Ceramics International 44 (2018) 8576–8581

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Ceramics International
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Synthesis and characterization of cobalt ferrite nanoparticles prepared by T

the glycine-nitrate process
⁎
Ali Malekia, , Nazanin Hosseinib, AliReza Taherizadehb,c
a
Department of Mechanical Engineering, Isfahan University of Technology, Isfahan 8415683111, Iran
b
Research Institute for Steel, Isfahan University of Technology, Isfahan 8415683111, Iran
c
Institute of Ceramic, Glass and Construction Materials, TU Bergakademie Freiberg, Germany

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

Keywords: In this research, microstructural evolution and magnetic properties of cobalt ferrite spinel (CoFe2O4) were
Cobalt ferrite studied. The ferrite was prepared by the glycine-nitrate process (GNP) followed by calcination process, and
Glycine-nitrate process subsequent high energy mechanical milling. The samples were characterized by X-ray diffraction (XRD), field
Magnetic properties emission scanning electron microscopy (FESEM), and vibration sample magnetometery (VSM) methods. The
Single domain size
results showed that the desired high purity spinel phase was formed through a complete combustion reaction
using the G/N ratio of 1.48. The as-synthesized powder revealed the coercivity and saturation magnetization of
900 Oe and 62.83 emu/g, respectively. The CoFe2O4 phase was stable after calcination at 500 °C for 2 h under
argon atmosphere and subsequent milling processes for 2 and 4 h. The highest coercivity value was obtained for
the calcined sample (975 Oe), whose average particle size exhibited noticeable conformity with the single
magnetic domain size of CoFe2O4 (~ 40 nm). For the 2 h-milled and 4 h-milled samples, the average particle size
was below the single magnetic domain size, causing a significant reduction in coercivity values (820 and 770 Oe,
respectively). The saturation magnetization was increased negligibly after the calcination process (63.22 emu/
g), while it was raised to 71.47 and 73.98 emu/g after 2 and 4 h milling, probably due to the cationic redis-
tribution during milling.

1. Introduction structural formula of CoFe2O4 is:

In recent decades, there has been significant progress in the field of
magnetic nanoparticles science with the uniform size distribution due
to their unique magnetic properties [1]. As an example, stable sus-
pensions of superparamagnetic nanoparticles, known as magnetic fluids
(or ferrofluids), are important candidates for numerous industrial ap-
plications [2]. An important category of magnetic materials is spinel
ferrites, which can be used for various applications such as magnetic
recording media [3], biomedicine (e.g. cellular labeling or cell se-
paration, contrast enhancers in magnetic resonance imaging, drug de-
livery, tissue repair, etc.) [4], microwave devices [5], and permanent
magnets [6]. It has been reported in the literature that the magnetic
properties of spinel ferrite nanoparticles synthesized by the sol–gel
process, mechanochemical synthesis, or other techniques are sig-
nificantly different from those of their bulk materials [7]. Cobalt ferrite
(CoFe2O4) is one of the most commonly investigated magnetic spinel
ferrites exhibiting such unique properties as high coercivity, magneto-
crystalline anisotropy, chemical stability, moderate saturation magne-
tization, wear resistance, and electrical insulation [8–10]. The
(Co12−+iFei3 +)[Coi2 +Fe23−+i] O42 −,
where the round and square brackets belong to tetrahedral and octa-
hedral lattice sites, respectively. Moreover, i is the inversion degree
signifying the fraction of tetrahedral sites (A-sites) occupied by Fe3+
cations. In the case of the normal spinel structure, Co2+ and Fe3+ ca-
tions occupy tetrahedral and octahedral sites, respectively (i = 0). As
for the inverse spinel structure, Fe3+ ions sit on tetrahedral sites, while
octahedral sites (B-sites) are filled by the remaining Co2+ and Fe3+ ions
(i = 1) [11]. It should be noted that CoFe2O4 usually reveals a mixed
spinel structure (0 < i < 1) comprising Co2+ and Fe3+ cations on both
tetrahedral and octahedral sites [12]. It is well known that the magnetic
properties of cobalt ferrite are considerably influenced by such factors
as sample preparation and the synthesis method used [10,13], cobalt
content [10], crystallite (particle) size [10,13,14], and cation dis-
tribution [13,14]. It has also been reported that the synthesis method
has a considerable effect on cation distribution inside the lattice of
CoFe2O4 nanoparticles. For instance, Sato Turtelli et al. [12] in-
vestigated the quantity of Co2+ cations in octahedral sites for CoFe2O4

