Nanodimensional spinel NiFe2O4 and ZnFe2O4 ferrites prepared by soft

mechanochemical synthesis
Z. . Lazarevi, . Jovaleki, A. Milutinovi, D. Sekuli, V. N. Ivanovski, A. Renik, B. Ceki, and N. . Romevi

Citation: Journal of Applied Physics 113, 187221 (2013); doi: 10.1063/1.4801962
View online: http://dx.doi.org/10.1063/1.4801962
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Nanodimensional spinel NiFe
2
O
4
and ZnFe
2
O
4
ferrites prepared by soft
mechanochemical synthesis
Z.

Z. Lazarevic,
1,a)

C. Jovalekic,
2
A. Milutinovic,
1
D. Sekulic,
3
V. N. Ivanovski,
4
A. Recnik,
5
B. Cekic,
4
and N.

Z. Romcevic
1
1
Institute of Physics, University of Belgrade, Pregrevica 118, Zemun, Belgrade, Serbia
2
The Institute for Multidisciplinary Research, University of Belgrade, Kneza Vi seslava 1, Belgrade, Serbia
3
Faculty of Technical Sciences, University of Novi Sad, Novi Sad, Serbia
4
Institute of Nuclear Sciences Vinca, University of Belgrade, P.O. Box 522, 11001 Belgrade, Serbia
5
Department for Nanostructured Materials, Jozef Stefan Institute, Ljubljana, Slovenia
(Received 3 October 2012; accepted 4 January 2013; published online 8 May 2013)
NiFe
2
O
4
and ZnFe
2
O
4
ferrites have been prepared by soft mechanochemical synthesis. The formation
of spinel phase and crystal structure of sintered powders were analyzed by X-ray diffraction, Raman
spectroscopy, and transmission microscopy. In order to conrm phase formation and cation
arrangement, Mossbauer measurements were done. Investigation of the magnetization as a function
of magnetic eld conrms an expected change of the degree of inversion in the spinel structure with
the sintering. The electrical DC/resistivity/conductivity was measured in the temperature range of
298-423 K. Impedance spectroscopy was performed in the wide frequency range (100 Hz-10 MHz) at
different temperatures. VC
2013 AIP Publishing LLC
[http://dx.doi.org/10.1063/1.4801962]
I. INTRODUCTION
Cubic nanosized spinel ferrites with the general formula
MFe
2
O
4
, where M is a divalent cation, belong to a family of
magnetic materials that can be used in many areas, such as
magnetic devices, switching devices, recording tapes, perma-
nent magnets, hard disc recording media, exible recording
media, read-write heads, active components of ferrouids,
color imaging, magnetic refrigeration, detoxication of bio-
logical uids, magnetically controlled transport of anti-cancer
drugs, magnetic resonance imaging (MRI) contrast enhance-
ment, and magnetic cell separation.
1
The interest for using of
these materials permanently increases because of their usabil-
ity under extreme conditions. It is well known that unique
magnetic, chemical, and mechanical properties of ferrite
materials strongly depend on the preparation conditions. One
of the most interesting ferrite is NiFe
2
O
4
and ZnFe
2
O
4
.
In normal spinel ferrites, all the divalent M
2
cations are
on the tetrahedral sites and the trivalent Fe
3
cations on the
octahedral sites. An example of normal spinel is a bulk
ZnFe
2
O
4
ferrite. The inverse spinel has the divalent cation
occupying the octahedral sites and the trivalent cations are
equally divided among the tetrahedral and remaining octahe-
dral sites. NiFe
2
O
4
ferrite is predominantly an inverse spinel.
Spinel ferrites can be presented with general formula:
(M
1k
Fe
k
)[M
k
Fe
2k
]O
4
, where the cation distribution factor
k =0 for normal spinels and k =1 for purely inverse spinel.
As is common, parentheses and square brackets denote cation
sites of tetrahedral and octahedral coordination, respectively.
2
It is widely accepted that the cation distribution in
MFe
2
O
4
(M=Ni, Zn), which determines many physical and
chemical properties, is a complex function of processing
parameters and depends on the preparation method of the ma-
terial.
3
Technological and scientic challenges coupled with
environmental considerations have prompted a search for
simple and energy-efcient synthesis and processing routes
of nanocrystalline spinel ferrites.
4
Among many types of
preparation and processing techniques (including, for exam-
ple, hydrothermal reactions,
5,6
coprecipitation,
79
combustion
synthesis,
10,11
the sol-gel method,
12,13
microwave process-
ing,
14,15
micro emulsion procedures,
16,17
and chemical syn-
thesis
18
), the nonconventional mechanochemical route
19
has
been recognized as a powerful method for the production of
novel, high-performance, and low-cost materials.
Novel approach to mechanochemical synthesis, based on
reactions of solid acids, based hydrated compounds, crystal
hydrates, basic and acidic salts, has been called soft mechano-
chemical synthesis.
20
The dissolved substances, compared to
the same substances in the solid state, substantially change
their nature. It can inuence on the composition and proper-
ties of the nal product. Peculiarities of soft mechanochemical
reactions consist in the high reactivity of surface functional
groups, notably, OH groups. Consequently, we investigated
possibilities of synthesis of NiFe
2
O
4
and ZnFe
2
O
4
ferrites by
soft mechanochemical technique and impact of this method
on the properties signicantly affected by particle size.
In this article, both ferrites have been prepared starting
from a mixture of (1) Ni(OH)
2
and Fe(OH)
3
and (2)
Zn(OH)
2
and Fe(OH)
3
powders in a planetary ball mill. The
aim of this work is to apply a new synthesis route to prepare
ultrane ferrites and to investigate their structural, magnetic,
and electrical properties.
II. EXPERIMENTAL PROCEDURE
For mixtures of crystalline powders, denoted by case (1)
and (2), the starting materials were: (1) nickel(II)-hydroxide
a)
Author to whom correspondence should be addressed. Electronic mail:
lzorica@yahoo.com. Tel.: 381 11 37 13 035. Fax: 381 11 3160 531.
0021-8979/2013/113(18)/187221/11/$30.00 VC
2013 AIP Publishing LLC 113, 187221-1
JOURNAL OF APPLIED PHYSICS 113, 187221 (2013)
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(Ni(OH)
2
, Merck 95% purity) and Fe(OH)
3
and (2) zinc(II)-
hydroxide (Zn(OH)
2
, Merck 95% purity) and Fe(OH)
3
in
equimolar ratio. Soft mechanochemical synthesis was per-
formed in air atmosphere in planetary ball mill (Fritsch
Pulverisette 5) for 25 h (case 1) and 18 h (case 2). Required
milling times for obtaining a single-phase ferrites were deter-
mined experimentally, in earlier paper.
21,22
The powder mix-
ture was pressed into pallet using a cold isostatic press
(8 mm in diameter and ~3 mm thick). The powder mixtures
were sintered at 1100

