1 s2.0 S0168583X11005908 Main
1 s2.0 S0168583X11005908 Main
1 s2.0 S0168583X11005908 Main
a r t i c l e
i n f o
Article history:
Received 16 March 2011
Received in revised form 7 June 2011
Available online 13 June 2011
Keywords:
Ferrites
Gamma irradiation
Cation distribution
Diffusion coefcient
Dielectric constant
a b s t r a c t
Polycrystalline samples of Li0.5Fe2.5O4 ferrite precursor were prepared by conventional standard double
sintering ceramic technique and then irradiated with three different doses of 60Co gamma rays. The crystal structure and phase orientation of the irradiated and unirradiated samples of Li0.5Fe2.5O4 ferrite was
done by using X-ray diffraction technique at room temperature. The lattice parameter of the studied samples increased due to the formation of Fe2+ ions under the ionizing effect of gamma radiation. The strain
in the materials due to the irradiation was calculated from XRD data. Scanning electron microscope (SEM)
studies indicate that the irradiation causes amorphization, especially at the grain boundaries. The cation
distribution was calculated from XRD data analysis. By using cation distribution structural parameters
such as theoretical lattice constant, ionic radii of available sites and the oxygen parameter u have been
calculated. The estimated cation distribution and other structural parameters shows strong inuence of
gamma rays on polycrystalline Li-ferrite. The magnetic properties of irradiated and unirradiated lithium
ferrite were performed by using pulse eld hysteresis loop technique at room temperature. Electrical
properties such as diffusion coefcient and dielectric properties were carried out with the inuence of
gamma irradiation. Activation energy of diffusion process decreased after irradiation. The increase of diffusion coefcient with increasing dose rate of gamma irradiation was reinforced by the increase of Fe2+
ions and the displacement of metal ions from its original sites under the effect of gamma irradiation.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Ferrite materials have attracted a considerable attention of the
researchers for last few decades due to their interesting soft magnetic properties and high frequency applications. Ferrites have
very high dielectric constants and are useful in designing good
microwave devices such as isolators, circulators etc. [1]. A proper
choice of cations along with Fe2+, Fe3+, and their distribution between tetrahedral A- and octahedral B-sites in the spinel lattice,
imparts useful and interesting electrical and magnetic properties
to the spinel ferrites. Lithium ferrite (Li0.5Fe2.5O4) is a spinel-type
soft ferrite with high saturation magnetization, high Curie temperature, and square-loop hysteresis properties. Because of its superior magnetic properties, lithium ferrite is used in microwave
and memory core applications. Li0.5Fe2.5O4 is an inverse spinel with
the Li1+ and three-fths of the Fe3+ ions occupying the octahedral
B-sites of the cubic spinel structure of the general formula AB2O4
[2]. The study of electrode materials for rechargeable lithium ion
batteries remains a major topic in the area of energy storage.
Transition metal oxides are promising candidates as cathode materials for lithium secondary batteries [36].
The irradiation with gamma rays produces defects in the materials which inuences the structural, morphological and magnetic
properties of ferrites. Regarding the change in structural properties
of these systems when irradiated by gamma rays, it has been reported that it may be due to breaking of ferrimagnetic ordering,
surface state pinning, cation inversion, etc. Recently, the material
scientists are doing numerous experiments to study the effects of
different irradiation such as swift heavy ions [7], laser [8], gamma
ray [9], on the properties of ferrite materials depending upon the
desired applications. The properties of lithium ferrites can be
tailor-made by irradiating them with gamma rays for microwave
applications. In the present work, we systematically report our
results on the effect of different gamma ray doses on the structural,
morphological, magnetic and electrical properties of Li-ferrite.
2. Experimental
Polycrystalline samples of Li0.5Fe2.5O4 spinel ferrite were prepared by using conventional double sintering ceramic technique.
The details of method of preparation were discussed in our previous reports [1012]. The sample prepared by using this method
was treated as a precursor for the gamma irradiation study. The
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M.L. Mane et al. / Nuclear Instruments and Methods in Physics Research B 269 (2011) 20262031
pellets of Li0.5Fe2.5O4 synthesized material was irradiated with different doses (1, 2 and 3 Mrad) of energetic 60Co gamma radiations
with the dose rate of 140 rad/min.