⁎
Corresponding author.
E-mail address: maleki110@cc.iut.ac.ir (A. Maleki).

https://doi.org/10.1016/j.ceramint.2018.02.063
Received 3 January 2018; Received in revised form 6 February 2018; Accepted 6 February 2018
Available online 07 February 2018
0272-8842/ © 2018 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
A. Maleki et al. Ceramics International 44 (2018) 8576–8581

prepared by sol-gel (SG) and ball milling (BM) methods. Their results βcosθ = kλ / d + ηsinθ , (1)
showed that the quantity of Co2+ in the octahedral sites of the SG
where β is the full width at the half maximum (FWHM) of XRD peaks, θ
sample was less than that in the BM sample, causing the smaller sa-
is the diffraction angle, k is the Scherrer constant (0.9), η is the strain,
turation magnetization in the BM sample, as compared with the SG
and λ is the X-ray wavelength. When βcosθ was plotted against sinθ
sample. Various preparation techniques such as sol-gel method
using all ferrite peaks, a straight line was obtained with the slope of η
[9,14,15], microemulsion [16], chemical co-precipitation [17], hydro-
and the y-intercept of 0.9λ / d . The morphology of calcined and ball-
thermal synthesis [18,19], microwave synthesis [20], mechanical mil-
milled powders was characterized by FESEM (TESCAN, Czech Re-
ling [21,22], and combustion synthesis methods [10,23] have been
public). The micrographs was used not only for qualitative observation
studied and employed to synthesize CoFe2O4 nanoparticles. Among
of the particles morphology, but also for quantitative image analysis of
them, the combustion synthesis route has received more attention for
each specimen by image J software. The reported particle size was the
preparing multi-component metal oxide nanoparticles, especially spinel
average of at least 60 individual particles diameter measurement. The
cobalt ferrites [10,11,23–25]. This arises from its relatively inexpensive
results of Williamson-Hall and image analysis methods were compared
precursor, high energy efficiency, short reaction time, and its moderate
in results and discussion. Additionally, the magnetic properties of all
heating temperature. In general, the combustion reaction occurs be-
samples were measured using a vibration sample magnetometer (VSM,
tween metal nitrates as the oxidizing agents and organic fuels as the
Meghnatis Kavir Kashan Co., Iran) at room temperature.
reducing agents. Given the fact that the fuel plays an important role in
the morphology and phase formation of the final product, the fuel and
3. Results and discussion
fuel to oxidant ratio must be selected carefully [14].
Glycine is a promising candidate used as an organic fuel in the
The stoichiometric G/N ratio was calculated based on the principle
combustion synthesis method. Actually, glycine-nitrate combustion
of propellant chemistry [30,31], considering the fact that the total
process (GNP) is performed by the self-combustion of glycine and metal
oxidizing and reducing valence of the oxidizers (metal nitrates) and fuel
nitrate, thus yielding high purity complex metal oxide powders with a
should be equal. The valence of reducing agents such as H, C, Co and Fe
uniform composition [26,27] and a nano-scale structure [26]. However,
was + 1, + 4, + 2 and + 3, respectively, whereas O was the oxidizing
most studies on the synthesis of spinel cobalt ferrite by using the