C for 2 h (Lenton-UK oven) without

pre-calcinations step. Heating rate was 10

C min
1
, with na-
ture cooling in air atmosphere.
The formation of phase and crystal structure of sintered
powders of the NiFe
2
O
4
and ZnFe
2
O
4
were approved via the
X-ray diffraction (XRD) measurements. Model Philips PW
1050 diffractometer equipped with a PW 1730 generator
(40 kV 20 mA) was used with Ni ltered CoKa radiation
of 1.78897 A

at the room temperature. Measurements were

done in 2h range of 15

80

with scanning step width of

0.05

and 10 s scanning time per step.

Raman measurements of mixture powder and sintered
sample were performed using Jobin-Ivon T64000 monochro-
mator. An optical microscope with 100 objective was used
to focus the 514 nm radiation from a Coherent Innova 99
Ar

laser on the sample. The same microscope was used to

collect the backscattered light. The scattering light dispersed
was detected by a charge-coupled device (CCD) detection
system. Room temperature Raman spectra are in spectral
range from 100 to 800 cm
1
.
TEM studies were performed using a 200 kV TEM
(JEM-2100 UHR, Jeol Inc., Tokyo, Japan) equipped with an
ultra-high resolution objective lens pole piece having a
point-to-point resolution of 0.19 nm, being sufcient to
resolve the lattice images of nanoparticles. Due to relatively
small size of the nanoparticles, selected area electron diffrac-
tion patterns (EDP) over the multiple nanocrystals were
recorded to obtain the characteristic diffraction rings with
structure-specic d-values.
The room temperature transmission
57
Fe Mossbauer
experiments were carried out by constant acceleration mode
using
57
Co(Rh) source. The spectra calibrated by laser and iso-
mer shifts are shown with respect to the a-Fe. The data analysis
was performed using WinNormos-Site
23
software including
the transmission integral correction for sample thickness.
The magnetization measurements were done at room
temperature using VSM 200 cryogenic magnetometer in
magnetic eld from 0 kOe to 680 kOe.
The electrical DC/resistivity/conductivity in the temper-
ature range of 298-423 K was measured on a SourceMeter
Keithley 2410. Impedance measurements were carried out in
the frequency range 100 Hz to 10 MHz on a HP-4194A im-
pedance/gain-phase analyzer using a HP-16048C test xture
at the temperature of 298-423 K.
III. RESULTS AND DISCUSSION
Figure 1 shows the XRD patterns of the synthesized
NiFe
2
O
4
and ZnFe
2
O
4
nano powders for 25 h and 18 h of
milling time and then sintered at 1100

C for 2 h. All XRD

peaks are indexed well with the standard pattern reported in
PCPDF card for NiFe
2
O
4
# 89-4927 and for ZnFe
2
O
4
# 89-
7412. The powder diffractograms present a series peaks
FIG. 1. X-ray diffraction patterns of the
(a) NiFe
2
O
4
and (b) ZnFe
2
O
4
powders
and sintered samples at 1100

C for 2 h.
187221-2 Lazarevic et al. J. Appl. Phys. 113, 187221 (2013)
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assigned to cubic spinel ferrite NiFe
2
O
4
and ZnFe
2
O
4
phases
which mean single ferrite phases are formed after appropri-
ate milling times. The average crystallite size has been calcu-
lated using Scherrers formula L = k
S
k
Co
/bcosh
hkl
, where L
is the particle size, k
Co
is the wavelength of X-ray radiation
(1.78897 A

