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Article history:
Received 12 August 2013
Received in revised form
21 February 2014
Available online 26 March 2014
In this study, nanocrystalline Mg1 xZnxFe2O4 soft magnetic ferrites are synthesized by varying x from
0.0 to 0.6 with a step size of 0.1. A new combustion synthesis approach is taken using glycine as fuel and
metal (Fe, Mg and Zn) nitrates as reactants. The effect of varying chemical composition, i.e. changing the
parameter x, on the structural and magnetic properties is evaluated. X-ray diffraction results conrm
that all samples crystallize in a spinel-type structure. Lattice parameter (a) is found to increase with the
substitution of Zn2 ions. The eld emission scanning electron microscopy (FESEM) is used for
morphological investigations. Magnetic properties of Mg1 xZnxFe2O4 ferrites are also evaluated by a
vibrating sample magnetometer (VSM). It is found that the saturation magnetization increases as the Zn
content goes up to x 0.4 and decreases afterwards. The change in saturation magnetization with Zn
content is attributed to the variation of cation distribution in the spinel structure as chemical
composition is modied.
& 2014 Elsevier B.V. All rights reserved.
Keywords:
Glycinenitrate process
Combustion synthesis
MgZn ferrite
Magnetic property
Nanocrystalline
1. Introduction
Cubic spinel ferrites are ferrimagnetic materials, made by a
close-packed array of oxygen atoms with tetrahedral and octahedral cavities, containing iron oxide as the main constituent with
various metal oxides [1,2]. They constitute an important class of
magnetic materials, which have attracted much interest in many
elds. This can be attributed to the unique and novel properties
and also wide variety of potential applications of these materials
in high-density magnetic recording, color imaging, microwave
devices, bio-processing, magnetic refrigeration, magneto-optical
devices, hyperthermia, information storage systems, gas sensors,
magnetic recording media, electronic industries, humidity sensors
and green anode materials, to name a few [28]. They have
recently been the subject of much research with regard to both
their theoretical foundations and the possibility of deriving new
materials based on ferrites for further applications [18].
Ferrites have the general formula (MFe1 )[M1 Fe1 ]O4,
where M is a divalent metal ion (e.g. Zn, Mg, Mn, Fe, Co, Ni or a
mixture of them). The magnetic cations in the cubic spinel lattice
can occupy A-type (divalent and tetrahedrally coordinated with
oxygen) or B-type (trivalent and octahedrally coordinated with
Corresponding author.
E-mail address: ahonarbakhsh@semnan.ac.ir (A. Honarbakhsh Raouf).
http://dx.doi.org/10.1016/j.jmmm.2014.03.027
0304-8853/& 2014 Elsevier B.V. All rights reserved.
22
S. Hajarpour et al. / Journal of Magnetism and Magnetic Materials 363 (2014) 2125
ceramic materials with high surface area and compositionally homogeneous powders in the nanometer range [6,1315]. This method
often provides ferrites at relatively low temperatures (o600 1C) and
no further processing of the combustion products is required [16,17].
As mentioned earlier, the new synthesis method bears a considerable
effect on the cation distribution, and consequently, modies the
magnetic properties.
This paper is focused on the preparation of Mg1 xZnxFe2O4
ferrites (with x 0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) by the GNP
method. The structure and magnetic properties of the assynthesized ferrite powders are discussed as dependent on the
zinc content.
H0r H0p
cp
2.2. Characterization
Structural studies on the as-prepared powders are conducted
using X-ray diffraction (XRD, Bruker D8) with Cuk radiation.
The lattice parameter of the spinel compounds is estimated from
the position of the (440) plane. The average crystallite size (D) and
the lattice strain () of all samples are evaluated based on the Xray diffraction line broadening by employing Scherrer's equation
and the tangent formula respectively. All structural parameters are
estimated by means of a commercial software package [18]. The
microstructure evaluation and morphological features of the
product powders are determined by eld emission scanning
electron microscopy (FESEM; Hitachi S-4160) of the gold-coated
samples. The room-temperature magnetic measurements are done
with a vibrating sample magnetometer (VSM, Meghnatis Daghigh
Kavir, Iran) in an operating range of 78.5 kOe.
x = 0.6
x = 0.5
x = 0.4
x = 0.3
x = 0.2
x = 0.1
x=0
S. Hajarpour et al. / Journal of Magnetism and Magnetic Materials 363 (2014) 2125
8M
Na3
Table 1
Data of crystallite size (D), lattice strain (), lattice parameter (a) and X-ray density
(dx) of Mg1 xZnxFe2O4.
X
D (nm)
a ()
dx(g/cm3)
0
0.1
0.2
0.3
0.4
0.5
0.6
46.7
34.4
49.4
49
39.7
34.3
46.1
0.00278
0.0033
0.00327
0.00273
0.00291
0.00331
0.00251
8.38
8.38
8.40
8.40
8.42
8.43
8.42
4.51
4.60
4.66
4.75
4.83
4.89
4.99
23
24
S. Hajarpour et al. / Journal of Magnetism and Magnetic Materials 363 (2014) 2125
Fig. 4. FESEM photomicrographs of MgZn ferrite: (a) low magnication and (b) high magnication.
4. Conclusion
of emu/g can be theoretically calculated by the following
equation [27]:
Ms
8nB
a3
S. Hajarpour et al. / Journal of Magnetism and Magnetic Materials 363 (2014) 2125
Acknowledgment
The authors would like to thank the Semnan University and
Shahid Chamran University for supporting this research.
References
[1] S.D. Shenoy, P.A. Joy, M.R. Anantharaman, J. Magn. Magn. Mater. 269 (2004)
217226.
[2] H. Dutta, M. Sinha, Y.C. Lee, S.K. Pradhan, Mater. Chem. Phys. 105 (2007)
3137.
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Magn. Mater. 284 (2004) 206214.
[4] K.A. Mohammed, A.D. Al-Rawas, A.M. Gismelseed, A. Sellai, H.M. Widatallah,
A. Yousif, M.E. Elzain, M. Shongwe, Physica B: Condens. Matter 407 (2012)
795804.
[5] M. Al-Haj, J. Magn. Magn. Mater. 299 (2006) 435439.
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(2013) 165169.
[7] Z. Pdzich, M.M. Buko, M. Krlikowski, M. Bakalarska, J. Babiarz, J. Eur. Ceram.
Soc. 24 (2004) 10531056.
[8] M. Sinha, H. Dutta, S.K. Pradhan, Physica E: Low-Dimens. Syst. Nanostruct. 33
(2006) 367369.
[9] D.C. Bharti, K. Mukherjee, S.B. Majumder, Mater. Chem. Phys. 120 (2010)
509517.
[10] J.C. Toniolo, M.D. Lima, A.S. Takimi, C.P. Bergmann, Mater. Res. Bull. 40 (2005)
561571.
[11] I. Shari, H. Shokrollahi, M.M. Doroodmand, R. Sa, J. Magn. Magn. Mater. 324
(2012) 18541861.
25
ARTICLE IN PRESS
Department of Physics, Cochin University of Science and Technology, Thrikkakara, Cochin 682 022, India
b
Physical Chemistry Division, National Chemical Laboratory, Pune 411 008, India
Received 15 March 2003; received in revised form 23 June 2003
Abstract
Nanosized ZnFe2O4 particles containing traces of a-Fe2O3 by intent were produced by low temperature chemical
coprecipitation methods. These particles were subjected to high-energy ball milling. These were then characterised using
X-ray diffraction, magnetisation and dielectric studies. The effect of milling on zinc ferrite particles have been studied
with a view to ascertaining the anomalous behaviour of these materials in the nanoregime. X-ray diffraction and
magnetisation studies carried out show that these particles are associated with strains and it is the surface effects that
contribute to the magnetisation. Hematite percentage, probably due to decomposition of zinc ferrite, increases with
milling. Dielectric behaviour of these particles is due to interfacial polarisation as proposed by Koops. Also the defects
caused by the milling produce traps in the surface layer contributes to dielectric permittivity via spin polarised electron
tunnelling between grains. The ionic mechanism is enhanced in dielectrics with the rise in temperature which results in
the increase of dielectric permittivity with temperature.
r 2003 Published by Elsevier B.V.
PACS: 75.50.K; 75.50.G; 75.30.P; 77.22.E; 81.20.W
Keywords: Magnetic nanoparticles; Zinc ferrite; High-energy ball milling; Superparamagnetism; Spinels; Strain parameter; Dielectric;
Interfacial polarisation; Spin polarised tunnelling; Lab VIEW
1. Introduction
Nanoparticles have been generating extensive
interest in recent years among researchers worldwide owing to their interesting physical and
chemical properties with respect to their coarser
sized cousins in the bulk [15]. Nanoparticles of
many ferrites have been successfully obtained by
*Corresponding author. Tel.: +91-484-2577404; fax: +91484-2577595.
E-mail address: mra@cusat.ac.in (M.R. Anantharaman).
0304-8853/$ - see front matter r 2003 Published by Elsevier B.V.
doi:10.1016/S0304-8853(03)00596-1
ARTICLE IN PRESS
218
S.D. Shenoy et al. / Journal of Magnetism and Magnetic Materials 269 (2004) 217226
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S.D. Shenoy et al. / Journal of Magnetism and Magnetic Materials 269 (2004) 217226
ZnFe2O4 is synthesized by coprecipitation methods with traces of a-Fe2O3 and these are subjected
to HEBM.
The dielectric properties of nano particle ferrite
materials are inuenced mainly by the method of
preparation, cation distribution, grain size, sintering temperature, oxygen parameter, the ratio of
Fe2+/Fe3+ ions and oxygen anion vacancies in
lattices [27]. So far, there exists no convincing
reports on dielectric properties of nano particle
ferrites which throws light on the conduction
mechanism of these materials in the ultrane
regime.
The effect of ball milling on the structural,
magnetic and dielectric properties of the ne
particles is investigated. This is intended to check
the claim by various researchers that ZnFe2O4
shows anomalous behaviour when prepared in the
nanoregime by employing coprecipitation methods. Moreover, this is a sequel to our investigations on ne particle normal spinel ferrites.
219
2. Experimental
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60
Relative Intensity (I/I0*100)
(121)
50
(231)
(-211)
40
30
20
0
100
200
Milling time (minutes)
300
8.46
a (A)
220
8.44
8.42
8.40
0
100
200
Milling time (minutes)
300
440(ZF)
-211( )
231( )
511(ZF)
Intensity (arb.unit)
400(ZF)
220(ZF)
121( )
311(ZF)
ZF300
ZF30
ZFP
20
60
40
80
100
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S.D. Shenoy et al. / Journal of Magnetism and Magnetic Materials 269 (2004) 217226
10.0
221
9.5
9.0
100
200
Milling time (minutes)
300
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222
0.03
ZF300
cos
0.02
ZF30
ZFP
0.01
a-Fe2 O3 ZnFe2 O4
-a-Fe2 O3 magnetic ZnFe2 O4 :
1.0
1.5
4 sin
2.0
0.015
Strain
0.010
0.005
0.000
0
100
200
Milling time (minutes)
300
3.2. Magnetisation
Fig. 7 shows typical results for magnetisation
curves taken at 300 K and 83 K for ZFP, ZF30,
ZF300, respectively. Room temperature curves
show typical superparamagnetic behaviour with
no hysteresis. That is, both retentivity and
coercivity are zero, which is in tune with the
results obtained by other researchers [9,29,3638].
Fig. 8 depicts the variation of saturation
magnetisation with milling time. The strain associated with ne particles, as a result of milling,
produces a disorder by displacement of ions, which
is one cause for an increase in magnetisation. In
ultrane particles large fractions of atoms are
located on the surface and therefore the surface
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223
25
83K
M s (emu/gm)
20
15
10
300K
5
0
0
100
200
Milling time (minutes)
300
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224
10
100 KHz
8
6
5 MHz
10 MHz
14
Temperature=353K
100 KHz
8
7
6
5 MHz
5
10 MHz
Dielectric permittivity
9
Temperature=300K
Dielectric permittivity
Dielectric permittivity
12
2
0
100
200
300
Milling time (minutes)
Temperature = 393K
12
100 KHz
10
8
5 MHz
6
4
10 MHz
2
0
100
200
300
Milling time (minutes)
100
200
300
Milling time (minutes)
Fig. 10. Variation of dielectric constant with milling time at different frequencies (at xed temperatures).
during ball milling may also contribute to dielectric permittivity which is predominant at lower
frequencies [48]. The non-uniformity of the structure increases with reduction in size according to
our XRD results. Hence this should increase the
dielectric permittivity of ball milled samples and
our results are in accordance with this (Fig. 10).
The traps formed at the grain boundaries are
not of uniform shape and may become the cause
for deviation from parallel alignment of moments
of individual grains. Electrons are then transferred
from one grain to another by a process called spin
polarised tunnelling in which electron spin is
conserved. Tunnelling probability of spin polarised electrons is larger when the magnetisation
of the particles is aligned [43]. This will increase
the dielectric permittivity with milling.
Fig. 10 clearly shows the enhancement of
dielectric permittivity at low frequencies. However, dielectric permittivity decreases at higher
frequencies since the mobility of charge carriers is
low at higher frequencies and cannot follow the
alternation of applied AC electric eld [49].
4. Conclusions
XRD results indicate that the particles formed
are ultrane and associated with strains. The
structural and magnetic studies on the milled
ZnFe2O4 samples indicate that zinc ferrite in the
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ZF30
100 KHz
500 KHz
1 MHz
5 MHz
9 MHz
10 MHz
300
350
400
Temp in K
10
500 KHz
1 MHz
5 MHz
9 MHz
10 MHz
4
300
12
100 KHz
350
400
Temp in K
Dielectric permittivity
ZFP
Dielectric permittivity
Dielectric permittivity
ZF300
10
225
100 KHz
500 KHz
1 MHz
8
5 MHz
6
9 MHz
10 MHz
4
300
350
400
Temp in K
Fig. 11. Variation of dielectric permitivity with temperature (at different frequencies).
Acknowledgements
One of the authors, MRA thanks Third World
Academy of Sciences (TWAS), Trieste, Italy for
nancial assistance received through project (Ref.
No. 00-118/RG/PHYS/AS). SDS and MRA thank
Inter University Consortium for Department of
Atomic Energy Facilities (IUC-DAEF), Govt. of
India for nancial support through project (Ref.
No. IUC/MUM/CRS-M-60).
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J. Magn. Magn. Mater. 189 (1998) 83.
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K.D. Becker, Physica B 234236 (1997) 617.
[14] G.F. Goya, H.R. Rechenberg, J. Magn. Magn. Mater.
196197 (1999) 191.
[15] V. Sepelak, P. Druska, U. Sleinike, Mater. Struct. 6 (1999)
100.
[16] B.S. Murty, S. Ranganathan, Int. Mater. Rev. 43 (1998)
101.
[17] K. Haneda, H. Kojima, J. Am. Ceram. Soc. 57 (1974) 68.
[18] J. Sort, J. Nogues, X. Amils, S. Surinach, J.S. Munoz,
M.D. Baro, Appl. Phys. Lett. 75 (1999) 3177.