element with the valence of − 2; also, the valence of N was considered
combustion method have been focused on the application of urea as an
zero. Regarding the mentioned individual valencies, the total oxidizing
organic fuel [10,11,23,25], while fabrication of CoFe2O4 by GNP is
valence (− 10 for Co(NO3)2 and − 30 for 2Fe(NO3)3) should be ba-
rarely reported. Therefore, CoFe2O4 magnetic nanoparticles were syn-
lanced by the total reducing valence in the glycine (+ 9). To release the
thesized via GNP and characterized in this research. Moreover, the ef-
maximum energy during the combustion reaction, the stoichiometric
fects of the calcination process and the subsequent mechanical milling
composition of the redox mixture had to satisfy − 40 + 9 × =0,
on magnetic properties have been discussed in details.
yielding x = 4.44 mol of glycine. Therefore, to prepare 1 mol of
CoFe2O4, the appropriate molar ratio of reactants was 1:2:4.44 of Co
2. Experimental
(NO3)2·6H2O, Fe(NO3)3·9H2O, and CH2NH2COOH; they reacted ac-
cording to the following reaction:
2.1. CoFe2O4 synthesis
Co (NO3)2 . 6H2 O + 2Fe (NO3)3 . 9H2 O + 4.44CH2 NH2 COOH + 0.5O2
Powder of CoFe2O4 nanoparticle was synthesized by GNP, based on
→ CoFe2 O4 + 35.1H2 O + 8.88CO2 + 6.22N2 + 0.51O2 (2)
the method reported in [28]. The analytical grades of Iron nitrate (Fe
(NO3)3·9H2O, Merk, 98%), cobalt nitrate (Co(NO3)2·6H2O, Iran Chem- This reaction indicated that the stoichiometric G/N ratio was 1.48.
istry, 99.9%), and glycine (CH2NH2COOH, Applichem, 98.5%) were The diffractogram of the as-synthesized powder is illustrated in
used as the raw materials in air without any protective atmosphere. To Fig. 1(a). It was obvious that the combustion had occurred at the
achieve a transparent aqueous solution, a small quantity of deionized stoichiometric ratio, leading to the formation of the desired cubic
water was added to a predetermined quantity of nitrates and glycine; CoFe2O4 spinel phase with a lattice parameter of ~ 8.3919 Ȧ . Since
this was followed by stirring for 30 min. To remove the excess water there was no peak of the reactants in the diffractogram, the reaction
and obtain a viscous gel (precursor), the solution was heated on a hot seemed to be complete. It was also noteworthy that there was no evi-
plate. Consequently, the temperature of the solution was gradually in- dence of any undesired phase in the XRD pattern of the as-synthesized
creased, leading to a spontaneous autoignition reaction in the precursor powder, indicating the high purity of the synthesized spinel. By con-
that was accompanied by the release of a large volume of the gaseous sidering all peaks of CoFe2O4, the average grain size of the as-synthe-
phase. The product was further ground in a mortar. It is worth noting sized powder was calculated to be ~ 28 nm based on Williamson-Hall
that the total combustion reaction took around 20 min to complete,
while the reaction duration after ignition was around 4–5 s. Then, the
as-synthesized powder was calcined at 500 ℃ for 2 h under argon at-
mosphere to eliminate any residual glycine, nitrates, or their undesir-
able decomposition products. The calcined powders were then ball
milled for 2 and 4 h in a high energy Spex mill using a stainless steel vial
and steel balls with the diameter of ~ 5 mm and the ball-to-powder
weight ratio of 10:1.