for Co-K
a
), b is the full width at half maximum
(FWHM) reduced for instrumental broadening, and k
S
is
Scherrer constant.
24
The average calculated particle sizes
have been found to be about 10 and 15 nm for the NiFe
2
O
4
and ZnFe
2
O
4
powders, respectively. The lattice parameters
for powders (given in Fig. 1) computed according to the rela-
tion a = k
Co
(h
2
k
2
l
2
)
1
=2
/(2sinh
hkl
) using respective (hkl)
values are less than that of the bulk material. This reduction
in lattice parameter may be attributed to surface tension
which can lead to the distortion of the lattice and redistribu-
tion of cations. The diffraction peaks in sintered samples
become sharper, which could be associated with the amount
of signicantly increased ferrite grains. It can be seen that
there are no other diffraction peaks except peaks of spinel
ferrites. The average grain sizes, calculated using Scherrer
formula, are about 92 nm for NiFe
2
O
4
and 48 nm for
ZnFe
2
O
4
. The grains grow dramatically with the tempera-
ture, which indicates that selected sintering temperature is
benecial for ferrite crystallization.
Raman spectroscopy is a nondestructive material charac-
terization technique sensitive to structural disorder. It provides
an important tool to probe the structural properties of mecha-
nochemically synthesized materials. Group theory predicts
ve rst order Raman active modes (A
1g
E
g
3F
2g
) in the
normal cubic spinel structure with symmetry Fd3m, and all
these modes were observed as clear, symmetrical peaks in the
spectrum of sintered ZnFe
2
O
4
ferrite at ambient conditions, as
shown in Fig. 2. In the case of the as-prepared powder sample
of ZnFe
2
O
4
, as well as in the case of as-prepared powder and
sintered NiFe
2
O
4
samples, all ve Raman peaks seem asym-
metric, or even dissociated. Deconvolution of spectrum dem-
onstrates that each peak can be presented like a doublet,
which is a characteristic of the inverse spinel structure.
25,26
In
the case of the as-prepared nanosized samples, a surface ten-
sion, characteristic for nano-particles, enables redistribution
of the cations compared to stable bulk conguration. The
octahedral sites are occupied by Zn(Ni) and by Fe ions. This
results in a distortion of bond distances; owing to differences
in ionic radii of Zn(Ni) and Fe ions, the metal-oxygen bond
distance shows a substantial distribution. The symmetry
becomes lower and the Raman spectra detect these changes
very effectively. Inverse spinel belongs to P4
3
22 tetragonal
space group, but it is common to assigned Raman modes as if
they were in a normal spinel, for simplicity.
In the cubic ferrites, the strongest modes above 600cm
1
correspond to symmetric stretching of oxygen in tetrahedral
AO
4
groups, so the modes about 690 cm
1
in the case of
NiFe
2
O
4
(and 630cm
1
in ZnFe
2
O
4
) can be considered as A
g
symmetry. E
g
at about 320 cm
1
(~250cm
1
) is due to sym-
metric bending of oxygen with respect to cation in tetrahedral
surrounding. F
2g
(2) at 470 cm
1
(~350 cm
1
) and F
2g
(3) at
570cm
1
(~450 cm
1
) correspond to the vibrations of octa-
hedral group: F
2g
(2) is due to asymmetric stretching and
F
2g
(3) is caused by asymmetric bending of oxygen. F
2g
(1) at
180cm
1
in the case of NiFe
2
O
4
, or ~160 cm
1
in the case
of ZnFe
2
O
4
, is due to translational movement of the whole
tetrahedron.
Figure 3 shows TEM images of NiFe
2
O
4
and ZnFe
2
O
4
nano ferrites obtained after appropriate milling time with
FIG. 2. Raman spectra of the (a)
NiFe
2
O
4
and (b) ZnFe
2
O
4
powders and
sintered samples at 1100

