The effect of cobalt substitution on magnetic hardening of magnetite

M. Mozaffari
a,n
, Y. Hadadian
b
, A. Aftabi
c
, M. Oveisy Moakhar
b
a
Department of Physics, Faculty of Science, University of Isfahan, Isfahan 81746-73441, Iran
b
Physics Department, Razi University, Taghebostan, Kermanshah, Iran
c
Department of Physics, University of Kurdistan, Sanandaj 66177-15175, Iran
a r t i c l e i n f o
Article history:
Received 4 July 2013
Received in revised form
9 October 2013
Available online 7 November 2013
Keywords:
Substituted spinel ferrite
Magnetite
Magnetic hardening
Coercivity
Curie temperature
a b s t r a c t
In this work cobalt-substituted magnetite (Co
x
Fe
1x
Fe
2
O
4
, x0, 0.25, 0.50 and 0.75) nanoparticles were
synthesized by coprecipitation method and their structural and magnetic properties were investigated.
X-ray diffraction was carried out and the results show that all of the samples have single phase spinel
structure. Microstructure of the samples was studied using a eld emission scanning electron microscope
and the results show that particle sizes of the prepared nanoparticles were uniform and in the 5055 nm
range. Room temperature magnetic properties of the nanoparticles were measured by an alternating
gradient force magnetometer and the results revealed that substituting cobalt for iron in magnetite
structure, changes the magnetite from a soft magnetic material to a hard one. So that coercivity changes
from 0 (a superparamagnetic state) to 337 Oe (a hard magnetic material), which is a remarkable change.
Curie temperatures of the samples were determined by recording their susceptibility-temperature (T)
curves and the results show that by increasing cobalt content, Curie temperature of the samples also
increases. Also T curves of the samples were recorded from above Curie temperature to room
temperature (rst cooling), while the curves in the second heating and second cooling have the same
behaviour as the rst cooling curve. The results depict that all samples have different behaviour in the
rst cooling and in the rst heating processes. This shows remarkable changes of the cation distribution
in the course of rst heating.
& 2013 Elsevier B.V. All rights reserved.
1. Introduction
Magnetic nanoparticles have received much attention in recent
years due to their underlying applications in targeted drug
delivery, medical diagnostic, genetic screening [15], biosensors
[6], ferrouids [7], gas sensing [8], catalyses [9,10], high-density
information storage devices [1113], etc. Magnetic properties of
the nanoparticles can be more complicated than those of their
bulk counterparts. In fact, all relevant magnetic properties (coer-
civity, blocking temperature, saturation and remanent magnetiza-
tions) are functions of particles size and shape and of surface
chemistry [14,15]. For example as size reduces to a denite size,
nanoparticles exhibit the so-called superparamagnetic regime,
which is of great interest in macroscopic quantum tunnelling of
spin states [16,17]. Among the various magnetic nanoparticles,
spinel ferrites have been extensively studied because of their
interesting magnetic properties. Specically magnetite and cobalt
ferrite, which both have spinel structure belonging to the space
group (Fd3m), play a key role in magnetic applications.
Magnetite with the formula Fe
3
O
4
is the most strongly magne-
tized material found in nature. At room temperature (RT) magne-
tite has a cubic inverse spinel structure which can be visualized as
a face centred cubic arrangement of the oxygen anions [18].
Structurally, the cations in Fe
3
O
4
are distributed between two
sites, as (Fe
3
)
A
[Fe
3
Fe
2
]
B
O
4
, where A and B indicate tetrahedral
and octahedral sites respectively [19]. In case of cobalt ferrite
with formula (Co

Fe
1
)[Co
1
Fe
1
]O
4
, tetrahedral (A-site) and
octahedral (B-site) sites are occupied randomly by Co
3/2
and
Fe
3/2
, respectively [20]. This type of cation distribution is called
partially inverse spinel structure and as the degree of inversion
which represents the ratio between divalent and trivalent ions on
both A and B sites, depends mostly on the thermal history of the
sample [21]. Also it has been reported that count upon synthesis
conditions, cobalt ferrite can form both normal and invers spinel
structure [22]. Cobalt ferrite has been extensively investigated
owing to its interesting properties such as high coercivity, mod-
erate saturation magnetization, high chemical stability, wear
resistant, and electrical insulation [23]. These benecial character-
istics make it as a suitable candidate for many applications
mentioned above.
Each application of spinel ferrite nanoparticles requires a
somewhat different set of magnetic properties in nanocrystals.
