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Synthesis and Reactivity in Inorganic, Metal-Organic, and

Nano-Metal Chemistry

ISSN: 1553-3174 (Print) 1553-3182 (Online) Journal homepage: http://www.tandfonline.com/loi/lsrt20

Characterization and Transport Properties of


Mixed Ferrite System Mn1-xCuxFe2O4; 0.0 x 0.7
M. A. Ahmed, A. A. Azab, E. H. El-Khawas & E. Abd EL Bast
To cite this article: M. A. Ahmed, A. A. Azab, E. H. El-Khawas & E. Abd EL Bast (2016)
Characterization and Transport Properties of Mixed Ferrite System Mn1-xCuxFe2O4; 0.0 x
0.7, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 46:3,
376-384, DOI: 10.1080/15533174.2014.988243
To link to this article: http://dx.doi.org/10.1080/15533174.2014.988243

Accepted author version posted online: 27


Apr 2015.

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Date: 20 October 2015, At: 22:11

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry (2016) 46, 376384
Copyright Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2014.988243

Characterization and Transport Properties of Mixed Ferrite


System Mn1-xCuxFe2O4; 0.0  x  0.7
M. A. AHMED1, A. A. AZAB2, E. H. EL-KHAWAS3, and E. ABD EL BAST3
1

Materials Science Lab (1), Physics Department, Faculty of Science, Cairo University, Giza, Egypt
Solid State Electronics Laboratory, Solid State Physics Department, Physics Division, National Research Center, Dokki, Giza, Egypt
3
Basic Science Department, Higher Technological Institute, Tenth of Ramadan City, Egypt
2

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Received 13 October 2014; accepted 9 November 2014

A series of Cu-doped Mn ferrites with the formula Mn1-xCuxFe2O4 (0.0  x  0.7) were synthesized by citrate auto combustion
method. The structural characterization and morphology of the samples were examined by X-ray diffraction (XRD), energydispersive X-ray analysis (EDX), and scanning electron microscopy (SEM). XRD and EDX conrmed the formation of single-phase
cubic spinel structure. The electrical conductivity (s), dielectric constant (e0 ), and dielectric loss factor (e00 ) were studied as a function
of temperature at different frequencies ranged from 100 kHz to 5 MHz. Increasing is observed in the values of s, e0 , and e00 with
substitution of copper up to x D 0.3. Above this value, a decrease in s, e0 , and e00 was detected.
Keywords: nanoferrite, SEM, EDX, conductivity, dielectric

Introduction
Mixed metallic oxides especially spinels having the general
formula AB2O4 are very important materials for technological applications. Mixed copper ferrites have high electrical
resistivity and consequently low eddy currents as well as
dielectric losses. They have several applications such as radiofrequency coils, transformer cores, rod antennas, and magnetic cores of read-write heads for high-speed digital tapes.
[13]
The studies of dielectric properties of ferrites offer much
valuable information on the behavior of localized electrical
charge carriers. This leads to a good explanation and also an
understanding of the mechanism involved in dielectric behavior of ferrites. It is well known that the conductivity and the
dielectric properties of ferrites are strongly dependent on frequency and temperature.[4,5] Hence, the study of such properties at different frequencies, temperatures and chemical
compositions provide valuable information about the kind
and amount of additives required to obtain high quality
materials for many applications. The properties of the nanocrystalline materials are varied from those of corresponding
bulk materials, due to their small grain size. Also in these
materials a large percentage of atoms are available at their
grain boundaries and therefore there are more chances for

Address correspondence to A. A. Azab, Solid State Electronics


Laboratory, Solid State Physics Department, Physics Division,
National Research Center, 33 El Bohouth St., Dokki, Giza,
P.O.12622, Egypt. E-mail: aliazab@hotmail.com
Color versions of one or more of the gures in the article can be
found online at www.tandfonline.com/lsrt.

interaction between the grains.[6] In the present work we


aimed to reach the critical concentration of Cu in the compound at which we optimize the transport properties to be
more applicable.