2.2. Characterization

XRD patterns of as-synthesized, calcined and ball-milled powders

were recorded in the 2 θ range of 10–100° (the scan speed of 3°/min)
using a Philips diffractometer (40 kV) with CuK α radiation
(λ = 0.15406 nm) to investigate structural changes after the above-
mentioned treatments. The average grain size (d) of cobalt ferrite was
estimated from broadening of XRD peaks using Williamson–Hall for- Fig. 1. Diffractogram of CoFe2O4 powder: (a) as-synthesized, (b) calcined, (c) 2 h-milled,
and (d) 4 h-milled.
mula [29], as follows:

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A. Maleki et al.
method. Indeed, using glycine as the fuel in GNP caused the formation
of a uniform mixture at atomic or molecular level prior to combustion.
It was mainly due to the chemical formula of glycine, which contained a
carboxylic group at one end and an amino group at the other end, re-
sulting in the completion of the nucleation process through the domi-
nant mechanism of rearrangement and short-distance diffusion of the
adjacent atoms during the autoignition (~ 4–5 s). As a result, the na-
nostructured cobalt ferrite powder was obtained via GNP. Additionally,
the long-distance diffusion of atoms and the significant grain growth
were hindered during GNP, because the combustion reaction rate was
high enough to maintain the stability of the initial nanostructure [32].
As shown in Fig. 1(b), the XRD pattern of the calcined sample in-
dicated no new peak, emphasizing the stability of CoFe2O4 after calci-
nation at 500 ℃ for 2 h under argon atmosphere. Generally, crystalline
modification and subsequent grain growth are accompanied by the
calcination process, causing a negligible increase in the peaks intensity
[33,34]. The average grain size of the calcined powder was estimated to
be ~ 41 nm via Eq. (2). For 2 h-milled and 4 h-milled samples (Fig. 1(c)
& (d)), the peaks intensity was slightly decreased after milling, which
could be attributed to the grain refinement phenomenon (~ 31 nm and
~ 22 nm, respectively). In addition, according to the XRD patterns of
the milled samples, the nanostructured powder of cobalt ferrite was a
stable phase not affected by milling.
The porous or foam-like morphology of the as-synthesized powder is
shown in Fig. 2(a). Such porous agglomerates are mainly formed due to
the release of a large volume of gaseous products during GNP [34,35].
As shown by the magnified micrograph (Fig. 2(b)), the approximate
average particle size of nanosize spinel, which was highly agglomerated
and difficult to be distinguished separately, was expected to be ~
30 nm. This was in a good agreement with the value of the average
grain size (~ 28 nm) obtained for the as-synthesized powder. It is worth
noting that the calcination process did not alter the foam-like
Fig. 2. The morphology of CoFe2O4 powder: a, b) as-synthesized, and c, d) calcined.
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Ceramics International 44 (2018) 8576–8581
morphology (Fig. 2(c)). The average particle size was estimated to be ~
40 nm (Fig. 2(d)) after calcination, which was very close to the esti-
mated average grain size (~ 41 nm).
During milling, the foam-like morphology was changed to a flake-
like one. The flake-like particles were considerably smaller than the
foam-like ones and each flake contained aggregates of nanosize spinel
particles (Fig. 3(a) and (c)). By taking into account the higher magni-
fication micrographs (Fig. 3(b) and (d)), one could conclude that the
average particle size after 2 and 4 h milling was ~ 29 nm and ~ 22 nm,
respectively. It is worth noting that the relatively low temperature of
the GNP reaction and the subsequent calcination process, as well as the
very short time of autoignition, resulted in the formation of weak ag-
glomerates which could be broken easily to fine particles by conducting
short milling times.
To evaluate the influence of calcination and mechanical milling on
the magnetic behavior of the synthesized CoFe2O4, the magnetic hys-
teresis loop was measured, as shown in Fig. 4. The magnetic properties
of each sample, including coercivity (Hc) and saturation magnetization
(Ms), as extracted from Fig. 4, along with their average grain and par-
ticle size, are listed in Table 1. By considering the data related to the
average grain and particle size in Table 1, it could be anticipated that
each spinel particle would contain a single grain.
According to the literature [36,37], the experimental investigation
on the relationship between coercivity and particle size can be sche-
matically depicted in Fig. 5.
Fig. 5 reveals that coercivity could be decreased by increasing the
particle size in the multidomain region, or by decreasing the particle
size in the single domain region. On the other words, when the particle
size is less than single magnetic domain limit, the spinel ferrite nano-
particles can behave as a superparamagnetic material [22]. The critical
particle size (Dc), below which the multidomain material changes to the
single domain material, is around 40 nm for CoFe2O4 spinel [37–39].
A. Maleki et al. Ceramics International 44 (2018) 8576–8581

Fig. 3. SEM micrograph of a, b) 2 h-milled, and c, d) 4 h-milled CoFe2O4 powders.

Fig. 5. The relationship between coercivity H (Oe) and the particle size D (nm) [37].

Fig. 4. The hysteresis loops of CoFe2O4 powders with different conditions.

For multidomain materials (D > Dc), the domain wall movement is the
main mechanism for the change of magnetization, causing the reduc-
Table 1
tion of coercivity with the particle size increase [39]. In this study, the
The coercivity, saturation magnetization, average grain size, and particle size of CoFe2O4
samples. average particle size (grain size) of the as-synthesized powder was ~
30 nm, which was below the reported Dc (~ 40 nm). It was increased up
CoFe2O4 Sample Hc (Oe) Ms (emu/ g ) Average grain Measured to ~ 40 nm after the calcination process at 500 °C for 2 h under argon
size (nm) based average
atmosphere, which was close to the value mentioned for the single
on Williamson- particle size
Hall method (nm) domain size of spinel cobalt ferrite; consequently, coercivity was in-
creased moderately (Table 1). Actually, this increase was due to the fact
As-synthesized 900 62.83 ~ 28 ~ 30 that the change of magnetization in this condition could not occur only
Calcined 975 63.22 ~ 41 ~ 40
by shifting the domain walls, which would normally happen in a weak
2 h-milled 820 71.47 ~ 31 ~ 29
4 h-milled 770 73.98 ~ 22 ~ 22
magnetic field [37]. After milling for 2 and 4 h, coercivity was notice-
ably decreased, reaching the value of 820 and 770 Oe, respectively. It