C for 2 h.
187221-3 Lazarevic et al. J. Appl. Phys. 113, 187221 (2013)
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corresponding EDPs. The nal grain size in the NiFe
2
O
4
(average ~ 10 nm) is about twice as large as that in the
ZnFe
2
O
4
(average ~ 20 nm), which is a consequence of dif-
ferent reaction paths in these two ferrite processing routes.
The formation of NiFe
2
O
4
phase started after longer milling
times on sparse nucleation sites and therefore the nal grain
size is lower than in the ZnFe
2
O
4
system where reactions
started sooner and there were more nuclei for the spinel
phase formation. The crystallites in both systems are rounded
and tend to agglomerate into larger clusters with diameters
of several hundreds of nanometers. Measurements of the dif-
fraction rings conrmed that they correspond to the crystal
planes of spinel structure.
Mossbauer spectroscopy was used to investigate the syn-
thesized NiFe
2
O
4
and ZnFe
2
O
4
nanopowders obtained after
25 h and 18 h of milling, respectively. The bulk NiFe
2
O
4
has
an inverse spinel ferrite structure with ionic bonding:
(Fe
3
)
A
[Ni
2
|Fe
3
|]
B
O
4
.
27
The bulk ZnFe
2
O
4
is a normal
spinel with formula (Zn
2
)
A
[Fe
3
Fe
3
]
B
O
4
.
28
Marked ions in
the parenthesis with sign (A) occupy tetrahedral sites, while
ions inside square brackets as [B], and occupy octahedral sites.
The obtained nanopowders NiFe
2
O
4
and ZnFe
2
O
4
spinels by
soft mechanochemical synthesis in a ball mill, might crystal-
lize in various sizes with cation redistribution described by the
following formula (M
2
1k
Fe
3
k
)[M
2
k
Fe
3
2k
]O
4
. The pa-
rameter k is a degree of inversion and M = Ni or Zn.
Estimation of the parameter k is the goal of this spectroscopy.
Also, we could get more information about nanoparticles
sizes.
The Mossbauer spectrum (Fig. 4) of NiFe
2
O
4
consists of
nine subspectra, precisely seven sextets and two doublets.
According to the Mossbauer parameters (Table I), the sextets
are divided into three types marked with letter L, M, and S.
The sextets marked with L represent resonance response of
ion
57
Fe from the large NiFe
2
O
4
nanoparticles. The existence
of magnetic ions on both (A) and [B] sites allows three types
of antiferromagnetic exchange interactions: (A)-(A), (A)-
[B], and [B]-[B]. The strongest interactions, according to the
Weiss model, are between Ni
2
or Fe
3
ions at tetrahedral
sites and Fe
3
ions at the octahedral sites.
29
The rst sextet in Table I for the NiFe
2
O
4
, with xed
value (0.25 mm s
1
) for the isomer shift, corresponding to
the
57
Fe ion in tetrahedral site, includes both exchange inter-
actions, (A)-(A) and (A)-[B], seen for tetrahedral site. The
second subspectrum has xed isomer shift, too, similar to
Refs. 30 and 31 Its origin is in [Fe
3
] at octahedral site.
The width of sextet (0.8(1) mm s
1
) indicates unregu-
larly local environment occurred by cation rearrangement
contributing change in magnitude of exchange interactions
[Fe
3
]-O
2
- [M
2
] and [Fe
3
]-O
2
-(M
2
). The lower isomer
shifts of (A) sites suggest that the (Fe
3
)-O
2
bonds on the
tetrahedral site are more covalent than bonds on the octahe-
dral sites. Such covalent bonds cause 3d-polarisation effects
FIG. 3. TEM images with corresponding EDP (insets in the upper right cor-
ners) of mechanochemically prepared NiFe
2
O
4
and ZnFe
2
O
4
powders from
starting compositions (a) Ni(OH)
2
Fe(OH)
3
and (b) Zn(OH)
2
Fe(OH)
3
after processing for 25 h and 18 h, respectively.
FIG. 4. Mossbauer spectra at room temperature of the mixture of powders
(a) Ni(OH)
2
Fe(OH)
3
and (b) Zn(OH)
2
Fe(OH)
3
after processing for
25 h and 18 h, respectively. The values of relative absorption are shown. The
subspectra are plotted above the main spectrum.
187221-4 Lazarevic et al. J. Appl. Phys. 113, 187221 (2013)
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on any 4s-electron density and create the hyperne eld of
valence shell opposite in sign to that from the hyperne eld
of core shell (1s, 2s, and 3s-electrons).
29,32
Taking into
account that tetrahedral and octahedral sites have different
point group of symmetry, (cubic) and [trigonal], we expect a
different distribution of electron density at both sites, creat-
ing a different electric eld gradient (EFG) and different ori-
entation of principle axes of a EFG tensor with respect to the
hyperne eld direction. In the tetrahedral site should be no
EFG, and the presence of any quadrupole shift shows devia-
tion from ideal structural ordering. Hence, one could recog-
nize the site of iron ion in large nickel spinel ferrite
nanoparticles by different sign of a quadrupole shift.
31,33
The third sextet (Table I) the hyperne eld (B) and the
quadrupole shift (2e) are very similar to those of the c-Fe
2
O
3
.
Appearance of maghemite in the mixture is excluded by value
of the isomer shift (d) for this sextet. The origin of this interac-
tion is therefore in octahedral positioned metallic
57
Fe ions, but
in disturbed surrounding with vacancies like in maghemite.
The sign M denotes two sextets which originate from
medium size nanoparticles. Due to the dominant structural
and magnetic disorder of the surface, these sextets are broad-
ened with average value of the isomer shift, larger quadrupole
shift and smaller magnitude of hyperne induction than at L-
sextets. The sign S denotes superparamagnetic doublets
which come from small volume nanoparticles. They are con-
sequence of inability to observe a hyperne eld due to uc-
tuations of magnetization directions and it is directly
inuenced by the nanoparticle volume. Remaining two sex-
tets do not belong to the NiFe
2
O
4
phase. The 6% of total reso-
nant absorption conrms the formation of a-Fe contaminated
with Ni, and the three percent of total tted area comes from
Fe
2
in tetrahedral site.
34
The Mossbauer spectroscopy of 25 h milled mixture
Fe(OH)
3
/Ni(OH)
2
reveals that more of 90% emergent iron
containing powder is in the NiFe
2
O
4
phase. Using a formula
[A
(A)
/A
[B]
= f
(A)
/f
[B]
k/(2k)], where A is area of subspec-
trum, and assuming that the ratio of the recoil-less fraction is
f
[B]
/f
(A)
= 0.94 at the room temperature, one could obtain
k.
35,36
According to the areas of measured sextets, only for
large size particles, the estimated value for the degree of
inversion is 70%, with uncertainty of 40%.
The Mossbauer spectrum(Fig. 4) of ZnFe
2
O
4
obtained for
18 h milled mixture Fe(OH)
3
/Zn(OH)
2
is composed of seven
subspectra. Three of them are doublets. The bulk franklinite
is normal spinel with weak superexchange interactions
between Fe ions via oxygen anions on the octahedral sublat-
tice. Hence, antiferromagnet ordering temperature is very low,
about 10.5 K.
37
At roomtemperature, it behaves as paramagnet
with the Mossbauer parameters: d =0.36(1) mms
1
and
D=0.35(1) mm s
1
.
38
In the present work, the two doublets
are characterized by d =0.32 mm s