Experimental
The spinel ferrite of Mn1-xCuxFe2O4; (x D 0.0, 0.1, 0.3, 0.5,
0.7) was prepared by citrate auto combustion method.[6] An
aqueous solution of Mn(NO3)2.4H2O, Cu(NO3)2.3H2O, and
Fe(NO3)3.9H2O from Aldrich were used. Nitrates complexes
of the metal ions components were mixed in stoichiometric
ratios and citric acid with a ratio (1:1) with constant stirring
to form the citrate-precursor mixture. The pH value of the
precursor solution was adjusted to about 7 by using drops of
ammonia solution. The solution again stirred during heating
the sample and then transformed into Xerogel; the dried gel
burns itself to form the powder, without further heat treatment the powders were pressed into pellets using uniaxial
press of pressure 1.9 108 Nm2. X-ray diffraction (XRD)
were carried out at room temperature
on a Bruker D8 with

Cu ka radiation (k D 1.5418 A) in 2u ranged from 10 to 80 .
Elemental analysis and surface morphology were analyzed
by EDX spectroscopy and scanning electron microscope
(SEM: Model JEOL JSM6400F).
The samples were good polished to obtain uniform parallel surfaces. Contacts on the sample surface were made
by silver paste and then checked for good conduction.
The dielectric constants (e0 , e00 ) and the ac conductivity (s)
were measured by the two probe method using LCR
meter model Hioki type 3532 (Japan) as a function of the

Mn1-xCuxFe2O4
temperature from 300 to 750 K at different frequencies
ranging from 100 kHz to 5MHz. The dc conductivity was
measured for the investigated samples in the same range
of temperature as that of ac conductivity. The temperature of the samples was measured using a K-type thermocouple connected to a Digi-Sense thermometer TC9500
(USA) with junction in contact with the sample.

Results and Discussion


Structure Characterization

of structure analysis as well as microstructure was


reported in our previously published work.[7]
Figure 2 shows SEM micrograph of Mn1-xCuxFe2O4
(0.0  x  0.7). The data reveals cluster size variation
with increasing CuC2 content. From a close look to the
micrograph one nd that, there is nearly stable values
from 0  x  0.3 after which a peculiar increase was
found at x D 0.5. This peculiarity does not appear for all
clusters, while the rest of the clusters have nearly the
same size. Such behavior is interpreted according to the
difference in ionic
radii between both Cu2C (0.73 A) and

2C
[8]
Mn (0.83 A). Another expected reason is the cation
redistribution among A and B sites in such a way that
Cu2C resides on octahedral sites instead of the small
amount of Mn2C ions. At large Cu content, one expect

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Figure 1 illustrates XRD patterns of Mn1-xCuxFe2O4, (0.0


 x  0.7), it reveals single-phase spinel structure. Details

377

Fig. 1. X-ray diffraction patterns of the Mn1-xCuxFe2O4 compound (0.0  x  0.7).

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378

Ahmed et al.

Fig. 2. SEM micrograph of the Mn1-xCuxFe2O4 compound (0.0  x  0.7).

the migration of Fe2C to the A site. More investigations


using Mossbauer spectroscopy is needed to obtain the
detailed distribution of iron ions among A and B sites.
The composition of Cu doped manganese ferrites has
been examined using the energy dispersive X-ray analysis
(EDX). X-ray analysis spectra of Mn1-xCuxFe2O4(x D 0,
0.1 and 0.5) samples are shown in Figure 3. From the
EDX spectrum, the presence of Mn, Cu, Fe and O are
conrmed; the appearance of Pt is due to platinum coating for SEM measurements. The quantitative analysis of
EDX spectrum in Table 1 revealed the relative atomic
ratio of all elements. These values are close to the
expected values for MnFe2O4, Mn0.9Cu0.1Fe2O4, and
Mn0.5Cu0.5Fe2O4.

conductivity with increasing temperature. These assure semiconducting like behavior of Mn1-xCuxFe2O4and ascribed the
increasing in the thermally activated mobility of charge carriers. The activation energy for the thermally activated hopping process was obtained by tting the dc conductivity data
with the Arrhenius relation.[9]
sdc T D so exp DE/kB T