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A. Maleki et al.
seemed that the reduction of the average particle size during milling
(see Table 1) below the single domain size could be the main reason for
this phenomenon. As stated before, in this condition, the magnetic
behavior of spinel ferrite nanoparticles turned to a superparamagnetic
one (Fig. 5). The particle size (grain size) for CoFe2O4 to become mostly
superparamagnetic is ~ 12 nm, in which the coercivity is zero [13]. In
fact, as the particle size is reduced to a certain value (~ 12 nm for
CoFe2O4), the ferromagnetic behavior is converted to a super-
paramagnetic one. At this condition, the room temperature thermal
energy overcomes the magnetostatic energy of the domain or the par-
ticles, exhibiting the zero hysteresis [37,40].
The second important observation in the hysteresis loops was the
change in the saturation magnetization (Ms) of the milled samples.
According to Fig. 4 and Table 1, Ms exhibited a marginal increase upon
the calcination process (~ 63.22 emu/g), while after 2 and 4 h milling,
it was remarkably increased to 71.47 and 73.98 emu/g, respectively.
The saturation magnetization is generally expected to decrease for the
finer grains as a result of the so called “dead” surface effect [13]. Ac-
tually, the “dead” surface is associated with the disorder of surface
spins. Based on this effect, when the grain size is decreased during
milling, the number of surface spins is increased, thereby causing a
subsequent reduction in Ms. However, the Ms values obtained in this
study were not consistent with this explanation. Here, it seemed that a
combination of surface effect [41] and redistribution of magnetic ca-
tions [12] could be the possible mechanism for the variation of sa-
turation magnetization. It is important to note that the magnetic mo-
ments of cations in the tetrahedral (A-site) and octahedral (B-site) sites
of spinel cobalt ferrite were aligned in an antiparallel manner. In an
ideal inverse spinel cobalt ferrite, where half of Fe3+ cations are located
in A-sites and the other half occupy B-sites, the magnetic contribution
of Fe3+ cations with the magnetic moment of 5 μB is mutually com-
pensated. Thus, the Co2+ cations with the magnetic moment of 3 μB, as
located in B-sites, are the only source of the net magnetic moment in the
ideal inverse spinel cobalt ferrite [12,42]. However, as already men-
tioned, CoFe2O4 is usually a mixed spinel representing Co2+ and Fe3+
cations in both A-sites and B-sites ((Co12−+i Fei3 +)[Coi2 +Fe23−+i] O42 −). The
general formula of the net magnetic moment per unit formula of
CoFe2O4 as a function of inversion degree can be expressed as [12]:
μ = μB − sites − μA − sites  =   {[3i+5(2−i)] − (5i+3(1−i))}(μB ) = (7 − 4i) μB ,
(3)
where μ is the net magnetic moment of the material, and μA − sites and
μB − sites are the magnetic moments of cations in A- and B-sites, respec-
tively. By increasing the inversion degree due to the movement of Co2+
cations from A-sites to B-sites and consequently, Fe3+ cations from B-
sites to A-sites, the net magnetic moment could be decreased and this
would occur along with the corresponding reduction in saturation
magnetization. On the contrary, if the opposite phenomenon occurs, the
saturation magnetization could be increased.
According to Table 1 and the aforementioned discussion, it seemed
that during milling for 2 and 4 h, the inversion degree was decreased as
a result of the change in the cationic redistribution, bringing about a
gradual increase in the net magnetic moment and subsequently, the
saturation magnetization. Moreover, it has been explained in the lit-
