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Article history:
Received 1 August 2015
Accepted 1 September 2015
Available online 7 September 2015
Cobalt ferrites nanoparticles CoxFe3-xO4 (1 x < 1.8) were synthesized by a solvothermal route. X-ray
diffraction, Transmission Electron Microscopy and magnetic measurements show a strong correlation
between the structural and the magnetic properties. The highest cobalt amount substituted samples
(x 1.6 and 1.8) show a jump at low temperature in the hysteresis loops in the range of low applied elds
(<10 kOe). This behavior has been explained by surface effects and interparticle interactions. A difference
has been found using two different estimation of the magnetic anisotropy: from the law of approach to
saturation and using the Neel-Brown approach. The last approach leads to an increase of the anisotropy
for x 1.6 and 1.8 coming from nite size effects. Surface effects have been pointed out using the Bloch
law tting. Zero Filed Cooling (ZFC) measurements exhibit a blocking temperature (TB) range from 294 to
240 K. Kneller's law tting of the coercive eld dependence on the temperature exhibits a non-neglected
interparticle interaction and a wide size distribution according to the difference found between TB and
the Kneller transition temperature TBK.
2015 Published by Elsevier B.V.
Keywords:
Nano-cobalt ferrites
Surface affects
Interparticle interaction
1. Introduction
Cobalt ferrite nanoscale materials have attracted a great
attention due to the continuous discover of new promising properties which differ from the bulk ones. Reduced sizes may present
interparticle interactions [1] and surface effects [2]. Cobalt Ferrites
nanoparticles are used in a wide variety of applications such as
recording media, microwave, biomedicine, photo-magnetism [36]. This can be related to their high cubic magnetic anisotropy,
their chemical stability and their high coercive eld [7]. These
samples have been synthesized by a several chemical and physical
routes in the purposes to nd the suitable one for the required
properties.
Cobalt ferrites, of the Spinel structure with AB2 O4 formula, can
3 Td 2 3 Oh
be described as A2
1t Bt At B2t O4 where Td , Oh refer to the
tetrahedral and octahedral sites respectively and t is the inversion
degree. It is called a normal (inverse) spinel if t is equal to 1 (0).
Accordingly, the magnetite Fe3O4 crystallizes in a completely inverse spinel structure. Fe3 , occupying the octahedral and tetrahedral sites by half, are antiferromagnetically coupled through the
magnetic superexchange interaction. Fe3 and Fe2 cations, located
* Corresponding author.
E-mail address: mohamed1saidani@gmail.com (M. Saidani).
http://dx.doi.org/10.1016/j.jallcom.2015.09.020
0925-8388/ 2015 Published by Elsevier B.V.
514
p
8
atheoretic p rA R0 3rB R0
3 3
(1)
Lattice constant ( )
8,42
8,40
8,38
1,0
Fig. 1. XRD patterns for CoxFe3-xO4 samples (a) and an example of tted diagram for
x 1 (b).
1,2
1,4
cobalt content x
1,6
1,8
x nominal
S1
S2
S3
S4
S5
1
1.20
1.40
1.60
1.80
1
1.19
1.32
1.34
1.50
515
become more and more broad. This result provides a wide particle
size distribution as conrmed also by TEM analysis.
Fig. 7aee display hysteresis loops for the whole samples recorded at 10, 50, 150, 250 and 300 K. As the temperature and the cobalt
content increase, hysteresis shape and parameters (coercive eld:
Hc, saturation magnetization: Ms and remanence magnetization:
Mr) exhibit a noticeable variations. At 300 K (Fig. 7d), CoFe2 O4 has
the typically hysteresis loops behavior for soft ferrimagnetic materials with a coercive eld of 263 Oe comparable to the value
found by Zhang et al. [21] for comparable sizes and a saturation
magnetization Ms 79 emu/g, close to the bulk value (80 emu/g)
[17]. The other samples present the superparamagnetism behavior.
At 10 K (Fig. 7a), S1, S2 and S3 behave as a ferrimagnetic systems
with an increase of the coercive eld due to the decrease of thermal
agitation [21]. The samples (S4 and S5) with the highest cobalt
amount, exhibit a strange dependence of the magnetization on the
applied magnetic eld at low temperatures (Fig. 7b and d); a jump
has been occurred in the eld-range from 0 to 0.45 kOe.
5. Discussion
5.1. Hysteresis shape
The behavior (see Fig. 7) found on the hysteresis loops can be
related to different effects. Raghunathan et al [22] have found a
516
10
x=1
x=1,2
x=1,4
x=1,6
x=1,8
0,05 CoxFe3-xO4
Moment (emu)
Size (nm)
6
0,00
40
4
1,0
1,2
1,4
cobalt content x
1,6
80
120
160
200
240
280
Temperature (K)
1,8
320
Fig. 4. Crystallite and grain sizes as a function of the cobalt content (from TEM and
XRD measurements).
number of nanoparticles
80
(a)
80
40
40
20
20
0
4
numbre of nanoparticules
(b)
60
60
80
10
12
(c)
10
11
12
(d)
40
60
40
20
20
0
4
10
0
4
10
517
Fig. 7. Hysteresis loops: (a) for S1, S2 and S3 at 10 K (b) for S4 and S5 at 10 K. (c) for S5 at 50, 150 and 250 K. (d) for S1-5 at 300 K and (e) a zoom of S2 (x 1.2) at 10 K.
b
MH Ms 1 2
H
H is the applied magnetic eld and b is a tting constant.