Table 1. EDX results of Mn1-xCuxFe2O4


Atomic %
Comp. X

Electrical Properties
Figure 4 shows the dc conductivity of Mn1-xCuxFe2O4(0  x
 0.7). The observed gure show an increase in dc

(1)

0
0.1
0.5

Chemical formula

Mn

Cu

Fe

Mn

Cu

Fe

8.45
10.81
3.57

0
1.09
3.73

15.05
22.74
13.83

76.5
65.35
78.87

1
0.9
0.5

0
0.1
0.5

2
2
2

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Mn1-xCuxFe2O4

Fig. 3. EDX spectrum of the Mn1-xCuxFe2O4 compound at x D 0.0, 0.1, and 0.5.

379

380

Ahmed et al.

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Fig. 4. The dependence of dc conductivity on the reciprocal temperature of the Mn1-xCuxFe2O4 compound (0.0  x  0.7).

where s 0 is the pre-exponential constant, DE is the activation


energy for dc conductivity, T is the absolute temperature,
and kB is the Boltzmanns constant. The activation energy for
low-temperature region (EI) and high-temperature region
(EII) are calculated and listed in Table 2. From the reported
data it is observed that the activation energy EII is higher
than EI. This trend is attributed to higher lattice vibration
which increase the scattering of charge carriers resulting in
decreasing conductivity and increasing EII.
Figure 5 shows ac conductivity of Mn1-xCuxFe2O4 (0 
x  0.7) as a function of temperature and different frequency. From the reported data it is observed that the
data reveals that s ac increase with both frequency and
temperature. The hopping of electron between Fe2C and
Fe3C ions on the B sites played role in conduction

Fig. 5. Variation of ac conductivity with the reciprocal of absolute temperature as a function of frequency of the Mn1-xCuxFe2O4
compound (0.0  x  0.7).
Table 2. The values of activation energy of EI and EII as a function of frequency at different concentrations of Mn1-xCuxFe2O4 (0 
x  0.7)
x D 0.0
Activation energy (eV)
Dc
100 kHz
800 kHz
2 MHz

x D 0.1

x D 0.3

x D 0.5

x D 0.7

EI

EII

EI

EII

EI

EII

EI

EII

EI

EII

0.391
0.129
0.129
0.086

0.774
0.516
0.516
0.573

0.369
0.069
0.069
0.069

0.626
0.297
0.297
0.319

0.369

0.614
0.270
0.258
0.310

0.016

0.029

0.626
0.172
0.172
0.129

0.369
0.069
0.065
0.258

0.595
0.344
0.258
0.258

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Mn1-xCuxFe2O4

381

Fig. 6. Variation of dielectric constant e0 with the absolute temperature as a function of frequency of the Mn1-xCuxFe2O4 compound
(0.0  x  0.7).

mechanism in spinel ferrites.[10] In general, the increase in


conductivity with increasing frequency can be explained
on the basis of Maxwell-Wagner theory and Koops
model.[1114] Accordingly the theory of dielectric structure
was formed by two conducting layers separated by ultra
thin insulating layer, which forms the grain boundaries.
The nonconducting layer or grain boundary is formed by
oxygen ions. These grain boundaries are more active at
lower frequencies; hence the hopping frequency of Fe2C
and Fe3C ions is less at lower frequencies. As the applied
frequency increases the conductive grains became more
active by promoting the hopping between Fe2C and Fe3C
cations, thereby increasing the hopping frequency. Thus,
we observe a gradual increase in conductivity with frequency. The increase in conductivity does not means that
the amount of charge carriers increases, but only the rate
of hopping of charge carriers between Fe2C and Fe3C ions
increases.[15] As temperature increases the mobility of hopping electrons increases as well as conductivity.
The dielectric properties can vary widely in ferrites as a
function of temperature, frequency of applied electric eld,
crystal structure, humidity and other external factors. The
dielectric response of ferrite materials can be described by the