erature that less Co2+ cations in B-sites (smaller inversion degree)
could decrease the magneto-crystalline anisotropy and consequently,
decrease the coercivity values [12]. This is consistent with the results of
coercivity achieved in this study (see Table 1). Recently, Ponce et al.
[42] have indicated that milling of CoFe2O4 nanoparticles prepared via
a hydrothermal method leads to the cationic redistribution. Actually,
the saturation magnetization of the unmilled sample was measured to
be 69.5 emu/g, whereas milling with zirconia balls up to 1.5 h resulted
in an increase of saturation magnetization to 71.4 emu/g. Additionally,
the cation swap between magnetic A- and B- sites in the normal spinel
ferrite ZnFe2O4 due to the mechanical milling has been observed by
Stewart et al. [43]. These two researches are in agreement with the
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Ceramics International 44 (2018) 8576–8581
cationic redistribution during milling in this study, which was followed
by the observed increasing trend of saturation magnetization.
4. Conclusions
In this paper, the structural evolution and magnetic properties of
cobalt ferrite spinel powders synthesized through the GNP method
followed by the calcination process were investigated at 500 °C for 2 h
under argon atmosphere, and high energy mechanical milling for 2 and
4 h. The findings could be summarized here:
1. The desired cubic CoFe2O4 spinel phase with high purity was formed
through a complete combustion reaction using the stoichiometric G/
N ratio of 1.48. The foam-like morphology of the as-synthesized
powder contained nanosize spinel particles (~ 30 nm) which were
highly agglomerated.
2. The foam-like morphology was retained during the calcination
process and the average particle size was increased to ~ 40 nm.
However, short-time milling of 2 and 4 h changed the morphology
into a flake-like one with the average particle size of ~ 29 nm and ~
22 nm, respectively.
3. The average particle size of the calcined powder could be matched
well with the reported value of the single magnetic domain size for
cobalt ferrite in the literature (40 nm), where the coercivity value
reached its highest value (975 Oe).
4. The average particle size of 2 h-milled and 4 h-milled samples was
decreased below the single magnetic domain size; therefore, the
magnetic behavior gradually turned to a superparamagnetic one,
and this was followed by the reduction of coercivity values (820 and
770 Oe, respectively).
5. The saturation magnetization of the as-synthesized powder was
62.83 emu/g, and this was followed by a negligible increase after
calcination (63.22 emu/g). However, it was noticeably increased to
71.47 and 73.98 emu/g after 2 h and 4 h milling, respectively. This
was mainly attributed to the cationic redistribution and the sub-
sequent reduction of the inversion degree during milling.
6. It seemed that the reduction in the inversion degree during milling
(less Co2+ cations in B-sites) resulted in the decrease of magneto-
crystalline anisotropy and consequently, coercivity values.
References
[1] X. Batlle, A. Labarta, Finite-size effect in fine particles: magnetic and transport
properties, J. Phys. D 35 (2002) R15–R42.
[2] R. Rosenweig, Ferrohydrodynamics, Cambridge Unversity Press, Cambridge, 1932.
[3] J.L. Simonds, Magnetoelectronics today and tomorrow, Phys. Today 48 (1995)
26–32.
[4] U. Hafeli, W. Schut, J. Teller, M. Zborowski, Scientific and Clinical Applications of
Magnetic Carriers, Kluwer Academic Press/Plenum Publishers, Amsterdam, 1997.
[5] M. Pardavi-Horvath, Microwave applications of soft ferrites, J. Magn. Magn. Mater.
215–216 (2000) 171–183.
