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Impedance and Modulus Studies of Magnetic Ceramic Oxide Ba2Co2Fe12O22

(Co2Y) Doped With Bi2O3

Article  in  Journal of Applied Physics · August 2011

DOI: 10.1063/1.3615935

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 JOURNAL OF APPLIED PHYSICS 110, 034107 (2011)

Impedance and modulus studies of magnetic ceramic oxide Ba2Co2Fe12O22

(Co2Y) doped with Bi2O3
M. M. Costa,1,2,a) G. F. M. Pires, Jr.,2 A. J. Terezo,3 M. P. F. Graça,4 and A. S. B. Sombra2,b)
1
Physics Department, Federal University of Mato Grosso - UFMT, 78060-900 – Cuiabá – MT – Brazil
2
Laboratório de Telecomunicações e Ciências e Engenharia de Materiais (LOCEM), Departamento de Fı́sica,
Universidade Federal do Ceará (UFC), Caixa Postal 6030, CEP 60455-760, Fortaleza, Ceará, Brazil
3
Chemical Department, Federal University of Mato Grosso – UFMT, 78060-900 – Cuiabá – MT – Brazil
4
I3N – Aveiro, Physics Departament, Aveiro University, Campus Universitário de Santiago, 3810 – 193,
Aveiro – Portugal
(Received 28 December 2010; accepted 21 June 2011; published online 15 August 2011)
Polycrystalline samples of a layered magnetic ceramic oxide, Ba2Co2Fe12O22 (Co2Y), doped with
Bi2O3 were prepared by the solid state reaction method. The dielectric impedance properties were
studied over the range of frequency between 1 Hz–1MHz and in the temperature range of 313–493
K, using the modulus formalism. The impedance plot showed a first semicircle at high frequency
which was assigned to the grain intrinsic effect and a second semicircle, at lower frequencies,
which corresponds to grain boundary polarization (conduction phenomenon). A complex modulus
spectrum was used to understand the mechanism of the electrical transport process, which indicates
that a non-exponential type of conductivity relaxation characterizes this material. The values of the
activation energy of the compound (calculated both from dc conductivity and the modulus
spectrum) are very similar, suggesting that the relaxation process may be attributed to the same
type of charge carriers. The dielectric measurements were studied by fitting the electrical modulus
with the Havriliak–Negami function, including the conductivity parameters. The study
demonstrates that the investigation of dielectric relaxation, conductivity, and loss of the ferrite
materials, as a function of temperature, are essential for future microwave absorption applications
C 2011 American Institute of Physics. [doi:10.1063/1.3615935]
of this material. V

I. INTRODUCTION Me ¼ Cobalt II, then Co2Y is formed. This ferrite is known

as ferroxplana ferrites because it possesses an easy plane
With the recent development of satellite communica-
(basal plane) of magnetization perpendicular to the c-axis.6,7
tions and consequent mobile applications, the miniaturiza-
The saturation (Ms) and remanence (Mr) magnetization
tion and high efficiency of devices for information and
for the studied samples at room temperature were observed,
communication technology have been required, especially
21.9 emu/g and 4.73 emu/g for pure, 22.2 emu/g and 3.51
on multilayer components. This rapid development of wire-
emu/g for 3% Bi2O3, 20.2 emu/g and 3.21 emu/g for 5%
less communication necessitates the design of new ceramics,
Bi2O3, 21.1 emu/g and 3.71 emu/g for 10% Bi2O3, respec-
sinterable at low temperature, and exhibiting good dielectric
tively.8 Of the results for the saturation (Ms) and remanence
properties.1–3
(Mr) magnetization found there is no direct correspondence
Low cost, easy manufacturing, and interesting electrical
with the addition of Bi2O3.
and magnetic properties make polycrystalline ferrite one of
The classic ceramics method for preparing Ba2Me2-
the most important materials in use today. As magnetic
Fe12O22 (Refs. 9, 10) ferrite requires a high calcination tem-
materials, ferrites cannot be replaced by any other magnetic
perature, which induces aggregation of the particles. Many
material because they are relatively inexpensive, stable, and
physical properties of polycrystalline ferrites are very sensi-
have a wide range of technological applications in trans-
tive to the microstructure. The grain (bulk) and grain bound-
former cores, high quality filters, high and very high fre-
ary are the two main components that determine the
quency circuits, and operating devices.4,5 Ferrite, as a
microstructure. Thus, information about the associated phys-
semiconductor, has attracted considerable attention in the
ical parameters of the components that constitute the micro-
field of technological applications in a wide range of fre-
structure is important in understanding the overall properties
quencies, extending from microwave to radio frequency. A
of the materials.11 The concept of dielectric relaxation is
Y-type ferrite is constructed from basic units of hexagonal
associated with ionic/electronic conductivity in layered ce-
barium, M ferrite, and cubic spinel ferrites, which retains a
ramic oxides under the influence of an ac field.
hexagonal structure, usually with the direction of magnetiza-
In this paper, the present study is mainly concerned with
tion parallel to the c-axis. However, if the metal,
the temperature and frequency dependence of the conductiv-
a) ity and the dielectric relaxation phenomena of layered ce-
Author to whom correspondence should be addressed. Electronic mail:
maurocosta@pq.cnpq.br. ramic oxides Ba2Co2Fe12O22 (Co2Y) doped with Bi2O3. The
b)
Electronic mail: sombra@ufc.br. Bi2O3 was used to lower the sintering temperature of the