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Research Article
Microstructure Characterization of Nanocrystalline Magnesium
Ferrite Annealed at Elevated Temperatures by Rietveld Method
Swapan Kumar Pradhan,1 Sumanta Sain,1 and Hema Dutta2
1 Department
2 Department
of Physics, The University of Burdwan, Golapbag, West Bengal, Burdwan 713104, India
of Physics, Vivekananda College, West Bengal, Burdwan 713103, India
1. Introduction
The synthesis of nanocrystalline spinel ferrites has been
investigated intensively in recent years due to their potential
applications in nonresonant devices, radio frequency circuits, high-quality filters, rod antennas, transformer cores,
read/write heads for high-speed digital tapes, and operating
devices [13]. Nowadays, these materials are largely synthesized in nanometric scale for new and improved properties
[46]. Magnesium ferrite, MgFe2 O4 (Figure 1), is a soft
magnetic n-type semiconductor material [7], which finds a
number of applications in heterogeneous catalysis, adsorption, sensors, and in magnetic technologies. Among the other
methods of preparation of nanocrystalline ferrite powders,
high-energy ball milling is a very suitable solid-state processing technique for the preparation of nanocrystalline ferrite
powders exhibiting new and unusual properties [811].
Ferrites have the general formula (M1x Fex)[Mx Fe2x ]O4 .
The divalent metal element M (Mg, Zn, Mn, Fe, Co, Ni,
or mixture of them) can occupy either tetrahedral eight (A)
or sixteen octahedral [B] sites of a cubic mineral spinel
(MgAl2 O4) structure as depicted by the parentheses or brack-
ISRN Ceramics
study for precise determination of several microstructural
parameters (change in lattice parameters, particle size, and
lattice strain), cation redistribution in terms of occupancy
factors of cations at dierent sites as well as relative phase
abundances of this multiphase nanocrystalline material containing a large number of overlapping reflections. However,
the selected area electron diraction pattern (SAED) of 9 h
milled sample could not detect the presence of any secondary
phase, and the pattern seems to be composed of single Mgferrite phase.
2. Experimental
Figure 1: Fragments from the bulk Mg-ferrite normal spinel: MgO tetrahedra, Fe-O octahedral; positions of Fe (blue) and oxygen
(red) atoms are shown.
3. Method of Analysis
In the present study, we have adopted the Rietvelds powder
structure refinement analysis [1622] of X-ray powder
diraction data to obtain the refined structural parameters,
ISRN Ceramics
such as atomic coordinates, occupancies, lattice parameters,
and thermal parameters, and microstructural parameters,
such as particle size and r.m.s. lattice strain. For instrumental
broadening correction, a specially processed Si standard [23]
was used. The Rietvelds software MAUDWEB 2.24 (Java
web start version) [18] is specially designed to refine simultaneously both the structural and microstructure parameters through a least-squares method. The peak shape was
assumed to be a pseudo-Voigt (pV) function with asymmetry. The background of each pattern was fitted by a
polynomial function of degree 4. To simulate the theoretical
X-ray powder diraction pattern containing all the MgO,
-Fe2 O3 , and Mg-ferrite (normal spinel) and Mg-ferrite
(inverse spinel) phases in a single pattern, the following
considerations were made:
(i) for MgO (cubic, space group: Fm3m (225), a =
0.42 nm (ICDD PDF no. 87-0653)), Mg2+ , and O2
in special Wycko positions 4a and 4b, respectively,
(ii) for -Fe2 O3 (rhombohedral, space group: R3c (167),
a = 0.5032 and c = 1.3733 nm (ICDD PDF no. 890599)) with Fe and O atoms in special Wycko
positions 12c and 18e, respectively,
(iii) for Mg-ferrite (cubic, normal spinel, space group:
Fd3m (227), a = 0.83998 nm (ICDD PDF no. 881943)) with Mg2+ (A-site), Fe3+ [B-site], and O2 in
the 8a, 16d, and 32e Wycko positions, respectively,
(iv) for Mg-ferrite (cubic, inverse spinel, space group:
Fd3m (227), a = 0.83998 nm (ICDD PDF no. 881943)) with 0.1 Mg2+ + 0.9 Fe3+ (A-site), 0.5 Mg2+
+ 0.5 Fe3+ [B-site], and O2 in the 8a, 16d, and 32e
Wycko positions, respectively.
3.1. Crystalline Structure Characterization by X-Ray Powder
Diraction. For microstructure characterization, the experimental profiles are fitted with the most suitable pV analytical
function because it takes individual care for both the particle
size and strain broadening of the experimental profiles. A
detailed mathematical description of the Rietveld analyses
has been reported elsewhere [1622]. Refinement continues
till convergence is reached with the value of the quality
factor, GoF very close to 1 (varies between 1.1 and 1.3),
which confirms the goodness of refinement. The Rietvelds
method was successfully applied for determination of the
quantitative phase abundances in multiphase materials [19
22]. The structure refinement along with size-strain broadening analysis is carried out simultaneously by adopting the
standard procedure [17, 18].
3.2. Size-Strain Analysis. The basic consideration of this
method is the modeling of the diraction profiles by an analytical function, which is a combination of Cauchy, Gaussian,
and asymmetry functions as well. It is well established
that the observed peak broadenings of the sample profiles
are mainly due to the presence of small particle size and
r.m.s. strain inside the particles. The particle size and strain
broadening can be approximated better with Cauchy and
Gaussian type functions, respectively [1923]. Being a linear
3
combination of a Cauchy and Gaussian functions, the pV
function is the most reliable peak-shape function and is
being widely used in the Rietvelds structure refinement
software. The process of successive profile refinements modulated dierent structural and microstructural parameters
of the simulated pattern to fit the experimental diraction
pattern. Profile refinement continues until convergence is
reached in each case, with the value of the quality factor
(GoF) approaches very close to 1.
ISRN Ceramics
6000
Intensity (a.u.)
4000
2000
1473 K
0
3000
2000
1000
0
1000
1273 K
500
1073 K
0
600
400
200
0
873 K
400
9h
200
0
MgFe2 O4
-Fe2 O3
20
30
40
50
2 (deg)
60
70
80
(a)
(440)
(511)
(400)
(311)
(220)
0.5 1/nm
(b)
ISRN Ceramics
5
1
1.1
1
0.9
0.9
0.8
Occupancy factor
Volume fraction
0.8
0.7
0.6
0.5
0.4
0.3
0.7
0.6
0.5
0.2
0.4
0.1
0
0.3
900
1000
1100
1200
1300
Annealing temperature (K)
1400
1500
Mixed spinel
Inverse spinel
-Fe2 O3
900
1000
1100
1200
1300
1400
1500
Inverse spinel
Fe in (A) site
Mg in [B] site
increases and that may result in decrease in Fe3+ cation deficiency nonstoichiometric Mg-ferrite phase matrix. Redistribution of cations inside mixed spinel leads to the complete
transformation of mixed spinel to inverse spinel in the
annealing temperature range 1073 K1273 K which results
the rapid increase in phase content of Mg-ferrite phase
with nearly inverse spinel lattice. Further annealing of the
sample after 1273 K for 1 h duration results complete solidstate diusion of unreacted -Fe2 O3 phase into the inverse
spinel lattice, and the composition of the Mg-ferrite becomes
completely stoichiometric.
In the present work, we found that the nanostructured
MgFe2 O4 prepared by high-energy milling is metastable
with respect to structural changes at elevated temperatures.
Sepelak et al. [24] also found that the thermal stability
of the mechanosynthesized product extends up to 623 K.
Above this temperature, a gradual crystallization of the
nanoscale MgFe2 O4 powders takes place. In the present case,
we found the thermal stability up to 1073 K. During the
annealing process, the nonequilibrium cation distribution
relaxes toward their equilibrium configuration.
The cation distribution in MgFe2 O4 , upon which many
physical and chemical properties depend, is a complex function of processing parameters and depends on the preparation method of the material [14]. The cation distribution in
mechanosynthesized spinel ferrites from Mossbauer spectra
and/or X-ray diraction patterns is not as straightforward
as is frequently claimed in the literature. Sepelak et al.
[24] reported for the first time the microstructure characterization and cation distribution in nanosized MgFe2 O4
synthesized in a one-step mechano-chemical process. They
also confirmed that the nonuniform cation distribution
within MgFe2 O4 nanoparticles by means of Mossbauer
spectroscopy is consistent with the results of Rietveld analysis
ISRN Ceramics
0.865
0.86
0.855
0.85
0.845
0.84
0.835
1.38
120
MgFe2 O4
100
900
1000
1100
1200
1300
1400
Annealing temperature (K)
1500
Inverse Spinel
Mixed Spinel
80
60
40
20
-Fe2 O3
1.375
26
24
22
20
18
16
14
12
850 900 950 1000 1050 1100
c
900
1000
a
0.53
1000
1100
1200
1300
1400
1500
1500
1400
1500
(a)
40
1400
Inverse spinel
-Fe2 O3
Mixed spinel
0.525
900
1100
1200
1300
Annealing temperature (K)
30
20
3
2
10
1
0
800
900
900
1000
1100
1200
1300
Annealing temperature (K)
Inverse spinel
Mixed Spinel
-Fe2 O3
(b)
ISRN Ceramics
The significant grain growth may be attributed to the complete ordering of inverse spinel lattice with proper placement
of cations at their respective tetrahedral and octahedral positions. Particle size of -Fe2 O3 phase slowly increases with
annealing temperature in a usual manner.
The r.m.s. lattice strain values of both -Fe2 O3 and
mixed spinel phases are in general decreasing in nature with
annealing temperature in a usual manner. The inverse spinel
phase grows with a large lattice strain. Initially, the inverse
spinel lattice could not release strain, rather strain increases
slightly with increasing temperature upto 1073 K. It suggests
that up to that temperature there was no significant change
in cation distribution in the lattice, and the small increment
in lattice strain may be attributed to the solid-state diusion
of -Fe2 O3 into the lattice.
The r.m.s. strain value drops suddenly to almost nil after
annealing the sample at 1273 K for 1 h duration. It is interesting to note that the mixed spinel is completely absent after
that temperature of annealing. It seems that the annealing
temperature favours distribution cations to their preferred
sites. As a result, lattice strain reduces to nil when samples
are annealed at higher range of temperature 1273 K1473 K.
It is also evident from the figure that in the same temperature
range particle size of inverse phase increases abruptly from
10 nm to120 nm which may be considered as particle size
growth of inverse spinel phase in a less constraint environment.
5. Conclusions
Nanocrystalline Mg-ferrite powders have been prepared by
high-energy ball milling of stoichiometric mixture of MgO
and -Fe2 O3 powders. Analysis of 9 h ball-milled samples
by Rietvelds method reveals the presence of mixed and
nearly inverse spinel nanocrystalline Mg-ferrite as major and
minor phases, respectively, with a small amount (3 wt%)
of unreacted - Fe2 O3 . Nanocrystalline ball-milled powder
was postannealed within 8731473 K temperature range.
Structural changes and microstructure characterization of
-Fe2 O3 and both the mixed and nearly inverse spinel Mgferrite phases in the postannealed samples have been investigated by Rietvelds analysis of X-ray powder diraction data
for the first time, to best of our knowledge. The following
important observations may be summarized as follows.
Distribution of cations among (A) and [B] sites in mixed
spinel matrix changes continuously, and occupancy of Fe3+
in (A) site (inverse spinel) increases with increasing annealing temperature. Mixed spinel structure changes to inverse
spinel after 1 h annealing at 1073 K. The composition of Mgferrite becomes completely stoichiometric one by solid-state
diusion of unreacted -Fe2 O3 into nearly inverse spinel
lattice after 1 h of annealing at 1273 K. Particle sizes of inverse
spinel do not increase considerably up to 1073 K and increase
suddenly with a large release in r.m.s. lattice strain after transformation of mixed spinel to a nearly inverse spinel structure.
The present study reveals that the nanocrystalline stoichiometric nearly inverse spinel Mg-ferrite can be formed
completely by postannealing the 9 h ball-milled powder
sample.
Acknowledgments
One of the authors, S. K. Pradhan, wishes to thank UGC
authority, India for providing grants for instruments under
DSA III and COSIST programs. The authors are also thankful to Dr. V. Petkov, Department of Physics, Central Michigan
University, USA for providing X-ray diraction facility.
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Ho3+ doping in CoFe2 O4 spinel ferrite and understanding of
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[12] N. W. Grimes, R. J. Hilleard, J. Waters, and J. Yerkess, An
X-ray diraction study of disorder in MgFe2 O4 and Mg(Cr,
Al)O4 , Journal of Physics C, vol. 1, no. 3, pp. 663672, 1968.
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[14] V. Sepelak, D. Schultze, F. Krumeich, U. Steinike, and K. D.
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141-142, pp. 677682, 2001.
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[20] H. Dutta, M. Sinha, Y. C. Lee, and S. K. Pradhan, Microstructure characterization and phase transformation kinetics of
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nanocrystalline Mg-Zn ferrite at elevated temperatures, Japanese Journal of Applied Physics, vol. 47, no. 11, pp. 86678672,
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[22] S. Sain, S. Patra, and S. K. Pradhan, Microstructure and optical band-gap of mechano-synthesized Cdx Zn1 -x S quantum
dots, Journal of Physics D, vol. 44, no. 7, Article ID 075101,
8 pages, 2011.
[23] J.G.M.V. Berkum, Strain fields in crystalline of materials, Ph.D.
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[24] V. Sepelak, A. Feldho, P. Heitjans et al., Nonequilibrium
cation distribution, canted spin arrangement, and enhanced
magnetization in nanosized MgFe2 O4 prepared by a one-step
mechanochemical route, Chemistry of Materials, vol. 18, no.
13, pp. 30573067, 2006.
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966, 2003.
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ARTICLE IN PRESS
Abstract
To prepare zinc-substituted spinel-type ferrite ne particles of M1xZnxFe2O4 (M=Mg, Mn, Co, Ni, Cu, (Li, Fe)
x=01) with good crystallinity and stoichiometry, the authors investigated a glycinenitrate process. The product
powder was an agglomerate of ne particles whose typical diameter was several tens of nanometers. X-ray diffraction
patterns revealed that the produced particles were mono-phase in almost all reaction systems. Energy-dispersive X-ray
spectroscopy microanalysis of the product particles (MnZnFeO) revealed that the distributions of Mn/Fe ratio and
Zn/Fe ratio were highly sharp both within the agglomerate and between agglomerates.
r 2004 Elsevier B.V. All rights reserved.
PACS: 75.50.y; 75.50.Gg; 81.20.Ka
Keywords: Combustion synthesis; Fine particles; Magnetism; Spinel ferrite; Crystallinity; Stoichiometry
1. Introduction
Magnetic ne particles have attracted much
interest in many elds [15]. One application of
magnetic materials utilizes their heating effects, i.e.
magnetic hysteresis energy losses. For example,
there are a considerable number of works on
Corresponding author. Tel: +81-298618490; fax: +81-
298618459.
E-mail address: kikukawa-n@aist.go.jp (N. Kikukawa).
0304-8853/$ - see front matter r 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2004.06.039
ARTICLE IN PRESS
N. Kikukawa et al. / Journal of Magnetism and Magnetic Materials 284 (2004) 206214
207
ARTICLE IN PRESS
208
N. Kikukawa et al. / Journal of Magnetism and Magnetic Materials 284 (2004) 206214
BET
Crystallite
size
20
10
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
ARTICLE IN PRESS
N. Kikukawa et al. / Journal of Magnetism and Magnetic Materials 284 (2004) 206214
209
ARTICLE IN PRESS
210
N. Kikukawa et al. / Journal of Magnetism and Magnetic Materials 284 (2004) 206214
ARTICLE IN PRESS
N. Kikukawa et al. / Journal of Magnetism and Magnetic Materials 284 (2004) 206214
211
Table 1
Magnetic properties of synthesized spinel-type ferrite particles
Run
No.