[6] G. Nabiyouni, M. Jafari Fesharaki, M. Mozafari, J. Amighian, Characterization and
magnetic properties of nickel ferrite nanoparticles prepared by ball milling tech-
nique, Chin. Phys. Lett. 27 (2010) 126401(1)–126401(4).
[7] C.N. Chinnasamy, A. Narayanasamy, N. Ponpandian, K. Chattopadhyay,
H. Guerault, J.M. Greneche, Magnetic properties of nanostructured ferrimagnetic
zinc ferrite, J. Phys.: Condens. Mater. 12 (2000) 7795–7805.
[8] K.S. Rao, G.S.V.R.K. Choudary, K.H. Rao, Ch Sujatha, Structural and magnetic
properties of ultrafine CoFe2O4 nanoparticles, Proc. Mater. Sci. 10 (2015) 19–27.
[9] W.P. Wang, H. Yang, T. Xian, J.L. Jiang, XPS and magnetic properties of CoFe2O4
nanoparticles synthesized by a polyacrylamide gel route, Mater. Trans. 53 (2012)
1586–1589.
[10] A. Franco, F.C. e Silva, High temperature magnetic properties of cobalt ferrite na-
noparticles, Appl. Phys. Lett. 96 (2010) 172505(1)–172505(3).
[11] Z. Zhou, Y. Zhang, Z. Wang, W. Wei, W. Tang, J. Shi, R. Xiong, Electronic structure
studies of the spinel CoFe2O4 by X-ray photoelectron spectroscopy, Appl. Surf. Sci.
254 (2008) 6972–6975.
[12] R. Sato Turtelli, M. Atif, N. Mehmood, F. Kubel, K. Biernacka, W. Linert,
R. Grössinger, Interplay between the cation distribution and production methods in
cobalt ferrite, Mater. Chem. Phys. 132 (2012) 832–838.
[13] A. Franco, F.C. e. Silva, V.S. Zapf, High temperature magnetic properties of Co1-
xMgxFe2O4 nanoparticles prepared by forced hydrolysis method, J. Appl. Phys. 111
(2012) 07B530(1)–07B530(3).
A. Maleki et al.
[14] R.S. Yadav, J. Havlica, M. Hnatko, P. Šajgalík, C. Alexander, M. Palou,
E. Bartoníčková, M. Boháč, F. Frajkorováa, Magnetic properties of Co1-xZnxFe2O4
spinel ferrite nanoparticles synthesized by starch-assisted sol–gel autocombustion
method and its ball milling, J. Magn. Magn. Mater. 378 (2015) 190–199.
[15] M. Shi, R.Z. Zuo, Y.D. Xu, Y.Z. Jiang, G.Y. Yu, H.L. Su, J.G. Zhong, Preparation and
characterization of CoFe2O4 powders and films via the sol–gel method, J. Alloy.
Compd. 512 (2012) 165–170.
[16] S. Burianova, J.P. Vejpravova, P. Holec, J. Plocek, D. Niznansky, Surface spin effects
in La-doped CoFe2O4 nanoparticles prepared by microemulsion route, J. Appl.
Phys. 110 (2011) 073902(1)–073902(7).
[17] Z.G. Zhu, X.Y. Li, Q.D. Zhao, Y. Shi, H. Li, G.H. Chen, Surface photovoltage prop-
erties and photocatalytic activities of nanocrystalline CoFe2O4 particles with
porous superstructure fabricated by a modified chemical coprecipitation method, J.
Nanopart. Res. 13 (2011) 2147–2155.
[18] Y. Zhang, Y. Liu, Z. Yang, R. Xiong, J. Shi, Synthesis of CoFe2O4 nanoparticles with
tunable magnetism by the modified hydrothermal method, J. Nanopart. Res. 13
(2011) 4557–4563.
[19] J.H. Peng, M. Hojamberdiev, Y.H. Xu, B.W. Cao, J. Wang, H. Wu, Hydrothermal
synthesis and magnetic properties of gadolinium-doped CoFe2O4 nanoparticles, J.
Magn. Magn. Mater. 323 (2011) 133–137.
[20] M. Ibrahim Amal, M.M. Abd El-Latif, M. Mahmoud Morsi, Synthesis and char-
acterization of nano-sized cobalt ferrite prepared via polyol method using con-
ventional and microwave heating techniques, J. Alloy. Compd. 506 (2010)
201–204.
[21] Y. Shi, J. Ding, H. Yin, CoFe2O4 nanoparticles prepared by the mechanochemical
method, J. Alloy. Compd. 308 (2000) 290–295.
[22] E. Manova, B. Kunev, D. Paneva, I. Mitov, L. Petrov, Mechano-synthesis, char-
acterization, and magnetic properties of nanoparticles of cobalt ferrite, CoFe2O4,
Chem. Mater. 16 (2004) 5689–5696.
[23] A. Franco, E.C. de Oliveira Lima, M.A. Novak, P.R. Wells, Synthesis of nanoparticles
of CoxFe(3−x)O4 by combustion reaction method, J. Magn. Magn. Mater. 308 (2007)
198–202.
[24] F. Nakagomi, S.W. da Silva, V.K. Garg, A.C. Oliveira, P.C. Morais, A. Franco,