0021-8979/2011/110(3)/034107/7/$30.00 110, 034107-1 C 2011 American Institute of Physics

V

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034107-2 Costa et al. J. Appl. Phys. 110, 034107 (2011)

Ba2Co2Fe12O22 (Co2Y) ceramic. We report the results of where x and e0 are the angular frequency and vacuum per-
systematic studies upon the impedance and complex modu- mittivity, respectively. In Eq. (1), r0 represents the dc-con-
lus properties. The temperature and frequency dependence of ductivity and the n parameter gives the exponent of the
the dielectric quantities are discussed. frequency dependence of e00 . Here, De represents the differ-
ence between e0 at a frequency of 0 Hz and e0 at infinite fre-
II. EXPERIMENTAL PROCEDURES quency (e1 ) and is also proportional to the area below the e00
relaxation peak. It is also proportional to the maximum value
A Y-type hexagonal ferrite powder with the stoichio-
of e00 . The relaxation time [f ¼ 1=ð2psÞ] is for not too small
metric composition of Ba2Co2Fe12O22 (Co2Y) was prepared
values of a and b (approximately the frequency of the maxi-
by the solid state reaction method. The starting materials
mum peak in e00 ). The exponents, a and b, describe the asym-
with an analytical reagent grade (high purity 99.999%) used
metry and broadness of the spectrum, respectively.
were BaCO3, Co2O3, and Fe2O3. These powders were mixed
Moreover, the width parameter, a, specifies the slope of the
together according to their molecular weight ratios and were
low frequency side of the relaxation in e00 . Here, b is the
milled for 1 h on a Fritsch Pulverisette 5 planetary mill sys-
asymmetry parameter. The value of  ab gives the slope of
tem. The mixed powders were calcinated at 1050  C in air
the high frequency side of the relaxation in e00 .
conditions for 3 h and then slowly cooled to room tempera-
The Havriliak–Negami function includes the Debye,
ture at a rate of 5 /min. The structure of the resulting pow-
Cole–Cole, and Cole–Davidson functions. In order to get
ders were investigated by x-ray diffraction (XRD) technique
these equations, the parameters of the Havriliak–Negami
at room temperature with a powder diffractometer
function have to be selected as follows: Debye (a ¼ b ¼ 1);
(DMAXB/Rigaku) using Cu Ka radiation (k ¼ 1.5405 Å) in
Cole–Cole (b ¼ 1); Cole–Davidson (a ¼ 1).13
a wide range of Bragg’s angles 2h (20  h  80 ), with a
scanning rate of 0.5 /min. The obtained XRD patterns con-
firmed the formation of the isolated CO2Y phase.12 III. RESULTS AND DISCUSSION
The samples under study were prepared using 10 wt. %
Bi2O3, which was mixed with the calcinated powder and A. Complex impedance spectrum analysis
5 wt. % PVA (polyvinyl alcohol). This compound was cold The complex impedance spectroscopy method14 has
pressed into cylindrical pellets of approximately 10–12 mm been used to analyze the electrical and dielectric properties
in diameter and 2.0 mm in thickness by applying a pressure of a polycrystalline sample and their interfaces with electron-
of 1.5 tons in a uniaxial hydraulic press system. The obtained ically conducting electrodes in a wide range of frequencies
pellets were sintered at 1150  C for 4 h in air atmosphere and (1 Hz–1MHz) at different temperatures (313–493 K). The
slowly cooled at a rate of 5 /min to room temperature. Dur- dielectric properties of a material are often represented in
ing this process the PVA that was used as binder was com- terms of complex dielectric permittivity, e*, complex imped-
pletely burnt out. ance, Z*, and electric modulus, M*, which are related to
The pellets were polished to make the opposing surfaces each other as: Z* ¼ ZRejZIm; M* ¼ 1/e*(x) ¼ j(xC0)Z*
as parallel as possible. Conductive silver paste was used on ¼ MRe þ jMIm, where (ZRe, MRe) and (ZIm, MIm) are the real
both sides in order to create good electrodes. The dielectric pa- and imaginary components of impedance and modulus,
rameters were measured using a computer-controlled imped- respectively, j ¼ H1 is the imaginary factor and x is the
ance analyzer (Solartron 1260) as a function of frequency (1 Hz angular frequency, x ¼ 2pf.
to 1MHz) in the temperature range between 313 and 493 K. The variation of ZRe, ZIm and ZRe versus ZIm of impedance
The microstructure analysis at room temperature of the at selected temperatures are shown in Figs. 1–3. The Fig. 1
samples pure and 10% Bi2O3, we observe that the grains are shows the variation of the real part of the impedance (ZRe) with
uniformly and densely distributed over the surface of the frequency at different temperatures (313–493 K). The observed
sample and grain size of the compound is found to be in the
range of 2–5 lm, the results show the effects of the addition
Bi2O3 in the morphology of the studied species and shows
that the grain size of the samples increased distinctly and the
porosity decreased.8,12 The interfacial polarization is a con-
sequence of inhomogeneities in the material, which is domi-
nated by grain boundaries. For samples with a better
densification, clearly shows strong contributions for the
dielectric impedance and modulus spectrum.
The theoretical dielectric analysis of the measured data
was performed using WinFit software from NovoControl.
The data was analyzed using the dielectric modulus formal-
ism (M* ¼ 1/e*) and fitted with the Havriliak–Negami (HN)
function, including the conductivity term,
 n ( )
r 0 De
e ¼ j þ b
þ e1 ; (1) FIG. 1. (Color online) ZRe vs frequency at several measurement tempera-
e0 x ½1 þ ðjxsÞa  tures of the Co2Y doped with 10% of Bi2O3.