LiFe5O8
MgFe2O4
MnFe2O4
CoFe2O4
NiFe2O4
CuFe2O4
ZnFe2O4
G66
G34
G24
G53
G08
G25
G49
Experimental results
Literature
Lattice
constant
(nm)
Saturation
magnetization
(emu/g)
Coercive
force (Oe)
Saturation
magnetization
(emu/g)b
Curie point
(K)b
0.8339
0.8391
0.8499
0.8386
0.8349
0.8382
0.8435
57
32
72
79
42
49
7.3
155
72
89
885
183
149
19
903
696
625
797
868
749
69
31
112
94
56
30
903
713
573
793
858
728
0.8333
0.83873
0.8499
0.83919
0.8339
0.8369
0.84411
(17-114)
(36-398)
(10-319)
(22-1086)
(10-325)
(25-283)
(22-1012)
Saturation magnetization and coercive force were measured at the magnetic eld of 15 kOe and at room temperature.
a
Powder diffraction le (PDF).
b
Ref. [33].
ARTICLE IN PRESS
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N. Kikukawa et al. / Journal of Magnetism and Magnetic Materials 284 (2004) 206214
4. Conclusion
In order to prepare zinc-substituted spinel-type
ferrite ne particles of M1xZnxFe2O4 (M=Mg,
Mn, Co, Ni, Cu, (Li, Fe) x=01) with good
crystallinity and stoichiometry, we investigated a
References
[1] K. Raj, B. Moskowitz, R. Casciari, J. Magn. Magn.
Mater. 149 (1995) 174.
[2] D.L. Leslie-Pelecky, R.D. Rieke, Chem. Mater 8 (1996)
1770.
[3] S.A. Majetich, J.H. Scott, E.M. Kirkpatrick, K. Chowdary, K. Gallagher, M.E. McHenry, Nanostruct. Mater 9
(1997) 291.
[4] R.H. Kodama, J. Magn. Magn. Mater. 200 (1999) 359.
[5] M. Sugimoto, J. Am. Ceram. Soc. 82 (1999) 269.
[6] P. Moroz, S.K. Jones, B.N. Gray, Int. J. Hyperthermia 18
(2002) 267 and references therein.
[7] (a) R. Hergt, W. Andrae, C.G. dAmbly, I. Hilger, W.A.
Kaiser, U. Richter, H.-G. Schmidt, IEEE Trans.
Magn. 34 (1998) 3745;
(b) A. Jordan, R. Scholz, K. Maier-Hauff, M. Johannsen,
P. Wust, J. Nadobny, H. Schirra, H. Schmidt, S.
Deger, S. Loening, W. Lanksch, R. Felix, J. Magn.
Magn. Mater. 225 (2001) 118;
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[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
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[21]
[22]
[23]
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[25]
[26]
[27]
213
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N. Kikukawa et al. / Journal of Magnetism and Magnetic Materials 284 (2004) 206214
Physica B
journal homepage: www.elsevier.com/locate/physb
Department of Mathematical and Physical Sciences, College of Arts & Sciences, University of Nizwa, P.O. Box 33, Code 616, Oman
Department of Physics, College of Science, Sultan Qaboos University, P.O. Box 36, Code 123, Al-khoud, Oman
c
Department of Chemistry, College of Science, Sultan Qaboos University, P.O. Box 36, Code 123, Al-khoud, Oman
b
a r t i c l e i n f o
abstract
Article history:
Received 23 August 2011
Received in revised form
10 December 2011
Accepted 13 December 2011
Available online 21 December 2011
Compositions of polycrystalline MgZn mixed ferrites with the general formula Mg1 xZnxFe2O4
(0 r x r 1) were prepared by the standard double sintering ceramic method. The structural properties
of these ferrites have been investigated using X-ray diffraction and infrared absorption spectroscopy.
The lattice parameter, particle size, bonds length, force constants, density, porosity, shrinkage and
cation distribution of these samples have been estimated and compared with those predicted
theoretically. Most of these values were found to increase with increasing Zn content. The energy
dispersive (EDS) analysis conrmed the proposed sample composition. The scanning electron microscope (SEM) and transmission electron microscope (TEM) micrographs showed aggregates of stacked
crystallites of about 200800 nm in diameter. Far infrared absorption spectra showed two signicant
absorption bands. The wave number of the rst band, n1, decreases with increasing Zn content, while
the band, n2 shifts linearly towards higher wave numbers with Zn contents, over the whole composition
range. The room temperature electrical resistivity was found to decrease as Zn-content increases.
Values of the vacancy model parameters showed that the packing factors Pa and Pb decrease, the
fulllment coefcient, a, remains almost constant and the vacancy parameter, b, strongly increases
with increasing Zn content in the sample. The small values of Pa, Pb, a and the strong increase of the
vacancy parameter, b, indicate the presence of cation or anion vacancies and the partial participation of
the Zn2 vacancies in the improvement of the electrical conductivity in the MgZn ferrites.
& 2011 Elsevier B.V. All rights reserved.
Keywords:
MgZn Ferrites
Spinel
IR
XRD
Electrical resistivity
Force constants
Vacancy model parameters
1. Introduction
Ferrites have been the subject of extensive investigation
because of their wide range applications such as information
storage systems, gas sensors, microwave devices and magnetic
recording and electronic industries. These materials are characterized by high electrical resistivity and unique magnetic and
electrical properties, which result in low eddy currents and
dielectric losses [13]. The crystalline structure of the spinel
ferrites has two sites, the tetragonal A-sites and octahedral
B-sites. These materials have the general chemical formula
3
2
3
2
(TM21
. The factor d represents the fracdFed ) [TMd Fe2 d]O
3
tion of Fe
ions at the A-sites. Magnesium ferrite, MgFe2O4, is
predominantly an inverse spinel and the degree of inversion
depends upon heat treatment [4]. The zinc ferrite, ZnFe2O4, has
the normal spinel structure, in which the Zn2 ions occupy the
tetrahedral sites where the octahedral B-sites are occupied by the
Fe3 ions. The IR spectra are important tools to investigate the
0921-4526/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2011.12.097
structural properties of the ferrite materials. They give information about the positions of the ions in the spinel lattice, the
vibration modes, the valance state of the ions and their occupation in the spinel lattice crystal. Moreover, the IR spectra scans
can be used to detect the completion of the solid state reaction,
cations distribution and the deformation of spinel structure. The
IR spectra absorption bands mainly appear due to vibrations of
the oxygen ions with the cations producing various frequencies in
the unit cell. The vibration frequency depends on the cations
mass, cationoxygen distance and the bonding force [5].
The vacancy model [6] describes the inuence of vacancies and
mixed valence on the transport processes in solid solutions with
the spinel structure. This model deals with four quantities; the
coefcients of ion packing at the tetrahedral and octahedral sites,
the fulllment coefcient of the unit cell, which determines the
degree of the ionic packing of the spinel structure, the difference
of Pauling electronegativities, which give an evaluation of the
ionic bonds strength in the tetrahedral and octahedral sites and
the vacancy parameter, which is a measure of the total vacancy
concentration in the sample.
Moreover, distinct relations were reported [7] to exist between
the ionic packing factors at the tetrahedral and octahedral sites
796
2. Experimental
Samples of the spinel series Mg1 xZnxFe2O4 (x 01 step 0.1)
were prepared using the conventional double sintering technique,
in which powders of high purity MgO, ZnO and Fe2O3 oxides were
mixed in required proportions in agate mortar. The mixture was
rst sintered at 1000 1C for 24 h in air medium followed by
cooling to room temperature. The powder was then remixed and
ground once more to promote homogeneity. Pellets of 13 mm and
23 mm thick are prepared using hydraulic press of 10 tons/cm2.
These pellets and the rest of the powder were sintered at 1050 1C
for 24 h followed by natural cooling to room temperature. The
nal total losses in sample masses were negligible (less than
0.1%). Moreover, the samples compositions were conrmed by
Mossbauer and the transmission electron microscope analysis.
The single-phase spinel structure was conrmed by the X-ray
diffraction spectrum of these samples. The X-ray diffraction
spectrum of these samples were examined using Phillips
The
PW1820 diffractometer with CuKa radiation (l 1.5404 A).
scans range was kept the same for all samples 2y 101001 using
a step size of 0.021 with sample time of 2 s.
Samples for recording IR spectra were prepared by mixing
small quantity of the powder of the samples with solid KBr. The
mixed powder of samples was then placed in a cylindrical disc and
pressed at 10 tons/cm2 by a hydraulic press. The IR measurements
of the prepared samples were recorded at room temperature in
the range from 400 up to 1000 cm 1 using PERKIN-ELMER-1430
infrared Spectrophotometer.
Samples for the DC resistance measurements at room temperature were prepared by rst grinding the surfaces to remove
any oxide, such as Fe2 , which might be caused by the distillation
off the sample surface, such as the Zn2 , during sintering at high
temperatures and to remove any contamination to the pellet
surfaces during the pressing process [8]. The pellets surfaces were
coated with a silver paste conductor to ensure a good electrical
contact between the sample and the two copper terminals for the
electrical resistance measurements.
The microstructure and sample morphology were examined
with analytical scanning electron microscope (ASEM) model
JSM-6510LA-JEOL and transmission electron microscope model
JEM-1400-JEOL.
Fig. 1. The X-ray diffraction pattern for the Mg1 xZnxFe2O4 samples.
Table 1
Values of rA, rB, aexp, ath and cation distribution of Mg1 xZnxFe2O4 ferrites.
x
aexp (A)
ra (A)
rb (A)
ath (A)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
8.378
8.393
8.405
8.409
8.417
8.421
8.430
8.439
8.442
8.448
8.450
0.6697
0.6840
0.6992
0.7142
0.7293
0.7445
0.7595
0.7746
0.7897
0.8047
0.8200
0.6652
0.6660
0.6664
0.6669
0.6674
0.6678
0.6683
0.6687
0.6692
0.6697
0.6700
8.483
8.508
8.532
8.556
8.581
8.605
8.630
8.654
8.679
8.703
8.728
(Mg.03Fe.97)A [Mg.97Fe1.03]B
(Zn.1Mg.1Fe.8)A [Mg.8Fe1.2]B
(Zn.2Mg.08Fe.72)A [Mg.72Fe1.28]B
(Zn.3Mg.08Fe.62)A [Mg.62Fe1.38]B
(Zn.4Mg.07Fe.53)A [Mg.53Fe1.47]B
(Zn.5Mg.05Fe.45)A [Mg.45Fe1.55]B
(Zn.6Mg.05Fe.35)A [Mg.35Fe1.65]B
(Zn.7Mg.04Fe.26)A [Mg.26Fe1.74]B
(Zn.8Mg.035Fe.165)A [Mg.165Fe1.835]B
(Zn.9Mg.03Fe.07)A [Mg.07Fe1.93]B
(Zn1)A [Fe2]B
8.70
8.65
8.50
8.45
8.40
8.40
8.35
8.25
0.0
0.2
0.4
0.6
0.8
1.0
Zn (x)
Fig. 3. Variation of the lattice parameter, aexp and ath with x. (The inset: shows
variation of aexp with rA.)
2
B
0.672
0.64
0.62
Table 2
Values of u, d, aexp, Ra and Rb as a function x.
x
aexp (A)
( 70.001)
RA (A)
(7 0.001)
RB (A)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0.3810
0.3814
0.3818
0.3822
0.3826
0.3830
0.3834
0.3838
0.3842
0.3846
0.3850
0.0060
0.0064
0.0068
0.0072
0.0076
0.0080
0.0084
0.0088
0.0092
0.0096
0.0100
8.378
8.393
8.405
8.409
8.417
8.421
8.430
8.439
8.442
8.448
8.450
1.901
1.910
1.919
1.925
1.933
1.940
1.948
1.956
1.962
1.970
1.976
2.045
2.046
2.046
2.043
2.042
2.040
2.039
2.038
2.036
2.034
2.032
2.050
1.98
2.045
8.45
8.55
8.30
aexp
ath
8.60
8.35
A Mg21xy
Fe31
Zn2x Mg2y Fe31xy
x y B
rB
8.50
8.75
797
1.96
1.94
2.040
RB
RA
1.92
2.035
1.90
0.670
0.60
2.030
0.0
0.58
0.4
0.6
0.8
1.0
Zn (x)
rA
0.668
rB
0.56
0.54
0.666
0.52
0.50
0.664
0.0
0.2
0.2
0.4
0.6
Zn (x)
0.8
1.0
798
3.3
Table 3
Variation of Rx, Rx0 , Rx00 , dexp, dxrd, DWH and DXRD with x.
x
Rx
(A)
Rx 0
(A)
Rx00
(A)
dexp
(g/cm3)
dXRD
(g/cm3)
DWH
(nm)
DXRD
(nm)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
3.104
3.119
3.133
3.144
3.157
3.168
3.181
3.194
3.204
3.216
3.227
2.820
2.815
2.810
2.802
2.795
2.787
2.780
2.774
2.765
2.757
2.749
2.964
2.969
2.974
2.975
2.979
2.980
2.984
2.987
2.989
2.991
2.992
2.80
2.85
2.83
2.91
2.96
2.97
3.03
3.14
3.10
3.26
3.45
4.16
4.21
4.26
4.31
4.36
4.40
4.45
4.49
4.53
4.57
4.61
33
43
57
32
48
70
52
46
58
53
33
58
76
101
56
83
123
92
81
102
92
57
relations [21]
p
RA a 3d 18
RB a
r
d
1
2
3d
2 16
d u0:375
3.1
r
11
4u2 3u
16
Rx00 a
R x''
3.0
2.9
R x'
2.8
2.7
2.6
0.0
0.2
0.6
0.4
0.8
1.0
Zn (x)
Fig. 5. Variation of the bond lengths Rx, Rx0 and Rx00 with x.
5
6
Rx
3.2
Values of Rx, Rx0 and Rx00 are shown in Table 3 and Fig. 5. It is clear
that values of Rx, Rx0 and Rx00 increase, decrease and increase
slowly, respectively, with Zn content. Similar results have been
reported for the CdZn [24] and CdNiZn [25] ferrite systems.
The changes in u cause a distortion of the octahedral sites
symmetry. This distortion results in shortening the octahedral
shared edge bringing the anions into close contact along those
edges. The calculated results for the octahedral shared edges, Rx0 ,
and the bond length, RB, for these samples support such explana corresponds to about
tions. The average value of Rx0 ( 2.79 A)
Cation-cation distances
p a 58 u
p
q a u 14 3
p
r a u 14 11
p
s a 13 u 18 3
ap
2
a4p
c 8 11
p
d 4a 3
3ap
e 8
3
p
f 4a 6
b
799
Fig. 6. The interionic distances and angles between cationscations and anionscations at the tetrahedral and octahedral sites in spinel ferrites.
Table 4
as a function of Zn(x).