(2)
symbols : exp-data
lines : Bloch's law fit
90
MS (emu/g)
518
x=1
x = 1,2
x=1,4
60
x = 1,6
x = 1,8
m mB mA
(3)
30
0
MMs
5585
100
200
Temperature (K)
300
(4)
Fig. 10. The magnetic moment by formula unit dependence on the cobalt content x.
0,60
80
M /M -10K
R S
MS-10K [emu/g]
100
60
0,52
0,48
0,44
1,0
1,2
1,4
1,6
Cobalt content x
Fig. 8. Ms vs the cobalt content x at 10 K.
1,8
1,0
1,2
1,4
1,6
Cobalt content x
Fig. 11. Mr to Msratio vs the cobalt content.
1,8
7. Magnetic anisotropy
According to Mr to Msratio values, it is permitted to assume that
samples have an axial anisotropy [35-37]. For cubic anisotropy, this
ratio is about 0.85 too high than our results. Hence, for a polycrystalline assembly of nanoparticles when neighboring magnetic
exchange interactions can be neglected (Mr/Ms y 0.5) the effective
anisotropy constant K can be deduced from the approach to saturation law and it is given by Ref. [31]:
Keff
1=2
105
b
MS
8
(5)
x= 1
x=1,2
x=1,4
x=1,6
x=1,8
2,4x10
K (erg/cm3)
2,0x10
1,6x10
1,2x10
KZFC
25KB TB
V
(6)
1,4x10
KEFF erg/cm3
519
7,0x10
8,0x10
40
80
120
160
200
Temperature (K)
240
280
Fig. 12. effective anisotropy constant for CoxFe3-xO4 samples as a function of the
temperature.
1,0
1,2
1,4
1,6
cobalt content x
Fig. 13. Effective anisotropy deduced from ZFC measurements.
1,8
520
8. Surface effects
For ordered magnetic systems, the temperature dependence of
the magnetization is related to the presence of low energy collective excitations known as magnons [46]. This phenomenon manifests by a decrease of the spontaneous magnetization as the
temperature increases. Thus, it allowed the development of a power law that describes the dependence of the saturation magnetization on the temperature known as Bloch T 3=2 law and given by
Refs. [35,47]:
MS T MS 01 BT a
(7)
T
HC HC0 1
TBK
0:5 !
(8)
HC0 and TBK are the coercive eld at 0 K and the superparamagnetic
blocking temperature. From this t, the Kneller's blocking temperature (TBK) has been extracted and the results are plotted in
Fig. 17. One can note that the results are in fairly agreement with
values estimated using ZFC for all cobalt content except for x 1.6
where Kneller's law t value deviates from the value estimated
form ZFC value. This discrepancy reects the strength of the
interparticle interaction [21]. Because S1-ZFC's curve presents the
sharper peak, the difference between the value estimated from ZFC
curve and the value extracted from the Kneller's law t is the
12
HC (kOe)
From M (H) curves, the coercive eld HC has been extracted and
the data are plotted in Fig. 15 (symbols). It can be shown that HC
depends on both the temperature and the cobalt content. Such
behavior has been observed for CoFe2O4 nanoparticles [2] and for
manganese-substituted cobalt ferrite by Melikhov et al [42]. HC
increases when the temperature decreases for all the samples
except S4 (1.6) which exhibits a weak value relative to the other
x=1
fit x=1
x=1,2
fit x=1,2
x=1,4
fit x=1,4
x=1,6
fit x=1,6
x=1,8
fit x=1,8
100
200
Temperature (K)
Fig. 14. Bloch's law constants dependence on x.
300
H -300 K (kOe)
C
0,3
521
0,2
0,1
Acknowledgment
0,0
1,0
1,2
1,4
1,6
1,8
Cobalt content x
Fig. 16. HC dependence on the cobalt content x at 300 K.
Temperature (K)
320
300
re de l'Enseignement
This work was supported by the Ministe
rieur, de la Recherche Scientique, Tunisia and l'Agence
Supe
Universitaire de la Francophonie (AUF) via the scholarship program
Eugen Ionesco. We thank also the Sectoral Operational Programme Human Resources Development (SOP HRD), nanced from
the European Social Fund and by the Romanian Government under
the project number POSDRU/159/1.5/S/134378 and by the structural founds project PRO-DD (POS-CCE, O.2.2.1., ID 123, SMIS 2637,
ctr. No 11/2009) for providing the infrastructure used in this work.
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280
260
240
1,0
1,2
1,4
1,6
1,8
Cobalt content x
Fig. 17. Blocking temperature versus cobalt content x for CoxFe3xO4 samples.
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