Author complimentary copy. Redistribution subject to AIP license or copyright, see http://jap.aip.org/jap/copyright.jsp
034107-3 Costa et al.
FIG. 2. (Color online) ZIm vs frequency at several measurement tempera-
tures of the Co2Y doped with 10% of Bi2O3.
behavior indicates that ZRe is related to the sample electric re-
sistance, and decreases with the rise of the frequency and tem-
perature. Therefore, the conduction should increase with the
rise of the temperature. At higher frequencies, the ZRe values at
different temperatures present a limit to the same point, sug-
gesting a possible release of space charge and a consequent
lowering of the energy barrier properties.15–18
Figure 2 represents the variation of the imaginary part of
the impedance (ZIm) with frequency at different temperatures.
This plot is suitable to evaluate the relaxation frequency, if it
exists, of the sample’s most resistive component. It is
observed that two peaks appear above the temperature of 313
K, indicating the presence of at least two dielectric relaxation
processes. This spectrum presents some important features:
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J. Appl. Phys. 110, 034107 (2011)
(a) the appearance of two peaks (shown by the arrows in the
spectrum), (b) the position of the peaks shift to the higher fre-
quency with the increase of the temperature, (c) the absolute
value of ZIm decreases and shifts to the higher frequency side
as the temperature increases, (d) the first peak shows the typi-
cal peak broadening, and the second peak shows the typical
peak symmetric, and (e) a decrease in the height of the peaks
with increasing temperature. The merging of all of the curves
above 1 kHz indicates a possible release of the space charge.
Broadening of the ZIm peaks with the rise in temperature indi-
cates a non-unique (i.e., multiple) relaxation time scale, whose
variance/distribution it is broadening at the higher frequency
side after the position of the peak maximum.16,19
The variation of the real versus the imaginary part of the
impedance at selected temperatures (i.e., 313–493 K) is
shown in Fig. 3, which is characterized by the appearance of
two semicircles for all temperatures.
The center of those semicircles are located below the
real axis (ZRe), indicating a non-Debye type of relaxation
process and the presence of a relaxation time distribution.
This suggests the presence of several different dielectric enti-
ties that contribute to the dipolar moment.
In all of the temperature ranges, these two depressed
semicircles were observed, centered at the low and high fre-
quency regions. For the lowest temperatures only one
depressed semicircle, in addition to a spike or part of a sec-
ond semicircle, is detected. The impedance spectra present-
ing a spike or depressed semicircle in the low frequency
region are assigned to dielectric polarization between the
sample surface and the electrode and are thus extrinsic to the
sample. This is known as the Maxwell–Wagner effect.20
FIG. 3. (Color online) ZRe vs ZIm at
several measurement temperatures of
the Co2Y doped with 10% of Bi2O3.
034107-4 Costa et al. J. Appl. Phys. 110, 034107 (2011)