dielectric constant as a complex quantity composed of a real


and an imaginary component:
e D e0 ie00

(2)

the rst term e0 is the real part of dielectric constant representing the amount of energy stored in a dielectric material, while
the second term e00 is the imaginary part of dielectric constant
which describes the dissipated energy. Figure 6 shows the
effect of temperature on dielectric constant (e0 ) for Mn1-xCuxFe2O4 (0  x  0.7) ferrites at different frequencies. It is clear
that e0 increases with temperature to reach maximum value
for the samples x D 0.0,0.1, and 0.3 with peak value shifted
to higher temperature with increasing frequency. It is
explained due to thermal activation, which enhances the
number of dipoles available for polarization when the sample
is at a high temperature.
The decrease of dielectric constant with increasing frequency is observed of copper ferrites and it is normal
behavior of spinel ferrites.[1618] This attributed to the
MaxwellWagner interfacial type of polarization,[11,12]
which is in agreement with Koops phenomenological

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382

Ahmed et al.

Fig. 7. Variation of dielectric loss factor e00 with the absolute temperature as a function of frequency of the Mn1-xCuxFe2O4
compound (0.0  x  0.7).

theory.[14] The decrease in polarization with increasing frequency is due to the fact that, beyond a certain frequency
of the electric eld, the electronic exchange between Fe2C
and Fe3C cannot follow the eld variation, and therefore
the real part of dielectric constant (e0 ) decreases with
increasing frequency.
Figure 7 shows the dielectric loss factor (e) of Mn1Cu
x
xFe2O4 (0  x  0.7), which has the same behavior as
that of e0 , where e increases with temperature and
decreases with frequency. This is because the dielectric
loss arises when the polarization lag behind the applied
alternating eld in which it is caused by the impurities
and imperfections in the crystal. According to the phenomenological Koops theory,[14] this was explained on
the basis of the fact that, in the low-frequency region, the
resistivity is high and the grain boundary effect is dominant, more energy is required for electron exchange
between Fe2C and Fe3C ions, as a result the loss is high.
In the high frequency region, when the resistivity is low, a
small energy is required for electrons transfer between the
two Fe ions at the octahedral site. The dielectric loss
shows its maximum value (Scherrer relaxation) at samples
x D 0, 0.1, and 0.5. Debye relaxation occurs when

hopping the frequency of charge carriers becomes approximately equal to that of an externally applied eld.[19] Also
at lower frequencies, high dielectric loss may be accrued
due to impurities, crystal defects, and moisture.
Figure 8 shows the composition dependence of Mn1xCuxFe2O4 (0  x  0.7) on the conductivity and dielectric constant values in which they increased up to x D 0.3
and after that they decreased. This is the same behavior
of the magnetic properties in the previous work.[7] The
increase of conductivity in ferrite compound is mainly due
to the hopping electron between ions of the same element
present at different valence state.
Mn2 C C Fe3 C $ Mn3 C C Fe2 C
Cu2 C $ Cu C C e C

In other words this may be due to the decrease in the lattice


parameter with increasing Cu content.[7] The hopping length
(BB distance) is affected directly on the conductivity whenever the length decreases, the conductivity will increases. The
reason for decreasing the conductivity is the exchange

383

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Mn1-xCuxFe2O4

Fig. 8. (a) Variation of dc conductivity with Cu2C content. (b,c) Variation of ac conductivity and dielectric constant with Cu2C
content at two absolute temperatures, 323 K and 373 K, and frequency 100 kHz of Mn1-xCuxFe2O4 compound (0.0  x  0.7).

interaction between Mn2C and Fe3C at B-site resulting in


decreasing the ratio of Fe3C/Fe2C.

conductivity, dielectric constant, and dielectric loss factor


increase with Cu2C substitution up to x D 0.3 and then
decreased.

Conclusion
X-ray and EDX measurements conrmed synthesis of
Mn1-xCuxFe2O4 in spinel structure by citrate nitrate auto
combustion method. SEM images showed that the cluster
size increased with increasing Cu2C up to x D 0.5. The ac

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