1
. Thus, obtained value
indicates cations redistribution, so newly formed particles
have to be described by some degree of inversion. Disjunction
on tetrahedral and octahedral contribution is not possible.
Large value of quadrupole splitting in both doublets is caused
by changes in tetrahedral and octahedral bond lengths and
angles incurred by milling process.
39
These two doublets
describe small particles of ZnFe
2
O
4
. The third doublet (marked
with an asterisk) has enormous quadrupole splitting value. Its
origin is in formed oxygen vacancies. An outbreak of one oxy-
gen anion at least induced more negative charge in iron nu-
cleus, which is reected on negative value of isomer shift for
this doublet. Its relative abundance in whole tted area is 2%.
Three remaining subspectra with origin in zinc spinel
ferrite phase are sextets and probably correspond to particles
TABLE I. Mossbauer parameters: A: relative area fraction of component; C: line width (FWHM); d: isomer shift with respect to a-Fe; D: quadrupole splitting
(2e-shift), and B: hyperne induction. Labels S, M, and L denote classied particles by their size. The xed parameters in the t are denoted by the superscript
f. The superscript * denotes damaged ZnFe
2
O
4
.
Sample Compound Size of particle
Mossbauers parameters
C d D/2e
A (%) (mm s
1
) (mm s
1
) (mm s
1
) B (T)
Fe(OH)
3
Ni(OH)
2
= NiFe
2
O
4
NiFe
2
O
4
L 14(4) 0.51(5) 0.25
f
0.14(1) 48.22(9)
NiFe
2
O
4
L 19(7) 0.8(1) 0.36
f
0.12(2) 45.7(2)
NiFe
2
O
4
L 6(1) 0.43(6) 0.46(1) 0.19(2) 50.8(1)
NiFe
2
O
4
M 19(6) 1.5(2) 0.56(5) 0.42(8) 41.5(6)
NiFe
2
O
4
M 17(3) 1.08(8) 0.17(2) 0.37(3) 24.8(2)
NiFe
2
O
4
S 5(1) 0.45(5) 0.311(7) 2.38(2)
NiFe
2
O
4
S 11(2) 1.3(2) 0.34(1) 0.94(7)
(Fe
2
) 3(1) 0.51(8) 0.92(2) 1.21(5) 29.5(2)
a-Fe 6(1) 0.61(9) 0.00(2) 0.30(4) 32.7(1)
Fe(OH)
3
Zn(OH)
2
= ZnFe
2
O
4
ZnFe
2
O
4
S 11(4) 0.8(1) 0.32(2) 0.9(1)
ZnFe
2
O
4
S 7(4) 0.55(11) 0.32(2) 1.89(6)
ZnFe
2
O
4
* 2(1) 1.0(4) 0.4(2) 3.6(3)
ZnFe
2
O
4
M 38(10) 1.7(1) 0.27(4) 0.37(6) 23.2(3)
ZnFe
2
O
4
M 19(8) 1.4(3) 0.44(6) 0.1(1) 34.4(4)
ZnFe
2
O
4
M 20(7) 1.3(1) 0.57(4) 0.53(7) 20(7)
a-Fe 3(1) 0.20(7) 0.01(2) 0.01(3) 33.3(1)
187221-5 Lazarevic et al. J. Appl. Phys. 113, 187221 (2013)
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of the medium size. It is a well-known fact that zinc substitu-
tion by Fe increases with decreasing particle size.
40,41
Short-
range AF correlation enables inter-lattice superexchange
interaction of type (Fe
3
)-O
2
[Fe
3
]. The line widths of all
subspectra originating in ZnFe
2
O
4
are broadened by different
iron ions environment induced by site alteration of cations.
Considering that there are no sextets that we can associate to
A-sites doubtless, we were not able to estimate a degree of
inversion in zinc ferrite nanoparticles. The Mossbauer spec-
troscopy of investigated mixture reveals that 97% of sample,
which contains iron ions, makes ZnFe
2
O
4
nanoparticles. The
remainder of 3% is created a-Fe in ball mill process.
The magnetization curves of the nickel and zinc ferrites
powder and sintered sample measured at room temperature
are shown in Fig. 5. We have characterized the magnetic
behavior of mechanochemical synthesized NiFe
2
O
4
and
ZnFe
2
O
4
focusing on the study of the size-dependent magnet-
ization. These measurements have revealed that the magnetic
behavior of soft mechanochemical synthesized NiFe
2
O
4
and
ZnFe
2
O
4
is different from that of the powder prepared using
the conventional ceramic method.
As can be seen (Fig. 5(a)), the magnetization of the
mechanochemical synthesized sample does not saturate even
at the maximum eld attainable (H
ext
= 80 kOe). This is in
contrast to the magnetic behavior of the bulk (sintered)
NiFe
2
O
4
, whose magnetization reaches a saturation value
easily. An absence of saturation can be attributed to the
effect of spin canting. Even in sintered mechanochemical
synthesized nickel ferrite, the surface/volume ratio is rather
great and the dangling bonds (uncompensated electrons) at
the surface of the particles can contribute to magnetization.
The measurement of the coercivity warrants the determi-
nation of the magnetization response with better accuracy
and resolution particularly at small applied elds. Hence, a
separate set of hysteresis curves was showed for each sample
with an applied eld of 1500 to 1500 Oe at room tempera-
ture (the inset M-H curves in Fig. 5(a)). The hysteresis curve
at low applied elds shows the values of the coercive eld,
H
c
~80 Oe for sintered sample and 36 Oe for as-prepared
sample. The remnant magnetization is M
r
~8 emu/g and
M
r
~2.4 emu/g for sintered and powder samples of NiFe
2
O
4
,
respectively. The extrapolated magnetization M
0
measured
on the spinel ferrite obtained by a soft mechanochemical
synthesis is higher than that for spinel ferrites produced by
other methods.
42
Lower value of magnetisation in the as-
prepared sample of NiFe
2
O
4
compared to sintered sample
implies a lowering of a cation distribution factor in a nano-
sized sample.
The magnetic properties of the NiFe
2
O
4
with an inverse
spinel structure can be explained in terms of the cations dis-
tribution and magnetization originates from Fe
3
ions at
both tetrahedral and octahedral sites and Ni
2
ions in octahe-
dral sites. Hysteresis loops in Fig. 5 for as-prepared samples
are typical for soft magnetic materials and the S shape
of the curves together with the negligible coercivity
(H
c
~80 Oe) indicate the presence of small magnetic par-
ticles exhibiting super paramagnetic behaviors. In super par-
amagnetic materials, responsiveness to an applied magnetic
eld without retaining any magnetism after removal of the
magnetic eld is observed. This behavior is an important
property for magnetic targeting carriers. In fact, the differ-
ence between ferromagnetism and superparamagnetism fab-
ricates in the particle size. Literature data imply that when
the diameter of particles is less than 50 nm, the particles
show the character of superparamagnetism.
The magnetization curves of the zinc ferrite measured at
room temperature are shown in Fig. 5(b). The curve has S
shape with low coercivity (H
c
~97 Oe) and extremely small
remanence magnetization. Sintered sample exhibits a para-
magnetic behavior, which is expected in the case of bulk, or
crystalline material with crystalline size of 100 nm order. Such
material is practically without internal tensions and in the case
of sintered ZnFe
2
O
4
a normal spinel structure with fully popu-
lated antiferromagnetic tetrahedral [B] sites is established.
([B][B] super exchange interaction is weak and bulk
ZnFe
2
O
4
became antiferromagnetic at about 10 K.) On the
other hand, in the as-prepared sample with nanosized crystalli-
tes can be recognized a super paramagnetic behaviour.
43,44
FIG. 5. The magnetic hysteresis curves of the (a) NiFe
2
O
4
and (b) ZnFe
2
O
4
powders and sintered samples at 1100