FIG. 4. (Color online) r vs frequency for several measurement temperatures
of the Co2Y doped with 10% of Bi2O3.
The small diameter of the high-frequency semicircle rep-
resents small bulk resistance, which decreases with the
increase of the temperature. This behavior indicates a ther-
mally activated conduction mechanism. In these types of
materials (ceramic materials), these semicircles in the imped-
ance formalism, are generally ascribed to grain (bulk) and
grain-boundary (interface) effects.21 Similar results were
observed for a similar sample composition where Bi2O3 was
replaced by PbO.12 Electrically, these two semi-arcs can be
represented by an equivalent circuit constituted by the parallel
combinations of resistance, R, and capacitance, C, connected
in series with another RC parallel connection. One branch is
related with sample intrinsic characteristics, i.e., with the grain
(bulk), and other with the interfaces, grain boundaries and sur-
face-electrodes.11,12,22 In the impedance formalism, the rela-
tive position of the semi-arc depends upon the resistance and
capacitance values. The resistance and capacitance of the
interfacial grain boundary is usually larger than the grain.
Thus, the semicircle at high frequencies corresponds to the
grain effect (bulk) and the second semicircle, at lower fre-
quencies, to the grain boundary (conduction phenomenon).
The grain boundary effect is not so obvious at the tempera-
tures of 313 and 333 K; however, above these temperatures
they are observable. It is important to remember that the im-
pedance spectra are reproducible within the experimental
error. This fact excludes the possibility that the lower fre-
quency loop might be due to other sources such as the con-
tacts between the electrodes and material surfaces.
B. Conductivity
The conductivity representation is a most prominent
representation to relate the macroscopic measurement to
the microscopic movement of the charge carriers. The fre-
quency dependence of the ac conductivity at various tem-
peratures is shown in Fig. 4. Figure 4 exhibits the typical
behavior of ionic materials, i.e., a dc plateau in the low fre-
quency region and an increase of the conductivity with the
increase of the frequency. The conductivity is found to be
frequency independent in the low frequency region and its
value is equal to the bulk conductivity of the sample
obtained from the impedance analysis. Similar results were
observed in previous work where PbO was used instead of
Bi2O3.12 The phenomenon of the conductivity dispersion is
generally analyzed using Jonscher’s law. Therefore, the
transport mechanism is explained by the thermally acti-
vated hopping process between two sites separated by an
energy barrier. Using the value of the conductivity at 1 Hz,
as presented in Fig. 4, it was found that as a function of
the temperature, it follows the Arrhenius relation,
r ¼ r0 exp½Ea =kT, where r0 is a pre-exponential factor,
Ea is the activation energy related with this conduction pro-
cess, k is the Boltzmann constant, and T is the temperature.
Table I presents the values of ZRe and rdc for all samples,
at 1 Hz. In this table, besides the 10% Bi2O3 sample
results, the ones of 3 and 5% are also presented. For the
10% Bi2O3, the obtained activation energy was 0.54 eV.
For all of the samples, a decrease of the impedance with
the increase of the temperature was observed.
C. Dielectric analysis
The conductivity formalism (r*) and the dielectric mod-
ulus formalism (M*), have been adopted to study the fre-
quency and temperature dependence of the conductivity of
ceramics,23,24 however, it has not been unambiguously
resolved which of these two formalisms can completely
describe the relaxation process.25
The electric modulus approach began when the recipro-
cal complex permittivity was discussed as an electrical analog
to the mechanical shear modulus.26 The usefulness of the
modulus representation in the analysis of the relaxation prop-
erties has been demonstrated for polycrystalline ceramic.27–29

TABLE I. The values of ZRe and rdc for all samples in 1 Hz.

