticles e may be attributed to the very tiny grain size of
the sample (less than 10 nm, shown in Fig. 3d), the S-shape hys-
teresis loop, and a certain degree of magnetization under the
applied external field.
The magnetization of AFe2O4, at room temperature, was found
to decrease in the order of CoFe2O4 > NiFe2O4 >> ZnFe2O4 under
similar calcination condition. At room temperature, it is generally
known that CoFe2O4 and NiFe2O4 are inverse spinel, while ZnFe2O4
is normal spinel. In the case of CoFe2O4 and NiFe2O4, Fe3þ (d5)
equally occupies both octahedral and tetrahedral sites, whereas
Co2þ (d7, 3 unpaired electrons) and Ni2þ (d8, 2 unpaired electrons)
occupy mainly octahedral sites. Net magnetic moments of Fe3þ are
antiparallel and mostly cancel out each other; therefore, net mag-
netic moments and spin alignments of Co2þ and Ni2þ dominate the
magnetization of inverse spinel ferrites. On the other hand, Zn2þ
(d10, no unpaired electrons) occupying tetrahedral sites is non-
magnetic, while Fe3þ with random spins resides in octahedral
sites, leading to the paramagnetic behavior observed in ZnFe2O4.
Due to the limitation of our VSM instrument which can perform
measurements only the room temperature, we could not provide
here additional magnetic susceptibility information on the
temperature-dependent magnetic property of AFe2O4, especially
their superparamagnetism. These expanded measurements on the
magnetization of AFe2O4 are recommended for future work.
4. Conclusions
Well known for their magnetic properties, the ferrite spinels
have expanded their potentials to catalysis, thanks to suitable
nanoporous feature obtained through novel synthesis methods.
Nanostructured AFe2O4 (A ¼ Ni, Co, Zn) spinels were successfully
synthesized via a co-precipitation method using an oxalate
precursor together with AOT. The BET surface area, pore size

Table 1
BET surface areas, BJH pore sizes and pore volumes of samples.

Sample BET surface dBJH (nm) Mesopore

area (m2 g1) volume (cm3 g1)

CoFe300, 1 h 201 3.7 0.27

CoFe500, 1 h 55 13.9 0.31
CoFe700, 1 h 18 51.1 0.28
NiFe300, 1 h 315 3.3 0.38
NiFe400, 1 h 203 4.2 0.35
NiFe500, 1 h 106 9.2 0.32
NiFe600, 1 h 51 18.5 0.29
NiFe700, 1 h 25 37.9 0.27
NiFe700, 2 h 23 44.1 0.24
NiFe700, 5 h 19 51.1 0.20
NiFe900, 1 h 6 106.1 0.02
ZnFe300, 1 h 273 3.3 0.24
ZnFe500, 1 h 58 9.2 0.26
ZnFe700, 1 h 16 44.1 0.21
Fig. 6. Pore size distribution of NiFe2O4 calcined at 700  C for 1, 2 and 5 h.
208 C. Luadthong et al. / Materials Chemistry and Physics 143 (2013) 203e208

area became smaller with increasing calcination temperature and

time. The magnetization effect was enhanced as the calcination
temperature and crystallinity of samples increased. Moreover, this
study revealed that the magnetization values measured at room
temperature were in the order of CoFe2O4 > NiFe2O4 >> ZnFe2O4
under the same calcination condition. The development of multi-
functional nanostructured materials can be applicable to hetero-
geneous catalysis and facilitated product separation such as
magnetic catalysts and magnetic adsorbents.

Acknowledgment

This work was supported by the Thailand Research Fund to K.F.

(RSA5580055) and the National Nanotechnology Center.

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