C for 2 h. The insets show low mag-
netization behavior.
187221-6 Lazarevic et al. J. Appl. Phys. 113, 187221 (2013)
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The estimated value of saturation magnetization is M
sat
=68 emu/g which is a result of the inversion of cations. The
largest super exchange interaction in spinel ferrites, in the case
of ZnFe
2
O
4
established between Fe
3
ions in (A) and [B] sites,
generates such high value of magnetization. Nano powder of
ZnFe
2
O
4
in the as-prepared sample is predominantly of mono-
domen crystallites, which is conrmed by a small remanence
magnetization, M
rem
=6.63 emu/g. Open hysteresis loop, with
coercive eld, H
coerc
=97 Oe (in combination with high mag-
netization), shows that ferromagnetic transition temperature is
well above the room temperature. The fact that magnetization
does not achieve a saturation in the magnetic elds up to
680 kOe implies a surface spin disorder. Ordering of these
spins in a magnetic eld contributes in the magnetic moment
of the monodomen ZnFe
2
O
4
crystallites, also.
The variations in electrical conductivity may be
explained by Verweys hopping mechanism.
45
According to
Verwey, the electrical conductivity in ferrite is mainly due to
hopping electron between ions of the same element present
in more than one valance state, distributed randomly over
crystallographically equivalent lattice sites. Ferrite structur-
ally forms cubic close packed oxygen lattice with the cation
at the octahedral, [B] and the tetrahedral, (A) sites. The dis-
tance between two metal ions on B sites is smaller than the
distance between two metals ions on (A) and [B] sites; there-
fore, the hopping between A and B has very small probabil-
ity compared with that for B-B hopping. The hopping
between A-A sites does not exist, due to fact that there are
only Fe
3
ions at (A) sites and any Fe
2
ions formed during
processing preferentially occupy [B] sites only.
46
The hop-
ping probability depends upon the separation between the
ions involved and the activation energy. The charges can
migrate under the inuence of the applied eld contributing
to the electrical response of the system.
Pollak
47
has shown that the conductivity is an increasing
function of frequency in the case of conduction by hopping
and a decreasing function of frequency in case of band con-
duction. Generally, the total conductivity is the summation
of the band and hopping parts
48
r = r
DC
(T) r
AC
(x; T):
The rst term represents the temperature dependent DC elec-
trical conductivity due to the band conduction and it is fre-
quency independent. The second term is frequency and
temperature dependent pure AC conductivity due to the hop-
ping processes at the octahedral site. It obeys the power law
form.
48
The DC conductivity on NiFe
2
O
4
and ZnFe
2
O
4
samples
was measured as a function of temperature. The effect of the
temperature on the electrical conductivity r
DC
for both
ferrite samples is illustrated in Fig. 6. The plot of log(r
DC
)
versus (1/T) shows that this dependence is linear for both sin-
tered samples in a certain temperature range. The observed
increase in the DC conductivity of sintered samples with
temperature shows their semiconducting nature. This is con-
rmation of the negative temperature coefcient of resist-
ance (NTCR)-type behavior of the pallets usually shown by
semiconductors. The conductivity of ferrites is known to
depend upon the purity of starting materials, sintering tem-
perature and sintering time, which inuence the microstruc-
ture and composition of the samples.
49
The increase in electrical conductivity r
DC
with temper-
ature is due to the increase in the thermally activated drift
mobility of charge carriers according to the hopping conduc-
tion mechanism. The activation energy for the thermally
activated hopping process was obtained by tting the DC
conductivity data with the Arrhenius relation
50
r
DC
(T) = r
0
exp
DE
kT