ZRe (103 X) rdc (X.m)1 ZRe (104 X) rdc (X.m)1 ZRe (104 X) rdc (X.m)1
Temp (K) BCFO3 BCFO3 BCFO5 BCFO5 BCFO10 BCFO10

313 193.41 1.64104 595 3.93106 1989 1.11106

333 162.35 1.92104 421 5.62106 1008 2.17106
353 90.36 2.51104 203 1.17105 472.4 4.67106
373 49.42 4.61104 90.2 2.64105 200.8 1.10105
393 28.52 7.91104 43.3 5.52105 88.3 2.51105
413 17.36 1.3103 21.8 1.09104 41.3 5.36105
433 10.52 2.15103 10.9 2.18104 20.1 1.11104
453 6.01 3.71103 5.48 4.35104 9.82 2.26104
473 3.27 6.88102 2.64 9.02104 4.84 4.58104
493 1.72 1.31102 1.25 1.90103 2.23 9.47104

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034107-5 Costa et al.
FIG. 5. (Color online) MRe as a function of frequency of the Co2Y doped
with 10% of Bi2O3.
In these samples, the frequency dependence of the real
part of the dielectric modulus (MRe) as a function of fre-
quency over a range of temperature is given in Fig. 5. It was
observed that the value of MRe is very low (approaching
zero) in the low frequency region. A continuous increase in
the MRe dispersion with the increase of the frequency shows
a tendency to saturate at a maximum asymptotic value (i.e.,
M1 ¼ 1/e1), for all the temperatures. This supports the sug-
gestion that the short range mobility of charge carriers is a
conduction process.30,31 These observations may possibly be
related to a lack of restoring force governing the mobility of
charge carriers under the action of an induced electric field.
These features indicate that the electrode polarization makes
a negligible contribution in the material.32
The frequency dependence of the imaginary part of the
electric modulus, MIm(f), exhibits a maximum in Fig. 6. It
may be noticed from Fig. 6 that the position of the peak
shifts toward higher frequencies as the temperature
increases. The frequency region below the peak maximum
determines the range in which charge carriers are mobile
over long distances. At the frequency above peak maximum
(high-frequency), the carriers are confined to potential bar-
riers, being mobile over short distances. The region where
FIG. 6. (Color online) MImas a function of frequency of the Co2Y doped
with 10% of Bi2O3.
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J. Appl. Phys. 110, 034107 (2011)
FIG. 7. (Color online) The Arrhenius plots shows the dependence of the rdc
and fmax (peak) vs 1000/T of the Co2Y doped with 10% of Bi2O3.
the peak occurs is indicative of the transition from long-
range to short-range mobility with increase in frequency.
This type of behavior suggests the existence of a temper-
ature-dependent hopping type mechanism for electrical con-
duction (charge transport). The broadening of the peak
shows the spread of the relaxation with a relaxation time
constant distribution. Furthermore, the appearance of peaks
in the modulus spectrum provides a clear indication of the
conductivity relaxation. The frequency of the MIm maximum
(fmax) gives the mean value of the relaxation time distribu-
tion, sr ¼ 1=ð2p  fmax Þ. Its variation as a function of temper-
ature is shown in Fig. 7. The variation of ln(rT) as a
function of 1/T and of ln(fmax) as a function of 1/T follow
the Arrhenius relation and present similar activation energy
values (Fig. 7; 54 eV). This indicates that the electric entities
responsible for the conduction and for the relaxation process,
observed in M*, are the same.33–37
Comparing these results with the ones previously pub-
lished with PbO (see Ref. 12) show that the presence of
Bi2O3 increases the activation energy.
In Fig. 6 the lines represent the theoretical adjustment
with the Havriliak–Negami equation. Here, the complex
modulus formalism, proposed by Macedo (see Ref. 23), was
adopted to study the dielectric relaxation mechanisms,
because it minimizes the electrode interface capacitance con-
tribution and others interfacial effects. Thus, the sample
intrinsic dielectric behavior can be easily observed.38 The
observed dielectric relaxation mechanism shifts to higher
frequencies with the increase of the measurement tempera-
ture indicating an increase in the difficulty of the dielectric
dipoles during depolarization. This relaxation, due to the
modulus formalism characteristics, should be attributed to
the intrinsic characteristics of the samples.
It is known that the conductivity and polarization phe-
nomena in ferrites has been largely attributed to the presence
of Fe2þions, which give rise to a heterogeneous hexagonal
structure, and the consequent electron exchange between
Fe2þ and Fe3þ. Moreover, if cobalt is introduced into the fer-
rite composition, which is the present case, the contribution
from the hole transfer between the Co3þ and Co2þ ions
should also be taken into consideration.39 In the conduction
process, the contribution of the holes is smaller than the elec-
trons, due to their lower mobility. Therefore, the electron
034107-6 Costa et al. J. Appl. Phys. 110, 034107 (2011)

TABLE II. Fit results.