Researching on a widespread range of several compositions and
Contents lists available at ScienceDirect
journal homepage: www.elsevier.com/locate/jmmm
Journal of Magnetism and Magnetic Materials
0304-8853/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jmmm.2013.10.039
n
Corresponding author. Tel.: 98 311 793 4741.
E-mail addresses: mozafari@sci.ui.ac.ir, mmozafari@hotmail.com (M. Mozaffari).
Journal of Magnetism and Magnetic Materials 354 (2014) 119124
sizes, reveals an existence of a potential for tuning the magnetic
properties and then vastly developing the range of applications.
For example by preparation and characterisation of various spinel
ferrites, MeFe
2
O
4
(MeFe, Co, Mg, Mn, Zn, etc.) changing the
amount of metals which exist in their composition, substituting
one or more for other one, changing the synthesis method [11] or
even changing the synthesis conditions, a desire characteristic can
be achieved.
Both Fe
3
O
4
and CoFe
2
O
4
in bulk form have inverse spinel
structures and their magnetocrystalline anisotropy constants (K)
are 14 and 380 kJ/m
3
respectively. This huge difference in K values
allows the possibility of controlling the magnetic properties of iron
oxide nanoparticles by substituting different amounts of cobalt for
iron [19]. Wide range applications of ferrites with small particles
leads to great expansion of methods for their preparation, such as
microwave plasma [24], Host template [25], microemulsion [26],
hydrothermal synthesis [27], solgel [28], sonochemical reaction
[29], forced hydrolysis [30], citrate precursor techniques [31],
electrochemical synthesis [32], solid-state reaction [33], combus-
tion methods [34], mechanical alloying [35], and coprecipitation
[5,11,3638]. As it is well known, chemical coprecipitation method
is an economical [39] and the most frequent way to produce
ultrane powders. This method is quite simple, fast and cheap
since it does not involve intermediate decomposition and does not
need calcining steps. In this work, a series of Co
x
Fe
1x
Fe
2
O
4
(x0.00, 0.25, 0.50 and 0.75) nanoparticles was synthesized by
coprecipitation method and the effect of Co substitution on the
magnetic properties of magnetite was investigated.
2. Experimental
As mentioned before Co substituted magnetite nanoparticles
with nominal formula of Co
x
Fe
1x
Fe
2
O
4
(x0.00, 0.25, 0.50 and
0.75) were prepared by the coprecipitation method. The starting
materials were corresponding stoichiometric quantities of high
purity FeCl
3
, FeCl
2
4H
2
O, CoCl
2
and NaOH (all of analytical grades)
from Merck Company, Germany. Stoichiometric ratios (1:2)
((Fe
2
Co
2
):Fe
3
) of FeCl
3
, FeCl
2
4H
2
O and CoCl
2
were dis-
solved in deionized double distilled water and a 5 M sodium
hydroxide (NaOH) solution, with a ratio (1:5) (metal chlorides:
sodium hydroxide) was added as fast as possible. Black precipi-
tates were obtained after the rapid addition of NaOH solution. The
precipitates were washed several times with deionized double
distilled water and were then dried at room temperature
over days.
To study the effect of annealing on magnetic properties of
the samples, sample with x0.50 (Co
0.5
Fe
0.5
Fe
2
O
4
) has been
chosen as a typical Co substituted magnetite and heated from
room temperature to 800 1C for 2 h by a rate of 8 1C/min and then
Fig. 1. (a) XRD patterns of the as-precipitated samples with x0.00 and 0.50. (b) XRD pattern of the sample with x0.50 annealed at 800 1C for 2 h in air.
M. Mozaffari et al. / Journal of Magnetism and Magnetic Materials 354 (2014) 119124 120
free-cooled to room temperature. Phase identication of the
prepared nanoparticles was carried out at room temperature by
X- ray diffraction method, using a BRUKER diffractometer D8
ADCANCED model and CuK radiation (1.5406 ). Magnetic
properties of the samples were investigated by an alternating
gradient force magnetometer (AGFM) of Meghnatis Daghigh Kavir
Co., Kashan, Iran. As MH curves of the samples were not saturated
up to the maximum measuring eld (79 kOe), their saturation
magnetization were determined by extrapolating of the high eld
parts of the curves to innity eld. In this order M1/H curves of
the high eld (H45000 Oe) parts of the MH curves were plotted
and extrapolated to 1/H-0. Morphology of samples was studied
by a eld emission scanning electron microscope (FESEM), using
a Hitachi S-4160 FESEM unit. Temperature dependence of the
AC susceptibility () of the samples was measured by a Bartington
MS2 system.