;
where r
0
is the pre-exponential factor with the dimensions of
(X cm)
1
K, DE is the activation energy for DC conductiv-
ity, T is the absolute temperature, and k is the Boltzmanns
constant. The slope of the log(r
DC
) versus (1/T) straight line
is a measure of activation energy of the NiFe
2
O
4
and
ZnFe
2
O
4
ferrites. Using Arrhenius equation, the determined
values of the conduction activation energy DE are 0.395 eV
and 0.452 eV for ZnFe
2
O
4
and NiFe
2
O
4
, respectively. If we
analyze the obtained values for the conduction activation
energy, one can see that NiFe
2
O
4
has a higher value com-
pared to ZnFe
2
O
4
sample. This showed that more energy is
required for electron exchange between Fe
2
and Fe
3
ions
for the NiFe
2
O
4
. As shown in Fig. 6, NiFe
2
O
4
has the lower
DC conductivity than the ZnFe
2
O
4
. It is in good accordance
with the fact that the higher activation energy is associated
with the lower electrical conductivity. Also, there is no re-
markable change in the slope in the measured temperature
range for both samples.
The variation of electrical AC conductivity of the both
ferrites is plotted against the change in frequency for differ-
ent temperatures and shown in Fig. 8. It is obvious that the
ZnFe
2
O
4
has a higher conductivity compared to NiFe
2
O
4
at
a certain temperature and at different frequencies. Also, it is
seen that the AC conductivity of both ferrites shows a grad-
ual rise at low frequencies, whereas at higher frequencies the
FIG. 6. Temperature dependence of DC electrical conductivity on NiFe
2
O
4
and ZnFe
2
O
4
samples.
187221-7 Lazarevic et al. J. Appl. Phys. 113, 187221 (2013)
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conductivity rises steeply. This behavior is more pronounced
in the conductivity of NiFe
2
O
4
, especially at lower tempera-
tures. The hopping of electron between Fe
2
and Fe
3
ions
on the B, octahedral, sites is responsible for conduction
mechanism in ZnFe
2
O
4
and NiFe
2
O
4
ferrites.
51
Also, various
reports show that the hole hopping between Ni
2
and Ni
3
on B site also contributes to the electric conduction in
NiFe
2
O
4
as the inverse spinel.
52
In general, the increase in conductivity with increase of
frequency can be explained on the basis of Maxwell-Wagner
theory.
53
According to this theory, dielectric structure was
formed by two layers. First layer consists of ferrite grains of
fairly well conducting, which is separated by a thin layer of
poorly conducting substances, which forms the grain bound-
ary. The non-conducting layer or grain boundary is formed
by oxygen ions. Thus, each grain possesses oxygen rich layer
on the surface as boundary. These grain boundaries are more
active at lower frequencies; hence the hopping frequency of
carriers between Fe
2
and Fe
3
ion is less at lower frequen-
cies. As the frequency of the applied led increases, the con-
ductive grains became more active by promoting the
hopping between Fe
2
and Fe
3
ions, thereby increasing the
hopping frequency. Thus, we observe a gradual increase in
conductivity with frequency.
On the other hand, the electrons in ferrites are localized
and the electrical conductivity is increased with an increase
in temperature due to the hopping of the charge carriers. As
temperature increases, the mobility of hopping also increases
thereby increasing conductivity. It is seen from Fig. 7 that
the conductivity of NiFe
2
O
4
and ZnFe
2
O
4
increases with the
increase in temperature which is a typical behavior of
semiconductors.
It is well known that there are two types of polarons,
small polarons and large polarons. In the small polaron
model, the conductivity increases linearly with increase in
frequency and in case of large polarons the conductivity
decreases with increase in frequency.
54
For the present sam-
ples, the plots indicate small polaron type of conduction.
The complex impedance spectroscopy
55
is a powerful
technique in solid states physics because of its ability to
understand the electrical conduction mechanism of the syn-
thesized materials. In the present analysis, the impedance
spectroscopy has been used as well-developed tool to sepa-
rate out the grain/bulk and grain boundary contribution to
the total conductivity of NiFe
2
O
4
and ZnFe
2
O
4
ferrite.
Depending on the electrical properties of the samples, the
AC response can be modeled with two semi-circles in the
impedance plane, the rst in a low frequency domain repre-
sents the resistance of grain boundary. The second one
obtained in a high frequency domain corresponds to the re-
sistance of grain or bulk properties.
56
Figure 8 shows the complex impedance plane plots of
sintered NiFe
2
O
4
and ZnFe
2
O
4
ferrites as a function of fre-
quency at different temperatures. Generally, two semicircles
are observed in the Cole-Cole plots of both samples between
the frequency range of 100 Hz-10 MHz. A larger one at low
frequency represents the resistance of the grain boundary
and a smaller one obtained at the higher frequency side cor-
responds to the resistance of grain of bulk properties. It is no-
ticeable that the impedance spectra of NiFe
2
O
4
and ZnFe
2
O
4
ferrites include both grain and grain boundary effects. This
FIG. 7. Frequency dependent AC conductivity behavior of (a) NiFe
2
O
4
and
(b) ZnFe
2
O
4
ferrites at different temperatures.
FIG. 8. Cole-Cole plots for the sample of the (a) NiFe
2
O
4
and (b) ZnFe
2
O
4
ferrites at different temperatures. Inset: proposed equivalent circuit model
for analysis of the impedance spectroscopy data.
187221-8 Lazarevic et al. J. Appl. Phys. 113, 187221 (2013)
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appearance of two semicircles indicates a phenomenon
which is typically related to the presence of a distribution of
relaxation time.
As one can see in impedance spectra of both ferrites, the
diameters of the semicircles exhibit decreasing trends with
the increase in temperature. It indicates that the conductivity
increases with increase in temperature supporting the typical
negative temperature coefcient of resistance behavior of
NiFe
2
O
4
and ZnFe
2
O
4
usually shown by semiconductors. On
impedance spectra is observed that NiFe
2
O
4
has a higher im-
pedance value of ZnFe
2
O
4
at all temperatures, so it is in
good accordance with the fact that the conductivity of
NiFe
2
O
4
is lower than conductivity of ZnFe
2
O
4
. The imped-
ance value of both samples is decreased by two orders of
magnitude, which is due to thermal activation mechanism.
The rise of temperature brings with an enhanced conductiv-
ity, and hence, decreasing the impedance values.
In order to correlate the electrical properties of the
NiFe
2
O
4
and ZnFe
2
O
4
sample with the microstructure of the
material, an equivalent circuit model consisting of two seri-
ally connected parallel R-CPE elements, shown in the inset
of Fig. 8, has been used to interpret the impedance spectra.
Here, R
g
and R
gb
represent the grain and grain boundary re-
sistance and CPE
g
and CPE
gb
are the constant phase ele-
ments for grain interiors and grain boundaries, respectively.
The resistance of the circuit represents a conductive path and
a given resistor in a circuit accounts for the bulk conductivity
of the sample. The constant phase element CPE is used to
accommodate the non-ideal behavior of the capacitance
which may have its origin in the presence of more than one
relaxation process with similar relaxation times. The imped-
ance of a CPE can be described as
57
Z
CPE
= A
1
(jx)
n
;
where x is the angular frequency, A and n (0 _ n _ 1) are
tted parameters. When n = 1, then the CPE describes an
ideal capacitor with C = A, while when n = 0 the CPE
describes an ideal resistor with R = 1/A. The capacitances
are generally associated with space charge polarization
regions. The CPE elements in the equivalent circuit model
have been used to describe non ideal Debye-like behavior
58
and enable taking into account phenomena occurring in the
interface regions, associated with inhomogeneity and diffu-
sion processes.
59
Analysis and simulation of impedance spectra were
performed using EIS Spectrum Analyzer software.
60,61
The different electrical parameters calculated from the com-
plex impedance plots at selected temperatures are shown in
Table II. In these types of ferrites, the value of the grain
boundary resistance is generally larger than the resistance of
the grain, R
gb
_ R
g
. Additionally, the semicircle representing
the grain boundaries lies on the lower frequency side since
the relaxation time of the grain boundaries is much larger
than that of the grains. Also, it is observed that the both resis-
tances decrease with increasing temperature. It indicates that
the conductivity of NiFe
2
O
4
and ZnFe
2
O
4
ferrites increases
with increase in temperature. The higher values of resistance
of both grain and grain boundary for the NiFe
2
O
4
mean this
ferrite has a lower conductivity than the ZnFe
2
O
4
. This
decrease in the resistance of grains and grain boundaries has
been suggested to be due to the thermal activation of the
localized charges. Two types of thermal activations, i.e., car-
rier density in the case of band conduction and carrier mobil-
ity in case of hopping, are responsible for the reduction in
the resistive properties with temperature.
52
For all the tem-
peratures, the capacitance of the grain boundary is larger
than that of the grain for both types of ferrite samples, which
can be explained on the basis that capacitance is inversely
proportional to the thickness of the media.
IV. CONCLUSIONS
In this paper, we obtained NiFe
2
O
4
and ZnFe
2
O
4
ferrite
by soft mechanochemical synthesis starting from the mixture
of appropriate powders and sintered at 1100