Temp.K r0 [S=cm] n De s [s] e1 a b

7 2 4 1
313 1.1310 1.00 2.1610 6.4210 9.0710 0.8656 0.3011
333 1.13107 1.00 1.81102 2.51104 8.20101 0.8662 0.2996
353 1.13107 0.63 1.03101 9.05105 1.93 0.8555 0.3296
373 1.13107 0.73 2.07102 3.36105 8.83101 0.8554 0.3426
393 1.13107 0.70 7.14103 1.51105 5.05101 0.8682 0.3101
413 1.28107 1.00 1.89102 5.65106 8.41101 0.8455 0.3834
433 1.28107 1.00 2.04101 2.76104 2.71 0.8510 0.4090
453 1.13107 1.00 3.40102 1.35106 1.12 0.8581 0.3927
473 2.46104 1.00 3.15101 6.47107 3.36 0.8516 0.4496
493 1.31103 1.00 1.13 3.27107 6.29 0.8521 0.5291

exchange between the Fe2þ and Fe3þ ions, which results in
local displacements in the direction of the applied external
electric field (while the hole exchange between Co3þ and
Co2þ is in the opposite direction), causes the dielectric polar-
ization in ferrites.39 Nevertheless, a charge exchange
between Co2þ and Fe3þ can also exist.40 However the polar-
ization of Fe2þ - Fe3þ is easiest and thus their number will
be reflected in the dielectric constant value. The results of
Fig. 6 indicate that this number should be the same for all
measurements. This is true if we assume that the maximum
measurement temperature used (493 K) is not enough to pro-
mote the modification of the oxidation state of this ion. In
Fig. 6, it can be see that until 393 K, a second relaxation pro-
cess occurs at higher frequencies. For the measurements at
higher temperatures, this behavior is not observed due to the
maximum frequency available (1 MHz). In this figure, the
lines represent the theoretical fitting that was made without
considering this high frequency phenomenon. All of the data
obtained from the fit process is registered in Table II.
From these results it is observed that with the increase of
the temperature there is an increase of e 1 (Table II). This
indicates an increase in the number of dipoles that contribute
to the increase of the dipolar moment. With the increase of
the measurement temperature, De presents a behavior very
similar to that of e 1 (Table II) suggesting that estatic is tem-
perature independent. The theoretical fitting was performed
assuming a conductivity term, r0, [see Table II and Eq. (1)].
It was observed that with the increase of the measurement
temperature the conductivity tends to increase. However, it
must be noted that for temperatures above 453 K, the values
of r0 are higher compared to that at low temperatures. The
increase of r0 indicates that by raising the temperature, the
number of charge carriers with enough energy to overcome
the potential barriers related to the conduction process
increases (see Ref. 38). The parameters, a and b, do not vary
significantly with temperature, indicating that the asymmetry
of the M00 spectrum is temperature independent. The b value
is small (<0.5), indicating a high broadness of the spectrum
and therefore, a high time relaxation distribution.
IV. CONCLUSION
The present work reports the results of our investigation
on the dielectric and impedance properties of the Bi2O3-
doped magnetic ferrite compound, Ba2Co2Fe12O22 (Co2Y).
The complex impedance plots reveal two semicircles
described by the grain (bulk) and grain boundary (interface)
effects. The modulus plot shows non-Debye behavior and is
asymmetric with respect to the peak maxima, and that the
peaks are considerably broader on both sides of the maxima
and suggest dielectric relaxation in the material. The activa-
tion energy, Ea, calculated from dielectric modulus spectra
and from the conductivity are the same (Ea ¼ 0.54 eV), indi-
cating that the relaxation and conductivity processes may be
attributed to the same type of entities. The dielectric analysis
using the dielectric modulus formalism (M* ¼ 1/e*) and fitted
with the Havriliak–Negami (HN) function, proved to be rea-
sonable in explaining the conduction mechanism in the
material.
The interfacial polarization is a consequence of inhomo-
geneities in the material, which is dominated by grain boun-
daries. For samples with a better densification, clearly shows
strong contributions for the dielectric impedance and modu-
lus spectrum.
For samples with lower Bi2O3 concentrations, the con-
ductivity and dielectric behaviors are similar to the one
observed with 10%. Comparing to the previously published
results with PbO instead of Bi2O3, it was observed that the
presence of Bi2O3 increases the activation energy.
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