Values of the interionic distances in (A)
x
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
2.0442
2.0445
2.0441
2.0417
2.0403
2.0379
2.0367
2.0355
2.0328
2.0309
2.0280
1.9010
1.9102
1.9187
1.9255
1.9331
1.9399
1.9478
1.9557
1.9623
1.9695
1.9758
3.6400
3.6577
3.6741
3.6870
3.7017
3.7146
3.7298
3.7449
3.7575
3.7713
3.7834
3.6568
3.6653
3.6725
3.6762
3.6816
3.6853
3.6912
3.6971
3.7003
3.7049
3.7077
2.9621
2.9674
2.9716
2.9730
2.9759
2.9773
2.9805
2.9836
2.9847
2.9868
2.9875
3.4733
3.4796
3.4845
3.4862
3.4895
3.4912
3.4949
3.4986
3.4999
3.5024
3.5032
3.6278
3.6343
3.6395
3.6412
3.6447
3.6464
3.6503
3.6542
3.6555
3.6581
3.6590
5.4417
5.4514
5.4592
5.4618
5.4670
5.4696
5.4754
5.4813
5.4832
5.4871
5.4884
5.1305
5.1396
5.1470
5.1494
5.1543
5.1568
5.1623
5.1678
5.1696
5.1733
5.1745
4.7
Table 5
Values of the interionic angles (in degrees) as a function of Zn(x).
3.6
3.5
4.6
x
h1
h2
h3
h4
h5
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
123.34
123.22
123.08
122.96
122.83
122.71
122.58
122.45
122.33
122.20
122.08
144.95
144.38
143.83
143.29
142.75
142.22
141.69
141.17
140.66
140.15
139.65
92.85
93.05
93.25
93.45
93.65
93.85
94.06
94.26
94.47
94.67
94.88
125.92
125.96
126.01
126.05
126.09
126.14
126.18
126.23
126.27
126.31
126.36
74.48
74.14
73.80
73.46
73.12
72.79
72.45
72.12
71.80
71.47
71.15
Density (g/cm3)
3.4
4.5
3.3
4.4
3.2
d xrd
4.3
3.1
d exp
4.2
3.0
2.9
4.1
2.8
4.0
0.0
ZM
Na3
dexp
m
V
11
Values of the calculated dXRD and dexp are shown in Table 3 and
plotted in Fig. 7 as a function of Zn content in the sample. Both
dexp and dXRD densities increase with increasing Zn content. The
true density, dXRD, is higher than the bulk density, dexp, for all
0.4
0.6
0.8
1.0
Zn (x)
Fig. 7. Variation of the dexp and dXRD densities with x.
10
0.2
12
800
0.34
Porosity
0.32
0.30
0.28
0.26
Fig. 10. EDS pattern of the surface of a solid piece of x 0.5.
0.24
0.0
0.2
0.4
0.6
0.8
1.0
Zn (x)
Fig. 8. Variation of the porosity, p, with x (the inset shows 2r vs. x).
0.010
B Cos (0)
0.008
0.006
0.004
Fig. 11. SEM micrograph for the surface of a solid piece of x 0.5.
0.303
0.304
0.305
0.306
Sin (0)
0.307
0.308
Fig. 9. Variation of b cos(y) vs. sin(y) for Mg1 xZnxFe2O4 ferrites. (the inset:
b cos(y) vs. sin(y) for one sample).
increase the sample density. These data reveal clearly that with
increasing Zn concentration in the ferrite apparent porosity of the
samples increase because of increase in lattice parameter. Meanwhile the sample volume shrinkage increases as Zn content increase.
The inset in Fig. 8 shows the sample diameter as a function of Zn
content. The increased sample porosity and volume shrinkage with
increasing Zn content might be attributed to the difference in specic
gravity and hence the lattice parameter of the ferrite components.
Similar results have been reported for the CdNiZn ferrites [25].
The average crystallite size, DXRD, of all samples were evaluated from the reected X-ray diffraction peaks using Scherrers
equation [28]:
DXRD
kl
b cos y
13
Fig. 12. TEM micrograph for crashed small solid piece of x 0.5.
b cos y
kl
2e sin y
DWH
14
Table 6
Values of n1, n2, Kt, Ko and r as a function of Zn(x).
x
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
n1 (cm 1)
571
572
571
570
568
566
562
562
562
564
564
n2 (cm 1)
432
432
434
436
438
436
439
438
440
446
447
Kt 105
(dynes/cm)
Ko 105
(dynes/cm)
q 108 (X-cm)
2.372
2.381
2.372
2.364
2.347
2.331
2.298
2.298
2.298
2.314
2.314
1.358
1.358
1.370
1.383
1.396
1.383
1.402
1.396
1.409
1.447
1.454
34.5
13.6
4.30
1.91
3.00
2.85
1.10
0.67
0.35
0.28
1.97
7 105
801
802
Rb (A)
2.02
2.03
2.04
Kt (dyne/cm) x 105
1.44
2.36
1.42
2.34
1.40
2.32
1.38
2.30
Ko (dyne/cm) x 105
1.46
2.38
1.36
1.90
1.95
2.00
2.05
Ra (A)
Fig. 14. The force constants Kt and Ko vs. bond lengths, Ra and Rb.
10.0
Log p (ohm-cm) x 10
35
p (ohm-cm) x 108
30
25
20
15
9.5
9.0
8.5
8.0
7.5
7.0
0.0
10
0.2
0.4 0.6
Zn (x)
0.8
1.0
5
0
0.0
0.2
0.4
0.6
Zn (x)
0.8
1.0
15
10
r xo 0:625uaRo
17
Pa
r xt
RA
18
Pb
r xo
RB
19
where rxt and rxo are the interstitial radii and RA and RB are the
average values of the ionic radii at the tetrahedral and octahedral
sites, respectively, u is the anion parameter, a is the lattice
parameter and Ro is the anion radius. It is claimed that [6] the
small values of the packing factors, Pa and Pb ( o1), testify to the
smaller ion distances and larger overlapping of the cation and
anion orbital, suggesting the existence of cation or anion vacancies while the opposite holds for larger values of Pa and Pb ( 1).
Table 7
Values of the ionic packing, fulllment, vacancy and Pauling electronegativity
coefcients of Mg1 xZnxFe2O4 ferrites.
x
rxt (A)
rxo (A)
Pa
Pb
b (%)
DvA
DvB
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0.5210
0.5302
0.5387
0.5455
0.5531
0.5599
0.5678
0.5757
0.5823
0.5895
0.5958
0.6642
0.6645
0.6641
0.6617
0.6603
0.6579
0.6567
0.6555
0.6528
0.6509
0.6480
0.778
0.775
0.770
0.764
0.758
0.752
0.748
0.743
0.737
0.733
0.727
0.998
0.998
0.997
0.992
0.989
0.985
0.983
0.980
0.975
0.972
0.967
0.649
0.647
0.646
0.646
0.646
0.646
0.646
0.645
0.646
0.646
0.648
3.668
4.000
4.399
5.066
5.625
6.279
6.793
7.270
7.971
8.535
9.254
2.986
3.000
3.002
3.006
3.010
3.012
3.016
3.019
3.023
3.027
3.028
3.177
3.170
3.166
3.162
3.158
3.155
3.150
3.146
3.142
3.138
3.135
20
a3th a3exp
a3th
n100%
21
wA
DwA wo
22
wB
DwB wo
23
24
25
where wmg 1.31, wZn 1.65, wFe 1.83 and wO 3.44. Calculations
of Pa, Pb, a, b, DwA and DwB coefcients for the Mg1 xZnxFe2O4
ferrites using Eqs. (16)(25) are shown in Table 7.
It is clear that values of the ion packing factor Pa decrease more
strongly than Pb and the fulllment coefcient a values remain
almost constant with increasing Zn content. The small values
( o1) of Pa, Pb, a and the strong increase of the vacancy parameter,
b indicate the presence of cation or anion vacancies and the
domination of the Zn2 vacancies at the tetrahedral sites. The
electrical conductivity in ferrites was explained on the basis of the
Verwey mechanism, i.e. exchange of electrons between the
adjacent Fe2 and Fe3 ions that are distributed randomly over
the octahedral sites. Since the hopping mechanism is the most
probable conduction mechanism in the MgZn ferrites the presence of the Zn vacancies in the MgZn ferrites might be partially
responsible for the improvement of the electrical conductivity
803
4. Conclusions
The analysis of the X-ray diffraction spectrum showed that the
Mg1 xZnxFe2O4 system, which has been prepared by the conventional solid state reaction technique with double sintering at
temperatures around 1000 1C is pure single-phase ferrite system.
Values of the theoretically and experimentally calculated lattice
parameter, a, increase with Zn content in the sample. The
variation was nonlinear for the experimental values of a. With
the exception of the volume shrinkage, some bonds length and
grain sizes the other lattice parameters increase with increasing
Zn concentration. The estimated values agree quite well with
those predicted theoretically. The EDS, SEM and TEM analysis of
the surface of a solid piece showed the existence of aggregates
of stacked nearly rounded to cubic crystallites of about
(200800) nm in diameter. The infrared spectra of these ferrites
give rise to two most prominent absorption envelopes. The high
frequency band, n1, lies in the range between 564 and 571 cm 1
was assigned to the Fe3 O2 and Zn2 O2 stretching vibrations at the tetrahedral sites. The second main absorption band,
n2, is present in the range between 432 and 447 cm 1, which is
assigned to the Fe3 O2 stretching vibrations at the octahedral
sites. The absorption bands n1 and n2 revealed the formation of
single-phase spinel structure with two sublattices: the tetrahedral (A) and octahedral (B) sites. These results showed that the
normal mode of vibration of tetrahedral clusters is higher (shorter
bond length) than that of octahedral clusters (longer bond
length). Calculated values of the bond lengths RA and RB and ionic
radii rA and rB support this interpretation. The force constants of
the tetrahedral site, Kt, decrease and the octahedral site, Ko,
increase with increase in Zn content x. This behavior has been
attributed to the variation in cationoxygen bond length and the
charge imbalance at the concerned sites. We can conclude that
the gradual increase of the Zn content, x, in the studied
Mg1 xZnxFe2O4 system leads to gradual transformation from the
inverse to normal spinel structure. The system transfer from an
almost inverse spinel MgFe2O4 (x0) to normal spinel ZnFe2O4
(x 1.0) leads to sharpening of the absorption bands. The room
temperature electrical resistivity is of order of (108109)O-cm.
The increase (decrease) of Zn (Mg) content lowers (raises) the
804
Acknowledgment
One of us (Kadhim Ahmed) would like to thank Dr. C.B. Kolekar
for useful comments.
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a r t i c l e i n f o
abstract
Article history:
Received 25 April 2012
Received in revised form
11 October 2012
Available online 26 October 2012
In this study, MgZn ferrite with the chemical formula of Mg0.6Zn0.4Fe2O4 is synthesized through a
modied combustion synthesis using glycine as fuel and metal (Mg, Zn and Fe) nitrates as reactants.
The technique, known as glycine-nitrate process, involves exothermic decomposition of a viscous
liquid, prepared by thermal dehydration of an aqueous solution containing metal nitrates and glycine.
The product powders produced at seven different molar ratios of glycine to nitrate (G/N ratio), varying
from 0.37 to 0.75, are agglomerates of ne particles whose typical diameter are several tens of
nanometers. Thermodynamic modeling of the combustion reaction indicates that as the fuel-to-oxidant
ratio increases, the amount of gases produced and the adiabatic ame temperature rise. X-ray
diffraction shows that samples crystallize in a spinel-type structure in all reactions. The morphology
of the powders is examined using eld emission scanning electron microscopy and transmission
electron microscopy. Through magnetic measurements conducted by a vibrating sample magnetometer, the maximum saturation magnetization (46 emu/g) is found to occur at the highest G/N ratio.
& 2012 Elsevier B.V. All rights reserved.
Keywords:
Glycine-nitrate process
Combustion synthesis
MgZn ferrite
Magnetic properties
Nanocrystalline
1. Introduction
Soft ferrites constitute an important class of magnetic materials which has attracted much interest in many elds [1,2]. They
have been the subject of extensive research owing to their wide
range of applications such as those in hyperthermia, information
storage systems, gas sensors, microwave devices, magnetic
recording media, electronic industries, humidity sensors and
green anode materials [16].
Zn-substituted ferrites exhibit very noticeable magnetic properties that have especially captured the attention of specialists for
high-frequency applications [7]. Mg1 xZnxFe2O4 series, commercially known as Ferrocube-Z, is customarily used as ferrite core
where effective coupling between an electrical current and
magnetic ux is required [4]. MgZn ferrite, with its wide usage
in power transformers, microwave devices and telecommunication is usually considered a favorable choice in the industry. High
resistivity, low coercivity and inappreciable eddy current loss
contribute to this favorability and are the reasons why MgZn
ferrite is capable of being utilized as a soft-magnetic material [2].
In order to form these ne spinel-type ferrite particles, various
wet methods have been devised including freeze-drying, spray-
n
Corresponding author at: Department of Materials, Faculty of Engineering,
Semnan University, Semnan, Iran. Tel.: 98 9365281698; fax: 98 21 88521951.
E-mail address: sadeghhajarpour@hotmail.com (S. Hajarpour).
0304-8853/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jmmm.2012.10.023
S. Hajarpour et al. / Journal of Magnetism and Magnetic Materials 329 (2013) 165169
the glycine-to-nitrate ion (G/N) ratio, which affects ame temperature, combustion rate, and product morphology and composition. The peak ame temperature is reported to be typically
obtained at a G/N ratio that corresponds to complete combustion,
producing H2O, CO2, and N2 as waste gases, with no atmospheric
oxygen required. The G/N ratio that corresponds to complete
combustion is referred to as the stoichiometric ratio [1,13,16].
There have been a limited number of reports on preparation
of spinel-type ferrites by GNP. This paper is a study of the
synthesis and properties of zinc-substituted spinel-type ferrite
Mg0.6Zn0.4Fe2O4, produced by GNP, at different G/N molar ratios
varying from 0.37 to 0.75. The effect of G/N ratio on morphology,
crystal structure, and magnetic properties is also examined.
2. Experimental procedure
DH0r DH0p
Cp
2500
Adiabatic flame temperature (C)
40
35
2000
30
25
1500
20
1000
500
15
Adiabatic flame temperature
Mole of gases evolved
0
0.35
10
166
5
0
0.45
0.55
0.65
0.75
Glycine to nitrate molar ratio
S. Hajarpour et al. / Journal of Magnetism and Magnetic Materials 329 (2013) 165169
Table 1
Enthalpy of formation and specic heat for the combustion synthesis of MgZn
ferrite.
Compound
DHf1 (kJ/mol)
Cp (kJ/mol K)
Mg(NO3)2
Zn(NO3)2
Fe(NO3)3
NH2CH2COOH
ZnFe2O4
CO2
H2O
N2
O2
790.1
482
671
528
1179.1
395
243
0.148
0.061
0.051
0.024
0.039
Intensity (a.u.)
(222)
(400)
(422) (511)
G/N ratio
D (nm)
a (A)
dx (g/cm3)
0.37
0.43
0.5
0.55
0.62
0.68
0.75
12.86
30.36
46.70
39.18
46.52
31.25
39.75
8.412
8.424
8.430
8.430
8.424
8.424
8.413
4.829
4.808
4.798
4.798
4.808
4.808
4.827
(220)
(111)
Table 2
Crystallite size (D), lattice parameter (a) and X-ray density (dx) of Mg0.6Zn0.4Fe2O4.