X-ray diffraction patterns for irradiated and unirradiated samples were performed on Philips X-ray diffractometer with Cu ka
radiations (wavelength k = 1.548 ) at room temperature in 2h
range of 2080. The morphological analysis of irradiated and
unirradiated samples was determined by scanning electron
microscopy technique. The compositional stoichiometry was conrmed by EDAX analysis. The cation distribution was calculated
from XRD data analysis. Magnetic measurements of irradiated
and unirradiated ferrite samples were performed on pulse eld
hysteresis loop tracer at room temperature. The DC electrical resistivity of the samples was measured using the two-probe method in
which silver paste was used as a contact material. The dielectric
constant was measured as a function of frequency by using the
LCR-Q meter (Model HP 4284 A). The infrared (IR) spectra in the
range of 400800 cm1 were recorded using PerkinElmer
spectrometer.
3. Results and discussion
3.1. X-ray diffraction analysis
X-ray diffraction patterns for the unirradiated and irradiated
samples Li0.5Fe2.5O4 was depicted in Fig. 1. The unirradiated sample
of Li0.5Fe2.5O4 ferrite shows single phase cubic spinel structure.
XRD patterns shows small shift of the reection peaks to lower values of 2h and increase of the peak intensities for irradiated samples. Due to gamma irradiation defects were created in the
crystal lattice and the compressive strain was produced. This result
shows distortion in the cubic spinel structure after gamma irradiation. c-Irradiation can inuence the crystallization process. The
lattice parameter was calculated from the following relation.
2
kh k l 1=2
2 sin h
(311)
500
400
300
DXRD
Ck
B1=2 cos h
where B1/2 is the full width of half maximum in (2h), h is the corresponding Bragg angle and C = 0.9. The variations of crystallite size
are shown in Fig. 2 and it shows the increasing trend with increasing dose rate of gamma irradiation. This is because the c-radiation
changed
the ferric ions to ferrous ions. The radius0 of the ferrous ions
0
(0.74
A), is larger than that of ferric ions (0.67 A
), which increased
the size of the crystal after c-radiation. Further, the number of ferrous ions at the octahedral sites which take part in the electron exchange interaction Fe3+ M Fe2+ and hence are responsible for the
increase of the crystal size because ferric ions of smaller diameter
moved from the A sites to B sites as ferrous ions of larger diameter
after c-radiation. Thus, the number of ferrous ions on the octahedral
sites plays a dominant role in the increase of the crystallite size due
to irradiation damage by c-rays [15].
The compressive strain produced in the irradiated samples and
effective crystallite size was determined from XRD line width using
Scherrer formula modied by WilliamsonHall equation [16].
b cos h
0:9k
4e sin h
D
200
36.4
36.6
8.336
(533)
(422)
(310)
8.334
3.5
3.4
a
D
3.3
36.2
36.0
(333)
35.8
(400)
35.6
(440)
35.4
(d)
(c)
(b)
3.2
8.332
3.1
8.330
3.0
2.9
8.328
2.8
(a)
2.7
8.326
20
30
40
50
60
(210)
(211)
(220)
100
70
80
2 (Degree)
Fig. 1. X-ray diffraction pattern (a) unirradiated, (b) 1 Mrad, (c) 2 Mrad and (d)
3 Mrad c-dose irradiated Li0.5Fe2.5O4.
Unirradiated
1 Mrad
2 Mrad
3 Mrad
Dose rate
Fig. 2. Variation of lattice constant (a) and crystallite size (D) for unirradiated and
c-irradiated Li0.5Fe2.5O4.
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M.L. Mane et al. / Nuclear Instruments and Methods in Physics Research B 269 (2011) 20262031
0.0044
0.0040
cos
Before
1 Mrad
2 Mrad
3 Mrad
0.0042
0.0038
0.0036
0.0034
0.0032
0.0030
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
4 sin
Fig. 3. WilliamsonHall plots for unirradiated and c-irradiated Li0.5Fe2.5O4.
Fig. 4. Scanning electron microscopy images (a) unirradiated, (b) 1 Mrad and (c)
3 Mrad c-irradiated Li0.5Fe2.5O4.
ath
i
p
8 ph
3 rA R0 3r B R0
3
where rA and rB are radii of tetrahedral (A) site and octahedral [B]
site, R0 is radius of oxygen ion i.e. (R0 = 1.32 ). The variation of theoretical values is similar to that observed for the experimentally
determined lattice parameter. The value of ath for the given cation
distribution was estimated to be 8.39 , which is close to the
experimental value of lattice parameter. The agreement between
theoretical and experimental values conrms the proposed cation
distribution is correct.
0
Using the values of a, radius of oxygen ion R0 = 1.32
A and rA
in the following expression, the oxygen positional parameter u
can be calculated, [24]
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M.L. Mane et al. / Nuclear Instruments and Methods in Physics Research B 269 (2011) 20262031
Table 1
3
Cation distribution, iron distribution parameter (d Fe3
A =FeB ), magnetic moment
(nB) and activation energy (E) for unirradiated and irradiated samples of the system
Li0.5Fe2.5O4.