3. Results and discussion
Fig. 1a shows XRD patterns of the as-precipitated samples with
x0.00 and 0.50. As it can be seen main peaks are related to
(2 2 0), (3 1 1), (4 0 0), (5 1 1) and (4 4 0) planes, which are
corresponded to the spinel structure. Also it is clear that diffraction
peaks are fairly broad, which is attributed to the small crystallite
size of the samples [11,16]. Fig. 1b illustrates the XRD pattern of
the sample with x0.50 annealed at 800 1C for 2 h in air. This
pattern depicts that all peaks are more intense and thinner than
those of the as-precipitated sample. It shows that heat treatment
increases crystallinity and crystallite size.
Fig. 2 shows FESEM images of the as-precipitated samples with
x0.00 and x0.50 as typical images of the samples. Other
samples have the same morphology too. These images illustrate
fairly homogeneous nanoparticles with mean particle sizes in the
range of 5055 nm.
MH curve of the as-precipitated sample with x0.00 (mag-
netite) is shown in Fig. 3. As can be seen, this sample shows no
coercivity, which is a superparamagnetic behaviour resulted from
the small particle size. Also Fig. 4 shows the hysteresis loops of the
samples with x0.25, 0.5 and 0.75 in addition to MH curve of the
sample with x0.00. As can be seen when Co is substituted for
iron in magnetite structure, coercivity is not zero now and the
samples dont show superparamagnetic behaviour. The obtained
magnetic parameters, including coercivity (H
c
), magnetization at
maximum measuring eld, extrapolated saturation magnetization
from Fig. 5, remanence (M
r
) and squareness (M
r
/M
s
) are tabulated
in Table 1. A comparison between these data shows that with
increasing Co content, coercivity and squareness are increased
regularly, while the saturation magnetization and remanence do
not possess regular variations. The increase in coercivity is a cause
of increase in magnetocrystalline anisotropy which is in turn due
to cobalt substitution [40]. Magnetocrystalline anisotropy is the
main key factor that determines superparamagnetic behaviour
of nanocrystals. Magnetocrystalline anisotropy serves as an
energy barrier (E
A
) to block the spin relaxation, which changes
the magnetic state from ferromagnet to superparamagnet. The
Fig. 2. The FESEM images of the as-precipitated samples with x0 (up) and
x0.50 (down).
-10000 -8000 -6000 -4000 -2000 0 2000 4000 6000 8000 10000
-150
-100
-50
0
50
100
150
M
H(Oe)
Fig. 3. Room temperature MH curve of the sample with x0.0.
-10000 -8000 -6000 -4000 -2000 0 2000 4000 6000 8000 10000
-150
-100
-50
0
50
100
150
M
H(Oe)
x=0
x=0.25
x=0.75
x=0.50
Fig. 4. Room temperature MH curves of the samples with x0.0, 0.25, 0.50
and 0.75.
M. Mozaffari et al. / Journal of Magnetism and Magnetic Materials 354 (2014) 119124 121
magnetic moment can be agitated in to superparamagnetic relaxa-
tion by thermal energy (k
B
T). The height of E
A
determines the
blocking temperature in which the thermal activation can over-
come E
A
and the nanocrystals transfer in to the superparamagnetic
state [41]. According to StonerWohlfarth single domain theory
[42] both of the magnetocrystalline anisotropy constant (K) and
the volume of nanocrystals (V) control the magnetic anisotropy
barrier, E
A
[41]. As mentioned above the mean particle sizes of the
nanoparticles are approximately similar, therefore disappearance
of superparamagnetic properties by Co substitution in magnetite,
can be due to the increase in magnetocrystalline anisotropy. Also
according to the one-ion crystalline eld model [40], by increasing
Co ion content, due to the increases of magnetocrystalline aniso-
tropy, the coercivity and squareness of the spinel ferrites increase
too [43].
The overall magnetization in spinel ferrites depend on (a) the
magnetic moment of each ion, (b) distribution of the ions between
A- and B-sites and (c) the fact that the exchange interaction
between ions in A and B-sites is usually negative and also the
strongest one [44]. Since bulk magnetite has a complete invers
spinel structure, the numbers of Fe
3
on the A- and B-sites are
equal and consequently their moments would be cancelled.
Thereby its overall magnetization is just resulted from the Fe
2
moments on the B-sites. As X. Li and C. Kutal reported from their
Mssbauer investigation [16], the cation distribution of the Co
substituted magnetite changes with the Co concentration. Cobalt
ferrite retains its invers spinel structure, even though the cation
distribution changes. The irregular variation of the saturation
magnetization and remanence can be related to the change of
Co
2
and Fe
3
ions distribution between the A- and B-sites.