8.435
(311)
G/N = 0.75
(440)
G/N = 0.68
G/N = 0.62
G/N = 0.55
8.43
8.425
8.42
8.415
G/N = 0.5
8.41
0.35
G/N = 0.43
G/N= 0.37
15
25
35
45
2 Theta (degree)
55
167
65
0.45
0.55
0.65
Glycine to nitrate molar ratio
0.75
However, the actual ame temperatures are much lower than the
theoretically calculated values owing to radioactive losses, incomplete combustion, and heating of air [12,16].
3.2. Characterization
l h2 k2 l2 2
2
sin y
1
DXRD
kl
bcos y
dx
ZM
Na3
168
S. Hajarpour et al. / Journal of Magnetism and Magnetic Materials 329 (2013) 165169
Fig. 4. FESEM and TEM photomicrographs of Mg0.6Zn0.4Fe2O4 produced by fuel-rich reaction (G/N 0.75): (a) FESEM, low magnication and (b) TEM, high magnication.
Table 3
Hysteresis loss, saturation magnetization (Ms), coercive force (Hc) and remanent
magnetization (Mr) of Mg0.6Zn0.4Fe2O4.
G/N ratio
Ms (emu/g)
Hc (Oe)
Mr (emu/g)
0.37
0.43
0.5
0.55
0.62
0.68
0.75
1523
3778
6834
11861
9310
7250
9013
24.91
40.50
42.49
44.44
40.63
44.05
46.61
18.56
45.06
68.50
74.34
82.06
81.47
77.54
1.28
5.02
6.79
8.29
7.37
7.79
8.69
90
Saturation magnetization
(emu/g)
60
50
80
70
60
50
40
30
20
10
40
0
0.35
30
20
0.45
0.55
0.65
Glycine to nitrate molar ratio
0.75
10
0
0.35
0.45
0.55
0.65
Glycine to nitrate molar ratio
0.75
P c /KS
Ms
S. Hajarpour et al. / Journal of Magnetism and Magnetic Materials 329 (2013) 165169
v2 D6 K 41
A3
4. Conclusions
A simple chemical process has been devised for producing
nanocrystalline MgZn ferrite powders using glycine as fuel and
metal nitrates as oxidant with different glycine to nitrate molar
ratios. It has been observed that the fuel-to-oxidant ratio bears a
signicant inuence on characteristics of the produced powder.
Thermodynamic modeling of the combustion reaction shows that
the amount of gas production and adiabatic ame temperature
are in direct relationship with G/N ratio. The main conclusions of
the work are listed below.
Acknowledgements
169
University of Mining and Metallurgy, Faculty of Materials Science and Ceramics, al. Mickiewicza 30, 30-059 Cracow, Poland
b
LG.Philips Displays Poland, ul. Zwierzyniecka 2, 96-100 Skierniewice, Poland
Abstract
This paper presents results of investigations on property changes of MgZn ferrite used commercially for deection yoke cores
sintered at temperatures ranging from 900 to 1400 C. Physical and mechanical properties were determined: apparent density,
strength, elastic properties. The most important magnetic properties as initial permeability, coercivity, saturation magnetic ux,
retentivity and Curie point temperature were determined. Microstructure evolution during sintering was observed and compared
with changes of mechanical and magnetic properties as well as electrical conductivity. Presented results could be helpful in
optimisation of ferrite heat-treatment conditions.
# 2003 Elsevier Ltd. All rights reserved.
Keywords: Ferrites
1. Introduction
From the early days of ferrites commercial application as a TV deection yoke MnZn ferrites were the
material of choice. These materials connected good
magnetic properties with low production costs. Introduction of High Denition Television (HDTV) changed
the situation. Signicant increase in horizontal grids
meant that ferrite material had to be eective at a higher
frequency. It means that ferrite used in HDTV application should have higher resistivity than the MnZn
one ( 102 .cm).1 Mentioned problem could be solved
with the utilization of MgZn ferrite. Although, the
most of magnetic parameters are better for MnZn
ferrites, the decisive parameter is resistivity much
higher for MgZn materials ( 106107 .cm). Processing of MgZn ferrites should be provided with care on
their densication, microstructure and mechanical
properties to assure possible high values of magnetic
properties.
The present work shows the results of investigation
on inuence of sintering conditions of commercially
utilised MgZn ferrite powder on product properties.
* Corresponding author. Tel.: + 48-12617-2397; fax: +48-126334630.
E-mail address: pedzich@uci.agh.edu.pl (Z. Pedzich).
0955-2219/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0955-2219(03)00386-8
The aim of the research was to optimise manufacturing of ferrite with suitable magnetic properties
accompanied with as good as possible mechanical
properties.
2. Experimental
All investigation, conducted in the presented work,
based on commercially utilized by LG.Philips Displays
Poland MgZn ferrite powder (containing a small
amount of Mn). This powder mixed with plastiers was
uniaxial pressed under 50 MPa. Samples in O-ring
shape were sintered in a furnace with Superkanthal 1900
heating elements in air atmosphere. The maximum sintering temperature ranged from 900 to 1400 C with
100 C steps. The heating rate was 10 C/min. The
soaking time at maximum temperature was 2 h in each
case.
Apparent density () and water wetability (W) of sintered samples were determined by the Archimedian
method. The strength of sintered bodies was estimated
by diagonal compression tests of O-rings. The destructive compression stresses ( u) were calculated utilizing
Frochts formulas:2
u P K=D-2dh
1054
Table 1
Results of densication parameters (, W), ultrasonic wave propagation velocity measurements (vL, vT), strength estimation of O-ring samples ( u)
and grain size changes (M,sM) for all sintered samples
Sintering
conditions
Apparent
density
(, g/cm3)
Wetability,
W(%)
Longitudinal
ultrasonic wave
velocity, vL (m/s)
Transverse
ultrasonic wave
velocity, vT (m/s)
Destructive
compressive
stress, u (MPa)
Mean grain
size, M (mm)
Mean grain
size deviation,
sM (mm)
Starting powder
900 C
1000 C
1100 C
1200 C
1300 C
1400 C
2.570.2a
3.100.2
4.070.2
4.460.1
4.460.1
4.480.1
17.2 0.3
10.5 0.3
2.7 0.3
0
0
0
2260.819.7
3885.418.0
6297.642.3
7127.8115.6
7181.9112.9
7250.292.6
1344.237.8
2375.730.8
3572.710.5
3864.832.5
3882.020.2
3914.825.9
0.750.07
3.180.46
9.480.82
12.082.10
10.941.31
6.790.39
0.5
0.5
1.0
1.4
4.1
10.6
16.9
0.21.0b
0.52.5b
0.6
2.1
5.5
8.3
a
b
where: P is a load at destruction moment; K the coecient of stress concentration (assumed in our calculations as (1); D, d and h are the external diameter,
internal diameter and height of the ring, respectively.
Tests were performed using ZWICK 1435 apparatus.
The microstructural analyses of sintered bodies
encompass SEM (Philips XL30) and optical microscopy
(Nikon Ephipot 300) observations of polished sample
surfaces after chemical etching. The microstructural
parameters as a mean grain size (M) and mean grain
size deviation (sM) were determined by Saltykovs
method.3
The X-ray diraction patterns analysis (Seifert
XRD7) was helpful in phase identication and calculation of unit cell parameter values for ferrite powder and
sintered materials.
Electrical conductivity of samples was measured using
Hewlett Packard HP33501A multimeter at temperatures
ranged from 200 to 700 C.
Longitudinal (vL) and transverse (vT) ultrasonic waves
propagation velocity measurements were performed
with INCO (Poland) equipment.
The basic magnetic parameters as Curie temperature
(TC), initial permeability (i), coercivity (Hc), saturation
magnetic ux (Bsat) and retentivity (Br) were determined
using dynamic methods.
3. Results
Table 1 summarized densication parameters (,W),
ultrasonic wave propagation velocity measurements
results (vL, vT), strength estimation of O-ring samples
( u) and grain size parameters (M,sM) for all sintered
bodies. Samples sintered at temperatures ranging from
1200 C and higher shows no wetability. Their apparent density is practically stable. In samples sintered at
lower temperatures signicant porosity can strongly
inuence measured properties (mechanical, elastic and
magnetic).
changes are the most probably due to the various occupation of cation positions in the spinel structure. The
iron and manganium cations valency changes
(Fe+2$Fe+3 and Mn+2$Mn+3) may cause the
cations to occupy dierent Wycko positions according
to their charge, a and d respectively.5
Description of microstructure evolution could be
completed with data included in Fig. 3, where the
cumulative curves of grain size distribution for materials
sintered at 11001400 C were plotted. These data show
that in samples sintered at 1300 and 1400 C an exaggerated grain growth occurred. Microstructures of the
mentioned ferrites are given in Fig. 4.
The basic magnetic property values are collected in
Table 2. The most suitable properties show materials
sintered at 1200 and 1300 C. They have the highest
values of initial permeability, saturation magnetic ux
and retentivity. The coercivity of these materials is the
lowest among investigated materials.
The measurement of electrical resistance as a function
of temperature allows us to calculate conductivity of the
1055
1056
Table 2
Basic magnetic properties of investigated samples
Sintering
conditions
Initial
permeability,
I, (mT)
Coercivity,
Hc, (Am)
Saturation
magnetic ux,
Bsat, (mT)
Retentivity,
Br, (mT)
Curie
temperature,
TC ( C)
900 C
1000 C
1100 C
1200 C
1300 C
1400 C
13
43
215
467
569
549
252
104
36
23
21
25
88
203
234
248
246
6.3
59
163
175
173
148
136
141
141
142
145
151
References
4. Summary
A concise characteristic of dierent ferrite properties
as a function of sintering temperature given above
shows that denition of the optimal method of ferrite
heat-treatment requires the reconciling of opposing
tendencies in temperature dependence of individual
properties.
ARTICLE IN PRESS
Abstract
Nanocrystalline MgZn-ferrite is prepared by ball milling the stoichiometric powder mixture of MgO, ZnO and a-Fe2O3. A nonstoichiometric ferrite phase is noticed to form after 3 h of milling when particles of starting materials became nano-sized. After 25 h of
milling, stoichiometric ferrite phase is formed with 9 nm particle size. Post annealing study of ball-milled sample reveals that the
nanocrystalline ferrite phase is stable up to 873 K and then starts to decompose into individual starting phases. However, heat treatment
of unmilled stoichiometric powder mixture even at 1473 K for 1 h duration does not result in formation of stoichiometric MgZn-ferrite
phase.
r 2006 Published by Elsevier B.V.
PACS: 61.72.y; 75.50.Gg; 75.50.Tt; 81.40.Lm
Keywords: (Mg,Zn) nanoferrite; XRD; Ball milling; Post-annealing
Corresponding author. Tel.: +91 342 2557282; fax: +91 342 2530452.
ARTICLE IN PRESS
M. Sinha et al. / Physica E 33 (2006) 367369
368
(101)
(220)
(202)
(111)
14000
(102)
(024)
(012)
16000
(116)
(110)
(018)
(214) (220)
(103)
(300)
(200)
(112)
(201)
(1 0 10)
ZnO
MgO
(Mg,Zn) Fe2O4
(113)
(200)
18000
Fe2O3
(100)
(104)
(002) (110)
20000
(PURE)
12000
3H
10000
8H
12H
8000
20H
20
30
40
50
60
(533)
(440)
(511)
(400)
(222)
(311)
(220)
6000
(111)
25H
70
80
2 (degree)
Fig. 1. X-ray powder diffraction patterns of unmilled and ball-milled
MgOZnOa-Fe2O3 mixture powders. The peak positions of different
phases are marked in the gure.
ARTICLE IN PRESS
(101)
(300)
(103)
(200)
(112)
(201)
(1 0 10)
(116)
(102)
(024)
(220)
(110)
ZnO
MgO
(Mg,Zn) Fe2O4
(018)
(111)
Intensity (arb.unit)
12000
PURE
10000
8H
8000
20H
References
25H
20
30
40
50
2 (degree)
(533)
(440)
(511)
(422)
(400)
(311)
(222)
(111)
(220)
6000
60
70
80
(311)
28000
(Mg,Zn)Fe2O4
26000
MgO
ZnO
24000
(220)
(620)
(533)
(622)
(444)
(440)
(422)
(200)
(400)
PURE
(102)
14000
(100)
(002)
(101)
(111)
(222)
18000
(111)
Intensity (arb.unit)
20000
(511)
(220)
22000
16000
369
Fe2O3
(113)
(200)
(012)
(100)
14000
(002) (110)
(104)
12000
8H
10000
20H
8000
25H
6000
4000
20
30
40
50
60
70
80
2 (degree)
Fig. 3. X-ray powder diffraction patterns of unmilled and ball-milled
MgOZnOa-Fe2O3 mixture milled for different times and annealed at
1473 K temperature for 1 h duration.
Wet chemical synthesis and gas sensing properties of magnesium zinc ferrite
nano-particles
D.C. Bharti, K. Mukherjee, S.B. Majumder
Materials Science Center, Indian Institute of Technology, Kharagpur 721302, West Bengal, India
a r t i c l e
i n f o
Article history:
Received 22 June 2009
Received in revised form
25 November 2009
Accepted 28 November 2009
Keywords:
Semiconducting oxide
Solgel growth
X-ray diffraction
Adsorption
a b s t r a c t
In the present work we have synthesized, magnesium ferrite, zinc ferrite, and magnesium zinc ferrite solid
solutions using an economic wet chemical synthesis route. To understand the phase formation behavior of
the synthesized powders, infra-red spectroscopy in conjunction with X-ray Rietveld renement analyses
has been performed. The structural characteristics of these ferrite powders are correlated with their
room temperature magnetic properties. Phase pure, low temperature synthesized magnesium zinc ferrite
nano-particles are investigated in terms of carbon monoxide and hydrogen gas sensing properties. The
response and recovery transients of conductance are modeled using Langmuir adsorption kinetics with
two active sites in the sensing elements used as CO sensors. For these two adsorption sites the activation
energies for response and recovery behavior, estimated from the temperature dependence of respective
time constants are found to be different. The difference in respective activation energies for response as
well as recovery is thought to be due to different chemi-adsorbed oxygen species in these two sites.
2009 Elsevier B.V. All rights reserved.
1. Introduction
Cubic spinel ferrites are one of the most attractive materials for
magnetic, catalysis, micro-electronic, as well as gas sensing applications [15]. The magnetic cations in cubic spinel lattice occupy A
(divalent, tetrahedrally coordinated with oxygen) and B (trivalent,
octahedrally coordinated with oxygen) types of crystallographic
positions. In this type of materials, ferrimagnetisms may result
from stronger AB antiferromagnetic interaction than the BB antiferromagnetic interaction. Magnesium ferrite (MgFe2 O4 (MFO)),
zinc ferrite (ZnFe2 O4 (ZFO)) and the solid solutions between these
two crystallize into cubic spinel structure and have several important technological applications. The cation distribution in MFO is
predominantly inverse whereas ZFO crystallizes in normal spinel
structure. The reported magnetic properties of these materials are
scattered and strongly depend on their synthesis routes. As for
example, for MFO powders prepared by high energy ball mill, secondary phase formation (e.g. MgO, Fe2 O3 ) as well as cation mixing
(inverse or mixed) is reported to be related to the milling time
[6]. In mechano-chemical synthesis too the co-existence of Fe2 O3
with MFO is related to milling time [7]. MFO prepared using double hydroxide precursor have secondary MgO co-existed with MFO
[8]. Efforts have been made to correlate magnetic properties with
secondary phase contents; microstructure and compositional heterogeneity.