C. It has been
shown that mechanochemical treatment of mixture with
starting materials leads to forming of the phase of NiFe
2
O
4
and ZnFe
2
O
4
after 25 and 18 h of milling time, respectively.
In the Raman spectra is observed all of the group theory pre-
dicted rst-order active modes characteristic for spinel struc-
ture. Raman modes of sintered NiFe
2
O
4
and ZnFe
2
O
4
are in
the form characteristic for normal spinel structure, and in the
case of powder, Raman spectra show a presence of cation
inversion. The Mossbauer spectroscopy of the iron contained
newly formed particles from mixture Fe(OH)
3
/Ni(OH)
2
revealed that 94% is NiFe
2
O
4
. The degree of inversion, esti-
mated from large particles, is 0.7. The sample formed from
mixture Fe(OH)
3
/Ni(OH)
2
contains ZnFe
2
O
4
in 97%. The
TABLE II. Impedance parameters calculated from the complex impedance plots at different temperatures.
Sample T (K) R
g
10
4
(X) C
g
10
11
(F) n
g
R
gb
10
6
(X) C
gb
10
9
(F) n
gb
NiFe
2
O
4
298 239.77 4.487 0.881 3.789 4.912 0.688
323 105.1 4.590 0.887 1.365 9.585 0.649
348 29.1 4.525 0.892 471.9 8.101 0.713
398 2.572 3.949 0.898 79.92 5.442 0.822
423 1.043 3.104 0.921 37.97 7.682 0.789
ZnFe
2
O
4
298 10.84 35.86 0.762 175.6 3.235 0.894
323 2.904 35.86 0.774 54.76 4.071 0.905
348 1.185 29.98 0.816 20.37 12.54 0.807
398 0.2342 30.02 0.831 3.281 37.32 0.729
423 0.1152 6.091 0.957 1.564 17.41 0.825
187221-9 Lazarevic et al. J. Appl. Phys. 113, 187221 (2013)
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certain degree of inversion apparent in Mossbauer subspectra
cannot be resolved. It is conrmed that zinc substitution by
Fe increases with decreasing particle size. Also, a high mag-
netization of a milled sample conrms cation inversion.
Sintered sample has a normal spinel structure, as a conse-
quence, paramagnetic behavior at 300 K. The higher values
of resistance of both grain and grain boundary for the
NiFe
2
O
4
mean this ferrite has a lower conductivity than the
ZniFe
2
O
4
. The values of the conduction activation energy DE
are 0.395eV and 0.452eV for ZnFe
2
O
4
and NiFe
2
O
4
, respec-
tively. This decrease in the resistance of grains and grain
boundaries has been suggested to be due to the thermal acti-
vation of the localized charges. The analysis of the complex
impedance data shows that the capacitive and reactive proper-
ties of the sintered ferrites are mainly attributed due to the
processes which are associated with the grain and grain
boundary. Also, it is seen that the radius of curvature of Cole-
Cole plots is decreased with increasing temperature, suggest-
ing a mechanism temperature-dependent on relaxation.
ACKNOWLEDGMENTS
This research was nancially supported by the Ministry
of Education, Science and Technological Development of
the Republic of Serbia through Project No. III 45003.
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