E.C.D. Lima, The influence of cobalt population on the structural properties of
CoxFe3- xO4, J. Appl. Phys. 101 (2007) 09M514(1)-09M514(3).
[25] A. Franco, F.L.A. Machado, V.S. Zapf, Magnetic properties of nanoparticles of cobalt
ferrite at high magnetic field, J. Appl. Phys. 110 (2011) 053913(1)–053913(5).
[26] N. Shaigan, W. Qu, D.G. Ivey, W. Chen, A review of recent progress in coatings,
surface modifications and alloy developments for solid oxide fuel cell ferritic
stainless steel interconnects, J. Power Sources 195 (2010) 1529–1542.
[27] D.H. Prasad, J.W. Sona, B.K. Kim, H.W. Lee, J.H. Lee, A significant enhancement in
sintering activity of nanocrystalline Ce0.9Gd0.1O1.95 powder synthesized by a gly-
cine–nitrate-process, J. Ceram. Process. Res. 11 (2010) 176–183.
[28] L.A. Chick, L.R. Pederson, G.D. Maupin, J.L. Bates, L.E. Thomas, Glycine–nitrate
8581
Ceramics International 44 (2018) 8576–8581
combustion synthesis of oxide ceramic powders, Mater. Lett. 10 (1990) 6–12.
[29] G.K. Williamson, W.H. Hall, X-ray line broadening from field aluminium and wol-
fram, Acta Metall. 1 (1953) 22–31.
[30] A.F. Junior, T.E.P. Alves, E.C.O. Lima, E.S. Nunes, V. Zapf, Enhanced magnetization
of nanoparticles of MgxFe(3-x)O4 (0.5 < x < 1.5) synthesized by combustion reac-
tion, Appl. Phys. A 94 (2009) 131–137.
[31] S. Bhaduri, S.B. Bhaduri, E. Zhou, Autoignition synthesis and consolidation of
Al2O3–ZrO2 nano/nanocomposite powders, J. Mater. Res. 13 (1998) 156–165.
[32] N.P. Bansal, Z. Zhong, Combustion synthesis of Sm0.5Sr0.5CoO3-x and
La0.6Sr0.4CoO3-x nanopowders for solid oxide fuel cell cathodes, J. Power Sources
158 (2006) 148–153.
[33] Q. Wang, R. Peng, C. Xia, W. Zhu, H. Wang, Characteristics of YSZ synthesized with
a glycine–nitrate process, Ceram. Int. 34 (2008) 1773–1778.
[34] B. Lin, W. Sun, K. Xie, Y. Dong, D. Dong, X. Liu, J. Gao, G. Meng, A cathode-
supported SOFC with thin Ce0.8Sm0.2O1.9 electrolyte prepared by a suspension
spray, J. Alloy. Compd. 465 (2008) 285–290.
[35] R.D. Purohit, B.P. Sharma, K.T. Pillai, A.K. Tyagi, Ultrafine ceria powders via gly-
cine–nitrate combustion, Mater. Res. Bull. 36 (2001) 2711–2721.
[36] E.C. Stoner, E.P. Wohlfarth, A mechanism of magnetic hysteresis in heterogeneous
alloys, Philos. Trans. R. Soc. A240 (1948) 599–642.
[37] D.S. Mathew, R.S. Juang, An overview of the structure and magnetism of spinel
ferrite nanoparticles and their synthesis in microemulsions, Chem. Eng. J. 129
(2007) 51–65.
[38] C.N. Chinnasamy, B. Jeyadevan, K. Shinoda, K. Tohji, D.J. Djayaprawira,
M. Takahashi, R. Justin Joseyphus, A. Narayanasamy, Unusually high coercivity
and critical single-domain size of nearly monodispersed CoFe2O4 nanoparticles,
Appl. Phys. Lett. 83 (2003) 2862–2864.
[39] Z.H. Hua, R.S. Chen, C.L. Li, S.G. Yang, M. Lu, B.X. Gu, Y.W. Du, CoFe2O4 nanowire
arrays prepared by template-electrodeposition method and further oxidization, J.
Alloy. Compd. 427 (2007) 199–203.
[40] S.R. Kulkarni, P.U. Londhe, N.B. Chaure, Electrical and magnetic properties of Al3+
substituted Mn–Ni–Zn nanoferrites, J. Mater. Sci.: Mater. Electron. 24 (2013)
4186–4191.
[41] 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.
[42] A.S. Ponce, E.F. Chagas, R.J. Prado, C.H.M. Fernandes, A.J. Terezo, E. Baggio-
Saitovitch, High coercivity induced by mechanical milling in cobalt ferrite powders,
J. Magn. Magn. Mater. 344 (2013) 182–187.
[43] S.J. Stewart, S.J.A. Figueroa, J.M. Ramallo López, S.G. Marchetti, J.F. Bengoa,
R.J. Prado, F.G. Requejo, Cationic exchange in nanosized ZnFe2O4 spinel revealed
by experimental and simulated near-edge absorption structure, Phys. Rev. B 75
(2007) 073408 (1)-073408(4).