From several recent literatures it is apparent that in nanocrystalline form, the properties of these ferrite materials are very
different from their bulk counterpart. As for example, below a critical particle size MFO exhibits super-paramagnetic behavior at room
temperature [9]. Since Mg2+ is diamagnetic, a weaker coupling
between Fe3+ cations reduces the anisotropic energy in MFO which
also yield super-paramagnetism at room temperature. These ultrane super-paramagnetic particles may have several applications
viz. as magnetic resonance imaging contrast agents, in ferro-uid
based technology, also in high density information storage device,
etc. Nano-crystalline ferrite particles have also reported to exhibit
superior gas sensing properties than their bulk counterpart [10].
Interestingly, some of these ferrite particles also exhibit distinct
selectivity for a specic gas in a gas mixture [11].
In the present work we have synthesized (Mg1x Znx )Fe2 O4
(0.0 x 1.0) solid solution particles using a simple, economic wet
chemical synthesis route. These powders are calcined in a temperature range between 300 and 900 C. The phase formation behavior
of MgFe2 O4 , ZnFe2 O4 and (Mg1x Znx )Fe2 O4 solid solution powders calcined at different temperatures are studied systematically
using Rietveld renement of the X-ray diffractograms. The morphology as well as room temperature magnetic properties of these
calcined powders are characterized using transmission electron
microscope (TEM) and a vibrating sample magnetometer vibrating
sample magnetometer (VSM).
We have also investigated the hydrogen and carbon monoxide
sensing performance of the low temperature synthesized phase
pure (Mg0.5 Zn0.5 )Fe2 O4 particles. The synthesized particles are
lightly pressed and sintered at low temperature in order to achieve
510
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
2. Experimental
Nano-crystalline magnesium zinc ferrite powders are prepared using a wet
chemical synthesis route using hydrated magnesium acetate (Mg(CH3 COO)2 2H2 O),
hydrated zinc acetate (Zn(CH3 COO)2 2H2 O) and iron nitrate (Fe(NO3 )3 9H2 O) as precursor materials. For the powder synthesis, stoichiometric precursor materials of
Mg, Zn and Fe cations are dissolved in hot acetic acid through continuous stirring.
Poly-vinyl alcohol (PVA) solution (2%) is added into the mixed precursor solution
(in 1:0.25 volume ratio) and the resultant precursor is repeatedly heated 80 C and
cooled in an ice bath to yield a gelled mass. The gel is dried in a vacuum oven kept
about 80 C overnight to form powder. The resultant powder, termed as dried powder, is crushed in a mortar pestle and calcined in a two step heat treatment schedule.
In the rst step, the powders are red at 400 C for 1 h for the removal associated
organics followed by a second step calcination in a temperature range between 600
and 900 C for 2 h. The powders prepared below 400 C are calcined in a one step
heat treatment process in respective temperature for 2 h for crystallization.
The phase formation behavior of the calcined powders are studied using Fourier
transformed infra-red (FTIR) spectroscopy and X-ray diffraction analyses. A transmission electron microscope (TEM) is used to study the microstructure evolution.
The room temperature measured magnetic properties of the synthesized powder is
characterized using a VSM. The synthesized powders are mixed with few drops of
10% PVA solution as binder and pressed in the form of thin circular discs (12 mm
diameter 0.1 mm thick) using a hydraulic press. The pellets are heated at 600 C
for 2 h in air. The above heat treatment ensures minimal particle growth, necking
between particles, sufcient handling strength and porous nature of the sensing element. The sintered pellets are polished on a velvet cloth and cleaned ultrasonically
for 2 min each in acetone followed by water and absolute alcohol. For the electrical
measurements, one of the surfaces of the sensing elements are sputter coated with
planar gold stripes of 7 mm length, 3 mm wide and separated from each other by
4 mm. The sensing element is placed in a reactor equipped with pressure contact
probes and heater assembly with precise temperature control. For gas sensing studies hydrogen and carbon monoxide gas diluted in N2 (10,000 ppm) and compressed
air (95%+ purity) is used as test and carrier gas, respectively. The ow rates of test
(dVtest /dt) as well as carrier gas (dVcarrier /dt) are controlled by mass ow controllers
interfaced with a PC. Both test and carrier gas with controlled ow rate is fed to
the reactor through a home made mixing unit. During the sensing measurements
continuous ow of test as well as carrier gas is maintained through the reactor to
the exhaust line of it. The concentration of the mixed gas (Cmixed gas ) in the reactor is
calculated using the following relation:
Cmixed gas =
(1)
S=
Ra Rg
Ra
100
(2)
rt2 + K0
r02
(3)
where Kt and Ko are the force constants associated with unit displacement of the CT O and Co O bonds, and rt and r0 represents
the corresponding components of displacement from equilibrium
in the direction of the appropriate bond. From the measured 1 and
2 frequencies the force constants for the tetrahedral and octahedral cations can be determined [15]. If more than one type of cation
is present in the respective sites, the effective mass (summation
of the product of respective masses and their weight fraction) will
inuence the force constant which eventually leads to the shift of
the tetrahedral and octahedral frequencies. Therefore, the shift of
the frequencies is related to the cation distribution in the tetrahedral and octahedral sites. Finally, depending on the distribution of
the cations the cationoxygen bond lengths in the tetrahedral and
octahedral sites will be changed.
We have recorded the FTIR spectra of as prepared as well as calcined MFO and ZFO powders at different temperatures (not shown).
Two important features are apparent from these gures, rst: the
mode frequencies for tetrahedral cation/(s) are invariant to the calcination temperature and second the width of the absorption mode
decreases with the increase in calcination temperature. The atomic
weight of Mg, Zn, and Fe are 24.31, 65.37, and 55.84. Therefore, any
change of their fractional contents in A (tetrahedral) or B (octahedral) sites would change the values of 1 and 2 appreciably.
However, both for MFO and ZFO it is observed that the mode frequencies for tetrahedral sites (1 ) are invariant to the calcination
temperature; therefore, it seems that the cation distribution does
not alter with calcination temperature in both powders. The second
observation indicates that the crystallinity of MFO/ZFO powders
improves with the increase in calcination temperature. Similar to
that for the end members MFO and ZFO, for all their solid solution
compositions, we have observed that the mode frequency due to
tetrahedral bond does not shift appreciably with calcination temperature. As observed also in case of the end members MFO and
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
511
Fig. 1. X-ray diffractograms of Mg1x Znx Fe2.0 O4 (0.0 x 1.0) powders calcined in the temperature range of 300900 C for 2 h in air.
ZFO, this indicates that cation occupancy in tetrahedral and octahedral site is invariant to the calcination temperature. However,
interesting variation of the mode frequency is observed when we
compare FTIR spectra of the solid solutions calcined at identical
temperatures. Thus, Fig. 2 shows the FTIR spectra of MZFO powders calcined at 900 C. Note that as the Zn contents in the solid
solution are increased the tetrahedral mode frequency is shifted
to lower wave number. This is expected as Zn has higher atomic
mass as compared to Mg ion in a specic crystallographic lattice
site.
512
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
Table 1
Rened structural and microstructural parameters of magnesium Ferrite powders
calcined at 300 C for 2 h.
Magnesium ferrite MgFe2 O4 (MFO)
Phase/(s) present (SG)
MFO cubic spinel (Fd-3m) 82 wt%
MgO cubic (Fm-3m) 18 wt%
Calcination temperature 300 C
Rened parameters (MFO)
Lattice parameter () 8.38 (0.0014)
Rms microstrain 0.0017%
Crystallite size (nm) 81.7 (2.09)
Density (gm cm3 ) 4.49 gm cm3
Rened parameters (MgO)
Lattice parameter () 4.23 (0.0011)
Crystallite size (nm) 145 (9.9)
Rened composition
(Mg0.14 Fe0.86 )T (Mg0.86 Fe1.14 )O O4
Statistical parameters
RWp 5.6%
RP 4.87%
Rwbp 4.47%
Rpb 4.23%
Table 3
Rened structural and microstructural parameters of ZFO powders calcined at 300 C
for 2 h.
Zinc ferrite ZnFe2 O4 (ZFO)
Rened composition
Phase/(s) present (SG)
(Zn0.92 Fe0.08 )T (Zn0.08 Fe1.92 )O O4
ZFO cubic spinel (Fd-3m) 93 wt%
Statistical parameters
ZnO cubic (P63mc) 7 wt%
RWp 6.93%
RP 5.15%
Calcination temperature 300 C
Rened parameters (ZFO)
Rwbp 8.55%
Lattice parameter () 8.43 (0.0014)
Rpb 6.54%
Rms microstrain 0.0085%
Crystallite size (nm) 38.0 (0.69)
Density (gm cm3 ) 5.37 gm cm3
Rened parameters (ZnO)
Lattice parameter () a = 3.25 (0.0011), c = 5.20
Crystallite size (nm) 100 (9.9)
Atom
(2 )
Atomic coordinates
MgT
FeT
MgO
FeO
O
0.125
0.125
0.5
0.5
0.255
0.125
0.125
0.5
0.5
0.255
0.125
0.125
0.5
0.5
0.255
1.21
1.21
0.37
0.37
0.713
Atom
(2 )
ZnT
FeT
ZnO
FeO
O
0.125
0.125
0.5
0.5
0.255
0.125
0.125
0.5
0.5
0.255
0.125
0.125
0.5
0.5
0.255
0.68
0.68
0.68
0.68
0.67
Table 2
Rened structural and microstructural parameters of MZFO (50:50) calcined at 300 C for 2 h.
Magnesium zinc ferrite (Mg0.5 Zn0.5 )Fe2 O4
Phase/(s) present (SG)
Cubic spinel (Fd-3m) 100 wt%
Calcination temperature 300 C
Rened parameters
Lattice parameter () 8.42 (0.0064)
Rms microstrain 0.0007%
Crystallite size (nm) 11.1 (0.143)
Density (gm cm3 ) 4.89 gm cm3
Statistical parameters
RW 5.04%
Rwnb 4.81%
R 4.05%
Rnb 4.23%
Rened composition
(Mg0.04 Zn0.46 Fe0.50 )T (Mg0.46 Zn0.04 Fe1.50 )O O4
Atom
(2 )
MgT
ZnT
FeT
MgO
ZnO
FeO
O
0.125
0.125
0.125
0.5
0.5
0.5
0.2555
0.125
0.125
0.125
0.5
0.5
0.5
0.2555
0.125
0.125
0.125
0.5
0.5
0.5
0.2555
1.28
1.28
1.28
1.12
1.12
1.12
1.21
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
513
Fig. 3. X-ray Rietveld renement plot of Mg0.5 Zn0.5 Fe2.0 O4 powders calcined at
300 C for 2 h in air.
Fig. 2. FTIR spectra of Mg1x Znx Fe2.0 O4 (0.0 x 1.0) powders calcined at 900 C for
2 h in air.
Fig. 4. Variation of the lattice parameter of Mg1x Znx Fe2.0 O4 (0.0 x 1.0) powders
calcined at 300 and 900 C for 2 h in air.
514
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
Fig. 6. The resistance transient of Mg0.5 Zn0.5 Fe2 O4 porous pellet in the presence
of different concentration of hydrogen gas, measured at an operating temperature
380 C.
behavior can also be explained using the depleted layer width (LD )
concept. For the semiconducting material the charge carrier concentration (n0 ) (and therefore the conductance) increases with the
increase in temperature. The relation between the depletion layer
width (LD ) with carrier concentration (n0 ) and response (S) is given
in Eqs. (4) and (5), respectively [18]
LD =
S=
Fig. 5. Room temperature magnetic hysteresis loops of Mg0.5 Zn0.5 Fe2.0 O4 powders
calcined at 300 and 900 C for 2 h in air.
the sensing element is switched back and forth between air and
test gas environment. The sensitivity is found to increase from
10% to 62% when the H2 concentration was increased from 100 to
1660 ppm. For a xed gas concentration (H2 /CO 1660 ppm), Fig. 7
shows the temperature dependent sensitivity of Mg0.5 Zn0.5 Fe2 O4
sensors. As shown in the gure, in case of CO sensing a maximum sensitivity (44%) is achieved at operating temperature about
320 C. However, in case of H2 sensing the sensitivity increases with
the operating temperature of the sensing element. The slope of S
vs. T, however, starts to decrease 350 C and as envisaged from
the gure, probably the sensitivity (S) would have a tendency to
decline beyond 380 C. Due to the limitation of the heating unit
we could not measure the sensitivity beyond 380 C. Several physical phenomena could be invoked to explain the observed behavior.
For example, such reduction of sensitivity at higher temperature
may be explained by the adsorptiondesorption principle. Thus the
enhancement of desorption rates at the sensor surface may lead to
the decreased sensitivity at higher temperature. Additionally, the
kT 1/2
0
n0 e2
n
LD
n0
(4)
(5)
where 0 is the static dielectric constant, n0 is the total carrier concentration, e is the carrier charge, k is the Boltzmann
constant, T is the absolute temperature, n is the change in
the carrier concentration. From these equations it is clear that
beyond a critical temperature, the sensitivity is reduced due to the
decrease in depletion layer width. Table 4 compares the H2 and
CO sensing characteristics of various cubic spinel ferrite reported
in recent literatures. Comparing these data, it is ascertained that
Mg0.5 Zn0.5 Fe2 O4 prepared by a simple economical wet chemical
synthesis route exhibit reasonably good CO and H2 sensing behavior.
The sensing mechanism for the reducing gases such as H2 (or
CO) involves the formation of electron accepting adsorbates on the
surface of ceramic oxides as described in several recent research
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
515
Table 4
H2 and CO sensing characteristics of various cubic spinel ferrites.
Composition
Synthesis route
Morphology
Measurement system
Sensor characteristics
Ref.
Topt ( C)
H2 (ppm)
CO (ppm)
ZnFe2 O4
CuFe2 O4
CuFe2 O4
ZnFe2 O4
CoFe2 O4
NiFe2 O4
CuFe2 O4
ZnFe2 O4
CdFe2 O4
MgFe2 O4
NiFe2 O4
BiFe0.6 Mn0.4 O3
CdFe2 O4
Molten salt
Solid state reaction
Thick lm
Powder
Dynamic
Static
250
332
45
20
200
1000
Chemical route
Thick lm
Dynamic
250400
40 (H2 )
40(CO)
NA
NA
Chemical route
Thick lm
Static
250400
40 (CO)
40 (H2 )
6000
6000
Chemical route
Solgel method
Coprecipitation
Pellet
Thick lm
Thick lm
Dynamic
Static
Static
400
300
350
Porous pellet
Dynamic
380
320
20 (H2 )
22 (CO)
25 (H2 )
25 (CO)
62 (H2 )
44 (CO)
200
1000
1660
1660
1000
1000
[19]
[20]
[21]
[22]
[23]
[24]
[25]
This work
Table 5
Fitted parameters for the response kinetics as a function of temperature at xed (1660 ppm) CO gas concentration.
response
Temperature ( C)
1
250
300
350
380
267.25
193.57
102.46
77.54
(s)
response
2
(s)
270.25
207.05
142.24
93.05
(6)
=
Ka Cgas
Ka Cgas + Kd
G0 (mho)
G1 (mho)
G2 (mho)
8.44e9
2.59e8
8.60e8
1.49e7
2.80e9
1.12e8
2.72e8
2.43e8
2.86e9
1.31e8
2.73e8
2.57e8
(7)
t
(8)
1
(9)
(10)
(11)
recovery
1
G(t)response = G0 + G1 1 exp
G(t)response = G0 + G1 1 exp
+ G2 1 exp
response
t
response
1
(12)
response
2
response
and 2
are the relaxation times for two differwhere 1
ent energetically different adsorption sites 1 and 2, respectively.