Fig. 6 shows the hysteresis loops of as prepared and annealed
sample with x0.50. As it can be seen the coercivity increases
signicantly (from 197 to about 1000 Oe which means it changes
more than ve times) after annealing, while saturation magneti-
zation decreases. High magnetic anisotropy of cobalt ferrite is
mainly because of presence of Co
2
ions on the B sites of the
spinel structure [22,45]. Many researchers have reported that
cation distribution of cobalt ferrite changes by heat treatment
[36,38,4548]. If one supposes initially all Co
2
ions were on the
B-sites (complete invers spinel structure), any heat treatments or
cation substitutions would result in the movement of some Co
2
ions out of the B-sites and this will reduce the level of anisotropy.
On the other hand, if initially some Co
2
ions are on the A-sites
(partial invers spinel structure), heat treatments or cation sub-
stitutions may lead to some being moved to the B-sites resulting in
an increase in anisotropy [46]. The increase in coercivity observed
after annealing is mainly a consequence of an increase in aniso-
tropy of the samples due to the cation redistribution, maybe
migration of some Co
2
ions from A- to B-sites. This migration
also can cause the decrease in the saturation magnetization after
annealing, as is illustrated in Fig. 6.
Fig. 7 illustrates temperature dependency of the ac suscept-
ibility of the as-precipitated samples. General trend of all T
curves is nearly the same, except for x0, which is magnetite.
Apart from T curve of magnetite, all other T curves achieve a
signicant broad peak just below their Curie temperatures, known
as Hopkinson peak [49]. Although values of T
C
depend on the
composition, Table 2, the verticality of the susceptibility drop just
below Curie temperature indicates the degree of composition
homogeneity of the sample [50,51]. As mentioned previously it
is proved that any heat treatment can change cation distribution.
So it might be a cause for broadening of the observed Hopkinson
y = -70391x + 116.4
y = -125340x + 141.1
y = -84558x + 93.791
y = -128399x + 158.76
75
85
95
105
115
125
135
145
155
1.0E-04 1.2E-04 1.4E-04 1.6E-04 1.8E-04 2.0E-04 2.2E-04
x=0.00
x=0.25
x=0.75
x=0.50
M (emu/g)
1/H (1/Oe)
Fig. 5. Variation of M with respect to 1/H of all samples and linear tting.
Table 1
Magnetic parameters of the samples.
x Values H
c
(Oe) M
(@9 kOe)
(emu/g) M
(extrapolated)
(emu/g) M
r
(emu/g) M
r
/M
s
0.00 0 108 116 0 0
0.25 64 119 141 6 0.042
0.50 198 84 93 9 0.96
0.75 337 144 158 24 0.15
-10000 -8000 -6000 -4000 -2000 0 2000 4000 6000 8000 10000
-120
-80
-40
0
40
80
120
M
H(Oe)
unannealed
annealed
Fig. 6. Hysteresis loops of the as-precipitated and annealed sample with x0.50.
Fig. 7. Variation of ac susceptibility with respect to temperature of the samples
with different x values, as labelled on the curves. Inset shows variation of Curie
temperature with respect to Co contents.
M. Mozaffari et al. / Journal of Magnetism and Magnetic Materials 354 (2014) 119124 122
peaks. To clarify this issue, T measurement was repeated. Fig. 8
shows the rst heating and the rst cooling T curves of the
sample with x0.50 and Fig. 9 shows the same measurement for
the second time. As can be seen the rst cooling and both second
heating and cooling curves are the same. This similarity shows
that cation distribution of the sample has changed during the rst
heating and nally cation distribution of the sample became
stable. Also it can be seen that Hopkinson peaks have been more
vertical than that of the rst heating curve.
Magnetite is unstable at temperatures above 250 1C and
changes to -Fe
2
O
3
rst and then to -Fe
2
O
3
, which is a para-
magnet at room temperature that is above its Nel temperature
(200 K) [52]. This can be clearly seen in its T curves (Fig. 10), in
which during the course of cooling measurement T curve has
been a horizontal line.
The Curie temperatures of all sample tabulated in Table 2,
shows that as cobalt content increases the Curie temperature will
increase consequently.
4. Conclusions
Results of this work show that it is possible to get single phase
Co substituted magnetite nanoparticles with a mean particle size
of 50 nm by coprecipitation method directly. The nanoparticles
obtained by this method have different cation distribution in
comparison with that of the bulk counterparts and it is possible
to change this cation distribution by annealing. Co substitution
increases coercivity of the magnetite, so it changes from a soft
ferrimagnetic to a hard one.
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