Cation distribution
Unirradiated
1 Mrad
2 Mrad
3 Mrad
(d)
A-site
B-site
Li0.04Fe0.96
Li0.05Fe0.95
Li0.06Fe0.94
Li0.07Fe0.93
Li0.46Fe1.54
Li0.45Fe1.55
Li0.44Fe1.56
Li0.43Fe1.57
0.62
0.61
0.60
0.59
nB (lB)
2.9
3.0
3.1
3.2
80
Unirradiated
1 Mrad
2 Mrad
3 Mrad
E (eV)
0.27
0.25
0.22
0.19
60
40
20
0
-6
-4
-2
-20
rA
rB
u
0.3865
0.685
0.3864
0.680
0.675
0.690
-40
0.3866
0.695
0.3863
Unirradiated
1 Mrad
2 Mrad
3 Mrad
Dose rate
Fig. 5. Variation of mean ionic radii at tetrahedral A site (rA), octahedral B site (rB)
and oxygen positional parameter for unirradiated and c-irradiated Li0.5Fe2.5O4.
1
1
u r A R0 p
3a 4
-60
-80
Fig. 6. Magnetic properties of irradiated and unirradiated Li0.5Fe2.5O4.
indicates that the saturation magnetization increases after irradiation by gamma rays. On irradiation the surface state pinning of domains are release and the magnetization of the particles is
increases [25]. Our results are contradictory with those reported
by Ghidini et al. [26] and Parvatheeswara Rao et al. [27]. This
may be due to the swift heavy ion irradiation produces adverse effect on the magnetic ordering and therefore on overall magnetization values of the system. In the present case of gamma irradiation,
with the dosage more Fe3+ ion tries to accommodate in octahedral
[B] sites which on contribute slightly positive to the magnetization
values.
3.5. Diffusion coefcient
The diffusion coefcient (D) of oxygen vacancies was estimated
from the relation [28]
rk B T
Ne2
D D0 eE=kB T
where
D0
r0 kB T
Ne2
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M.L. Mane et al. / Nuclear Instruments and Methods in Physics Research B 269 (2011) 20262031
-5
4000
Unirradiated
1 Mrad
2 Mrad
3 Mrad
-7
-1
Log D (m .sec )
-6
-8
-9
2000
1000
Unirradiated
1 Mrad
2 Mrad
3 Mrad
-10
3000
-11
1
1.0
1.2
1.4
1.6
1.8
2.0
log f
2.2
-1
1000/T (K )
Fig. 7. Variation of diffusion coefcient with temperature for irradiated and
unirradiated Li0.5Fe2.5O4.
Fig. 8. Variation of dielectric constant (e0 ) with frequency for irradiated and
unirradiated Li0.5Fe2.5O4.
ions to B sites. The electron exchange interactions Fe3+ M Fe2+ result in a local displacement of electrons in the direction of the electric eld which determine the polarization of the ferrites. The
increase in dielectric constant, which is accompanied by slight decrease in activation energy, with increasing gamma irradiation and
can be attributed to the increase in Fe2+ ions. This leads to increase
in the Fe2+/Fe3+ ratio present in Li0.5Fe2.5O4 and in turn increases
the rate of electron exchange between Fe2+ and Fe3+ ions. Further,
the increase in the dielectric constant by gamma-irradiation can be
interpreted as follows:
c Fe2 $ Fe3 e
This reversible interaction leads to the formation of some Fe2+
ions and at the same time causes an increase in Fe2+/Fe3+ ratios.
e0
Cp d
e0 A
M.L. Mane et al. / Nuclear Instruments and Methods in Physics Research B 269 (2011) 20262031
der. Diffusion of oxygen vacancies through the studied samples increases after irradiation. These results suggest the oxygen diffusion
in ferrite under consideration occurs by means of structural vacancies with gamma irradiation. The increase in dielectric constant,
which is accompanied by slight decrease in activation energy, with
increasing gamma irradiation and can be attributed to the increase
in Fe2+ ions after irradiation. The IR spectra showed also the defect
which was produced after g-irradiation.
34
Transmission (%)
32
30
(d)
28
(c)
26
2031
References
(b)
2"
24
(a)
22
1"
1'
3
2
20
800
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2'
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Wavenumber (cm )
Fig. 9. The infrared absorption spectra for (a) unirradiated, (b) 1 Mrad, (c) 2 Mrad
and (d) 3 Mrad c-dose irradiated Li0.5Fe2.5O4.
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