Similar to response the recovery is also found to t well assuming two energetically different adsorption sites using the following
equation
recovery
G(t)
G0
+ G1
exp
t
recovery
1
+ G2 exp
t
2 recovery
(13)
Table 6
Fitted parameters for the recovery kinetics as a function of temperature at xed (1660 ppm) CO gas concentration.
recovery
Temperature ( C)
1
250
300
350
380
124.92
115.69
103.25
94.35
(s)
recovery
2
124.92
120.68
112.14
105.65
(s)
G0 (mho)
G1 (mho)
G2 (mho)
9.26e9
2.66e8
8.76e8
1.66e7
2.17e9
1.35e8
2.43e8
1.82e8
2.18e9
1.33e8
2.68e8
1.88e8
516
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
Fig. 8. Conductance transient for response and recovery of Mg0.5 Zn0.5 Fe2 O4 sensors
for 500 ppm carbon monoxide measured at 300 C. The solid lines are calculated
using Eq. (12) (for response) and Eq. (13) (for recovery) (see text).
recovery
recovery
E + Q
A
(14)
2kT
E
D
(15)
2kT
response
response
Fig. 9. Plots of ln 1
and ln 2
as a function of 1000/T for Mg0.5 Zn0.5 Fe2 O4
gas sensor in presence of 1660 ppm CO gas.
In light of the above analyses, we are making an attempt to comment on the nature of site 1 and site 2 as the different adsorption
sites in the magnesium zinc ferrite sensing elements. Note that as
compared to site 2, site 1 always exhibits faster response as well
response
recovery
response
recovery
as recovery kinetics (1
, 1
< 2
, 2
). This in
turn indicates faster CO adsorption and CO2 molecule desorption
from site 1 as compared to that from site 2. Probably, the sensor
block has macro-porous region (between secondary particles) and
meso-porous regions (between primary particles i.e. crystallites)
[29], then gas diffusion in macro-porous region (molecular) will be
faster (lower ) as compared to that in meso-porous regions (Knudsen diffusion). Finally, the difference in the respective activation
energies for site 1 and 2 (as derived from response and recovery
kinetics) probably indicates different types of oxygen are chemiadsorbed in these two sites. Further research is required to clarify
these issues.
4. Conclusions
In the present work we have synthesized multifunctional magnesium ferrite, zinc ferrite and magnesium zinc ferrite solid
solution nano-powders using chemical solution synthesis route.
Through FTIR analyses in conjunction with XRD Rietveld renement it is found that at a temperature as low as 300 C, MgFe2 O4
crystallizes into a mixed spinel structure with the degree of inversion () 0.89. The degree of inversion is invariant to calcination
temperature. However, it is difcult to obtain phase pure MgFe2 O4
powders. The MgFe2 O4 powder calcined at a temperature as low
as 300 C exhibits ferrimagnetic behavior with remnant and saturation magnetization 7.01 and 38.45 emu g1 , respectively. Zinc
ferrite also crystallized into a mixed spinel structure, however, with
the degree of inversion () only 0.16 it can be considered as a
normal spinel. Similar to that of magnesium ferrite, the degree of
inversion is also found to be invariant to calcination temperature.
The measurement of magnetization vs. magnetic eld supports
paramagnetic ordering of zinc ferrite at room temperature. From
the FTIR analyses it is observed that the tetrahedral mode frequency is shifted to lower wave number with the increase of Zn
contents in Mg0.5 Zn0.5 Fe2 O4 solid solutions. This is expected as Zn
has higher atomic mass as compared to Mg ion in a specic crystallographic lattice site. The continuous range of the solid solution is
conrmed by systematic change in the lattice parameter as a function of Zn contents in MFO lattice. The Mg0.5 Zn0.5 Fe2 O4 powder
yields saturation magnetization 26 emu g1 .
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
The gas sensing performance of magnesium zinc ferrite is studied varying the carbon monoxide and hydrogen concentration in
the test gas (1001660 ppm) for various operating temperature (in
the range of 250380 C) of the sensing elements. It is argued that
for magnesium zinc ferrite sensors the chemi-adsorption of the
reducing gas and desorption of the reaction product (carbon dioxide
or water molecules) are the rate limiting processes for response and
recovery mechanisms, respectively. Through the analyses of conductance transients it is demonstrated that for the sensing of carbon
monoxide gas, both the sensor response and recovery behavior can
be modeled assuming a two site Langmuir adsorption kinetics. It
is found that for both the adsorption sites, at constant temperature T, Langmuir adsorption isotherm behavior is obeyed. For a
xed carbon monoxide concentration from the linear variance of
ln response vs. 1/T, the activation energies for the carbon monoxide
gas adsorption at two different adsorption sites are estimated to
be 0.57 eV (for site 1) and 0.46 eV (for site 2). Similar to response
kinetics ln recovery also follows a linear relationship with 1/T. The
activation energies for the desorption from site 1 and 2 are estimated to be 0.13 and 0.07 eV, respectively. Both for response and
recovery, the time constant for site 1 are faster than that for site
2. Similar to the response kinetics, for a xed temperature T, site 1
yields faster recovery than site 2. At lower temperatures, probably
the recovery trends for these two sites are reversed. Based on the
above ndings, nally it is argued that macro-porous regions of the
sensing elements are responsible to yield faster response as well as
recovery kinetics as compared to regions with meso-porous structures. The results are also indicative to the fact that the natures of
the chemi-absorbed oxygen species are also different in these two
different adsorption sites.
Acknowledgments
The above research work is partially supported by the research
grant from Department of Information Technology vide grant No.
20(7)2006-NANO. One of the authors (Mr. Kalisadhan Mukhejee)
also wishes to acknowledge the partial nancial support through
517
Electroceramics Group, Materials Science and Engineering Department, Shiraz University of Technology, 71555-313, Shiraz, Iran
Chemistry Department, School of Sciences, Shiraz University, Shiraz, Iran
c
Nanotechnology Research Center, Shiraz University, Shiraz, Iran.
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 1 June 2011
Received in revised form
31 December 2011
Available online 20 January 2012
Cobalt ferrite nanoparticles were synthesized by the chemical co-precipitation, normal micelles and
reverse micelles methods of iron and cobalt chlorides. X-ray diffraction analysis, Fourier Transform
Infrared (FTIR) and Vibrating Sample Magnetometer were carried out at room temperature to study the
structural and magnetic properties. X-ray patterns revealed the production of a broad single cubic
phase with the average particle sizes of 12 nm, 5 nm and 8 nm for co-precipitation, normal micelles
and reverse micelles methods, respectively. The FTIR measurements between 400 and 4000 cm 1
conrmed the intrinsic cation vibrations of spinel structure for each one of the three methods.
Moreover, the average particle sizes were lower than the single domain size (128 nm) and higher than
the super-paramagnetic size (23 nm) at room temperature. The results revealed that the magnetic
properties depend on the particle size and cation distribution, whereas the role of particle size is more
signicant.
& 2012 Elsevier B.V. All rights reserved.
Keywords:
Cobalt ferrite
Magnetic nanoparticle
X-ray diffraction
1. Introduction
Traditionally, magnetic materials have played a great number
of crucial roles in the daily life [1]. Among magnetic materials,
magnetic ceramics have been paid special attention due to
chemical stability as well as high electrical resistivity. One of
the most magnetic ceramics is spinel. According to the magnetic
theory, the most important spinels are oxides 2, 3 or MFe2O4 [2,3].
Among spinel ferrites, CoFe2O4 has received special attention
because of its large magneto-crystalline anisotropy, high coercivity, moderate saturation magnetization, large magneto-strictive
coefcient, chemical stability and mechanical hardness [4].
CoFe2O4 has an inverse spinel structure, where oxygen atoms
constitute an face center cubic (FCC) lattice and where half of the
Fe(III) ions occupies the tetrahedral A, site and where the other
half, together with Co(II) ions is located on the octahedral B site.
The different processing methods [57] inuence the particle size
and cation distributions between the A and B sites, as well as
the magnetic properties. The diameter of the nanoparticles is
much smaller than the critical single-domain diameter, thereby
avoiding the formation of the magnetic domain walls that
2. Experimental method
2.1. Materials
I. Shari et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 18541861
1855
1856
I. Shari et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 18541861
Fig. 1. (a) crystal structure of cobalt ferrite and XRD patterns of (b) co-precipitation, (c) normal micelles and (d) reverse micelles.
Table 1
Crystallite size, degree of crystallinity and Rietveld renement parameters.
Synthetic
method
Degree of
crystallinity
Crystallite
size (nm)
Rwp
Rp
w2
CNP
NNP
RNP
79.93
70.57
71.50
11.70
5.58
7.63
9.53
9.92
8.50
6.81
7.60
6.51
1.38
1.65
1.12
Table 2
Experimental lattice parameter (aexp), theoretical lattice parameter (ath), XRD
crystallite size (D), oxygen positional parameter (1/4,1/4,1/4) (U3m), oxygen
positional parameter (3/8,3/8,3/8) (u).
Synthetic Formula
method
CNP
NNP
RNP
Fig. 2. Conguration of the ion pairs in spinel ferrites with favorable distances and
angles.
aexp
(nm)
ath
(nm)
A
B
Fe30:84
Co20:84
Fe31:16
O4 0.8403 0.8402 0.2614
Co20:16
A
B
Fe30:99
Co20:99
Fe31:01
O4 0.8391 0.8399 0.2603
Co20:01
Co2 Fe3 A Co2 Fe3 B O4 0.8401 0.8401 0.2611
0:12
0:88
0:88
1:12
0.3830
0.3832
0.3831
A
B
these two sites can be expressed as:Co2x Fe31x
Co21x
Fe31
x O4 ,
where the square practices contain the ions on the octahedral
I. Shari et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 18541861
r B 12
r 2Co
1xr 3Fe
M e O
M e Me
b a=421=2
p a5=8u
q au1=43
c a=8111=2
r au1=8111=2
d a=431=2
s a1=3u 1=831=2
e 3a=831=2
f a=461=2
p
RA a 3 u14 RO
1=2
RO
RB a 3u2 2:75u 43
64
The
where RO is the radius of the oxygen ions (R1.32 A).
agreement between ath and aexp (Table 2) achieved from X-ray
data indirectly conrms the cation distribution deduced from
X-ray intensity calculations. The small deviation between ath and
aexp may be due to the presence of some ferrous ions Fe(II)
(r2Fe 0.078 nm) on octahedral sites with larger radii than Fe(III)
(r3Fe 0.0645 nm) [24]. The oxygen, positional parameter and
anion parameter (u) for each composition were calculated using
the formula:
3m
1=2
h
i
1xr 2Co
1 xr 3Fe
1857
2R2 2
where R BO=AO.
Table 3 shows the average ionic radius per molecule of the
octahedral and tetrahedral sites (rA and rB), tetrahedral site radius
(Rt), octahedral site radius (Ro), ionic radii(r), tetrahedral edge
(Edt), shared octahedral edge (Edso), unshared octahedral edge
(Eduo) and average bond lengths, (AO and BO), /rMe r(O 2)S.
The highest value of BO length in the normal micelles methods
can be explained by the highest Co(II) ( 0.0745 nm ) occupancy
with a higher ionic radius, as compared to Fe(III) (0.0645 nm) [25].
Both Tables 4 and 5 list the inter-ionic distances and bond
angles [25,26] for cobalt ferrite, which were calculated by use of
the experimental values of crystallographic parameters based on
the Eq. (5). These parameters are necessary to give full description
of the crystallographic structure, and they are also in connection
with the magnetic properties. In order to explain this connection
in the normal micelles method the Fe(III) (5 mB) concentration of
the A site is higher than that of the B site, or the Co(II) (3 mB)
of the A site is lower than that of the B site, the magnetic
y1
y2
y3
y4
y5
CNP
NNP
RNP
122.690
122.636
122.658
142.150
142.348
142.181
93.879
93.965
93.930
126.144
126.175
126.155
72.744
72.603
72.661
Table 3
Tetrahedral site radius (Rt), octahedral site radius (Ro), ionic radii(r), tetrahedral edge (Edt), shared octahedral edge (Edso), unshared octahedral edge (Eduo), average bond
lengths(AO and BO).
Synthetic method
RA (nm)
RB (nm)
rA (nm)
rB(nm)
Edt (nm)
CNP
NNP
RNP
0.0616
0.0616
0.0617
0.0715
0.0711
0.0714
0.0662
0.0646
0.0657
7 0.0002 nm
0.0687
0.3162
0.0694
0.3163
0.0689
0.3164
Edso (nm)
Eduo (nm)
AO (nm)
BO (nm)
0.2776
0.2772
0.2776
0.2974
0.2970
0.2973
0.1982
0.1966
0.1977
0.2008
0.2014
0.2009
Table 4
Inter-ionic distances for CoFeO system.
Synthetic method
b (nm)
c (nm)
d (nm)
e (nm)
f (nm)
p (nm)
q (nm)
r (nm)
s (nm)
CNP
NNP
MNP
0.2971
0.2967
0.2970
0.3484
0.3479
0.3483
0.3638
0.3634
0.3638
0.5458
0.5450
0.5457
0.5146
0.5139
0.5144
0.2033
0.2029
0.2032
0.1936
0.1936
0.1937
0.3708
0.3708
0.3710
0.3678
0.3673
0.3677
1858
I. Shari et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 18541861
Table 6
Tetrahedral molecular weights (M1), band frequency (u1) and force constant (kt).
Synthesis method
M1 (kg) 10 3
u1 10 2 m 1
kt 102 (N/m)
CNP
NNP
RNP
56.36
55.88
56.23
594
609
594
1.515
1.579
1.512
Table 7
Saturation magnetization, coercivity, remanence, maximum magnetic eld and
canted layer thickness measured at 27 1C.
Synthetic method MS (emu/g) HC (Oe) Mr (emu/g) Hmax (kOe) tshell (nm)
CNP
NNP
RNP
58.4
12.6
29.4
286.0
23.7
25.2
12.45
0.17
0.84
18.0
18.4
17.6
0.74
0.80
0.87
I. Shari et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 18541861
1859
Table 8
Theoretical magnetization per unit chemical formula 9MA MB9 and predicted
magnetization for bulk status were compared with reference [33] (MS-b) and
measured magnetization for nanosized synthesized powders (MS-n).
Synthesis
method
MA
(mB)
MB
(mB)
9MA MB9
(mB)
MS-b
(emu/g)
MS-n
(emu/g)
CNP
NNP
RNP
4.670
4.980
4.752
8.330
8.020
8.248
3.660
3.040
3.496
87.2
72.5
83.3
58.4
12.6
29.4
3.3.2.1. Size effect. Below the critical single domain the particle
size of cobalt-ferrite (DC 128 nm) for three samples the
coercivity decreases as a result of a reduction in the particle
volume, strain size and magnetic anisotropy barrier to block the
ips of the magnetic moments. Based on the following
discussions, the coercivity is at the highest level for the
particles obtained from the co-precipitation route as result of
reducing in the particle volume, grain size and magnetic
anisotropy. According to the StonerWohlfarth theory [37], by
decreasing the particle size in the single domain region, KV
decreases based on Eq. (10)
EA KV sin2 y,
10
1860
I. Shari et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 18541861
PC K 41 D6
3
0 MS A
11
3.3.2.2. Cation distribution. There are some reasons that show the
difference in coercivity for nanoparticles obtained by the normal
and reverse micelle methods. In addition, the particle size can be
explained by the cation distributions. While quantum couplings
may not be the same on A and B sites with tetrahedral and
octahedral symmetries, respectively, the contribution to the
magnetic anisotropy from the LS couplings in Fe(III) and/or
Co(II) cations may not be the same when the cation distribution
changes.
3.3.2.3. Some particles below the super-paramagnetic limit. The
presence of further super-paramagnetic particles (zero coercivity
and zero remanence at room temperature) in the smaller distributed
particles leads to a decrease in HC. The average size of all the
particles is smaller than the critical single domain size (128 nm),
(Table 2) [38] and larger than the critical super-paramagnetic size at
room temperature (23 nm) for cobalt ferrite [36]. However, the
probability of nding further particles below the superparamagnetic limit at room temperature for the fewer particles
obtained from micro-emulsion methods is higher, as compared to
the co-precipitation method.
4. Conclusions
In this paper, CoFe2O4 powders were synthesized by three
widely used wet chemical methods, that is, co-precipitation,
normal micelle and reverse micelle methods with one starting
material/uniform chemical composition. The data obtained from
XRD, FTIR and VSM revealed that:
1. The crystallite size has a stronger effect on the magnetic
properties than the degree of crystallinity and the cation
distribution, respectively. Furthermore, the size effect covers
the role of slight difference of cation distribution.
2. The higher crystallinity in the coprecipitation sample might be
an additional contributing factor in the higher saturation
magnetization.
3. The nanocrystalline CoFe2O4 shows the absorption bands
600 and 400 cm 1, respectively. The high frequency band
u1 around 600 cm 1 is attributed to the tetrahedral complexes
and the band u2 400 cm 1 corresponds to the octahedral
complexes.
4. The magnetic properties of the sample strongly depend on the
size of the nanoparticles. In our study, the magnetic properties
of Co ferrite are slightly dependent on the distribution of the
cations between A and B sites and depends considerably
on the particle size.
Acknowledgments
The authors wish to thank the Department of Chemistry of Shiraz
University and the Department of Chemistry at Shiraz University of
Technology, especially Dr. R. Khalifeh for his kindly constructive
scientic advice and Dr M. N. Soltani-Rad for his support.
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Solid State Ionics and Energy Devices Laboratory, Department of Physics, Bharathiar University, Coimbatore 641046, India
School of Physics, Alagappa University, Karaikudi 630003, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 September 2011
Received in revised form
24 January 2012
Available online 22 February 2012
CdFe2O4 particles were synthesized by the microwave assisted combustion method using two different
fuelsglycine and urea. Microwave heating provides higher chemical yield within a minute. The
synthesized particles were characterized by X-ray diffraction (XRD), Fourier transform infrared
spectroscopy (FTIR), scanning electron microscope (SEM), ac impedance spectroscopy, vibrating sample
magnetometry (VSM) and electron spin resonance (ESR) methods. XRD analysis shows the cubic
structure of CdFe2O4. The high and low frequency absorption bands of CdFe2O4 were found using FTIR
analysis. Spherical morphology was revealed from the SEM images. ESR and VSM measurements reveal
the antiferromagnetic behavior of CdFe2O4. The electrical conductivities of CdFe2O4 synthesized using
glycine and urea are 6.5 10 7 S cm 1 and 4.7 10 8 S cm 1 respectively at 240 oC. At elevated
temperatures an occurrence of increase in conductivity was observed, which indicates the semiconducting behavior of CdFe2O4. The dielectric spectral analysis reveals that dielectric constant of CdFe2O4
decreases with frequency and increases with temperature.
& 2012 Elsevier B.V. All rights reserved.
Keywords:
Cadmium ferrite
Microwave-assisted combustion synthesis
Reaction mechanism
Structural
Magnetic and electric property
1. Introduction
Nanomaterials exhibit different physical and chemical properties compared to their bulk materials. It is well known that by
controlling the size of the particles it is possible to tune their
properties [1]. Recently magnetic nanoparticles of spinel ferrites
were focussed by many researchers because of their interesting
electrical and magnetic properties. Spinel type oxides with the
general formula AB2O4 have considerable application in information storage devices, magnetic bulk cores, magnetic uids, microwave absorbers, catalysts and medical diagnostics. Among them,
CdFe2O4 has normal spinel structure where Cd2 ions occupy the
tetrahedral (A) sites and Fe3 cations occupy octahedral sites.
Several synthetic approaches have been used to prepare CdFe2O4
particles including the combustion method [2], co-precipitation [3,4],
ball milling [5,6], sol gel [7], pulsed laser deposition (PLD) [8] and so
on. Detailed studies on their structural [2,5], and magnetic properties
[3,5,6] and electrical conductivity [8] have been investigated and
reported. CdFe2O4 is an important complex oxide in gas-sensing
materials. Many works have been carried out with regard to their
high sensitivity to volatile suldes such as CH3SH, H2S, and (CH3)2S,
and selectivity to ethanol was analyzed [4,7,8].
In the recent years, microwaves are used to synthesize many
organic and inorganic compounds with novel structures due its
Corresponding author.
E-mail address: selvankram@buc.edu.in (R. Kalai Selvan).
0304-8853/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2012.02.018
2. Experimental procedure
CdFe2O4 was prepared by the microwave assisted combustion
method using a domestic LG microwave oven operating at a
V. Vasanthi et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 21002107
Step 1:
+ NH2CH2COOH
Cd(NO3)2.4H2O
2101
Subsequently, the prepared CdFe2O4 particles were characterized by various techniques in order to analyze their structural,
morphological, magnetic and electrical properties. The compound
formation was studied by x-ray diffraction technique using
BRUKER Germany, D8 Advanced model with 2.2 kW Cu anode
as a source. Fourier transform infrared spectroscopy (FTIR) spectral analysis was done using Shimadzu/Nicolet instruments in the
range of 4000500 cm 1 and the morphological analysis was
performed through scanning electron microscope (SEM). The
magnetic properties were studied by vibrational sample magnetometer (VSM) Lakeshore 7410 and electron spin resonance
spectroscopy (ESR) JEOL JES-FA200. The electrical properties of
the material are studied using a computer controlled impedance
analyzer HIOKI 3532 LCR HITESTER at the frequency ranging from
50 Hz to 10 kHz. For conductivity measurements, the powder was
pressed into a pellet having diameter of 1 cm and a silver paste
was applied on both surfaces of the pellet before being sandwiched between two electrodes of the sample holder to get a
better ohmic contact. Hereafter, the synthesized CdFe2O4 particles
Basic
condition
2NH3+CH2COO- + Cd2+
H 2O
O
O
+
C- CH2NH3+
Cd2+
H3NH2C -C
O
O
H2O
unstable
Step 2:
2NH3+CH2COO- + Fe3+
Fe(NO3)3.9H2O + NH2CH2COOH
H2O
O3N
O
Fe
3+
C - CH2NH2
O
O3N
H2O
unstable
Step 3:
H2O
O
O
+
H2O
C- CH2NH3+
Cd2+
H3NH2C -C
O
O
H2O
O3N
O
3+
Fe
C-CH2NH2
O
O3N
H2O
decomposition
CdFe2O4
Scheme 1. Reaction mechanism of formation of CdFe2O4.
2102
V. Vasanthi et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 21002107
(620)
(533)
(440)
(422)
(511)
(220)
(311)
Intensity (a.u)
(c)
(b)
60
Transmittance %
50
(a)
40
30
20
10
10
20
30
40
50
2 (degree)
60
70
0
4000
80
Fig. 1. XRD pattern of (a) as-prepared CdFe2O4-A, (b) 800 1C calcined CdFe2O4-A
and (c) 800 1C calcined CdFe2O4-B.
3500
3000
2500
2000
1500
Wavenumber (cm-1)
1000
500
Table 1
XRD and FTIR parameters.
Sample
Grain
size D
(nm)
Lattice
constant
a (A)
Cell
volume
3
V (A)
Dx
(g/cm3)
ra
rb
CdO
FeO
Tetrahedral
site v1*
Octahedral
site m 2*
kt 102
(N/m)
ko 102
(N/m)
Avg.
k 102
CdFe2O4 -A
CdFe2O4-B
45
43
8.809
8.795
683.680
680.470
5.597
5.623
0.77
0.76
0.72
0.72
2.07
2.07
2.12
2.12
578.66
586.38
416.64
416.64
2.80
2.88
1.02
1.02
1.91
1.95
V. Vasanthi et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 21002107
2103
1400
60
1200
1000
50
600
40
(b)
400
Intensity
Number of Particles
800
30
20
200
(a)
0
-200
-400
10
-600
-1000
-800
-1200
-1400
0
200
400
600
Field (mT)
800
1000
50
1.2
40
0.8
Magnetization (M), emu/g
Number of Particles
(b)
30
20
10
(a)
0.4
0.0
-0.4
-0.8
0
0.2 0.4 0.6 0.8 1.0 1.2 1.4
Particle size (m)
-1.2
-20000
-10000
0
10000
Applied Field (H), Oe
20000
2104
V. Vasanthi et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 21002107
250 C
o
270 C
o
290 C
240 C
o
260 C
o
280 C
3000
2500
250 C
o
270 C
o
290 C
Z Sin ,x10
Z Sin , x10
150
3500
240 C
o
260 C
o
280 C
200
100
50
2000
1500
1000
500
0
0
25
50
75
100
125
150
175
200
225
50
o
310 C
o
330 C
o
350 C
1500
2000
2500
3000
3500
20
10
300 C
o
320 C
o
340 C
400
Z Sin ,x10
Z Sin , x10
30
1000
300 C
o
320 C
o
340 C
o
360 C
40
500
500
310 C
o
330 C
o
350 C
300
200
100
0
0
10
20
30
40
50
100
Z Cos , x10
200
300
Z COS ,x10
400
500
Fig. 6. Complex impedance plots for (a) CdFe2O4-A and (b) CdFe2O4-B at various temperatures.
Table 2
Impedance and conductance parameters of CdFe2O4-A.
T (1C)
240
250
260
270
280
290
300
310
320
330
340
350
360
Cb
(pF)
38.960
53.060
62.145
41.000
45.080
61.520
59.570
59.970
67.630
67.840
76.700
74.890
77.006
Rb (O) 104
20.430
15.000
12.811
9.708
7.064
5.176
4.454
3.793
3.363
2.934
2.595
2.362
2.298
ac conductivity 10 6 (S cm 1)
ColeCole plot
Conductance
0.635
0.865
1.013
1.330
1.838
2.509
2.916
3.424
3.862
4.428
5.005
5.498
5.653
0.650
0.881
1.020
1.320
1.770
2.450
2.900
3.389
3.838
4.389
4.840
5.382
5.680
op (Hz) 104
N (S cm 1 kHz 1) 10 8
m (cm2/Vs) 1020
2.13
3.12
3.71
4.73
6.93
7.51
7.62
9.93
10.40
11.21
11.94
12.88
16.34
1.56
1.47
1.46
1.51
1.41
1.80
2.10
1.98
2.18
2.35
2.40
2.64
2.20
2.59
3.74
4.36
5.46
7.84
8.50
8.59
10.60
10.90
11.60
12.20
12.70
16.10
l
S cm1
ARb
V. Vasanthi et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 21002107
2105
Table 3
Impedance and conductance parameters of CdFe2O4-B.
T (1C)
240
250
260
270
280
290
300
310
320
330
340
350
360
Cb
(pF)
26.060
21.310
27.520
23.590
42.450
37.747
44.057
53.028
31.760
45.660
34.530
46.440
45.023
ac conductivity 10 7 (S cm 1)
Rb (O) 104
30.540
24.900
19.287
13.490
7.501
6.026
4.517
3.336
2.506
1.743
1.152
0.857
0.707
ColeCole plot
Conductance
0.417
0.511
0.660
0.943
1.690
2.110
2.819
3.817
5.080
7.306
11.050
14.860
18.000
0.470
0.510
0.661
0.943
1.720
2.100
2.880
3.900
5.190
7.490
11.100
15.000
17.900
op (Hz) 104
N (S cm 1 kHz 1) 10 8
m (cm2/Vs) 1020
1.50
2.49
3.73
4.53
6.45
6.98
9.04
12.55
17.69
23.14
32.70
42.70
51.60
1.39
1.07
0.94
1.12
1.47
1.69
1.82
1.81
1.73
1.95
2.00
2.18
2.19
1.83
2.97
4.38
5.26
7.31
7.76
9.89
13.39
18.70
24.00
34.68
43.00
51.00
2.0
250C
260C
270C
280C
290C
300C
310C
320C
330C
340C
350C
360C
1.0
240C
260C
280C
300C
320C
340C
1E-4
ac, S.cm-1
1.5
240C
1E-5
250C
270C
290C
310C
330C
1E-6
0.5
0.0
0.1
1E-7
1
10
x
104
100
(Hz)
8
7
6
5
240C
250C
260C
270C
280C
290C
300C
310C
320C
330C
340C
350C
360C
4
3
2
1
0
0.1
101
10
100
x104 (Hz)
Fig. 8. Plot of imaginary part of impedance with frequency of CdFe2O4-A at
different temperatures.
102
103
104
Frequency (Hz)
105
106
so sdc Aon
V. Vasanthi et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 21002107
eer e0 je00 e0 j
s
oe0
2500
240C
260C
280C
300C
320C
340C
360C
2000
'
1500
250C
270C
290C
310C
330C
350C
1000
106
240C
260C
280C
300C
320C
340C
360C
105
104
''
2106
250C
270C
290C
310C
330C
350C
103
102
101
100
101
102
103
104
Frequency (Hz)
105
106
Fig. 11. Relation between the dielectric loss (e00 ) and frequency at different
temperature for CdFe2O4-A.
500
4. Conclusion
0
101
102
103
104
Frequency (Hz)
105
106
Fig. 10. Relation between the dielectric constant (e0 ) and frequency at various
temperature for CdFe2O4-A.
V. Vasanthi et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 21002107
2107
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Department of Materials Science and Engineering, Faculty of Engineering, Shahid Chamran University, Ahvaz, Iran
Electroceramics Group, Materials Science and Engineering Department, Shiraz University of Technology, 71555-313, Shiraz, Iran
a r t i c l e i n f o
abstract
Article history:
Received 6 December 2011
Received in revised form
20 May 2012
Available online 28 June 2012
In this study, Nanocrystalline MnMgZn ferrite with the chemical formula MnxMg0.5 xZn0.5Fe2O4
(x 0, 0.1, 0.2, 0.3, 0.4, 0.5) was successfully synthesized by the glycine-nitrate autocombustion process
using glycine as a fuel and nitrates as oxidants. The as-synthesized powders were characterized by the
X-ray diffraction analysis, eld emission scanning electron microscopy, Fourier transform infrared
spectroscopy (FTIR) and vibrating sample magnetometer. The X-ray diffraction data was used to
determine the lattice constant, cation distribution and the oxygen position parameter. The results
reveal that the nanocrystalline MnMgZn ferrite has an average crystallite size of 3567 nm and
particle size of 40 nm. The lattice parameter increases linearly with an increase in the Mn content. The
FTIR analysis conrms the intrinsic vibrational frequencies of the tetrahedral and octahedral of the
spinel structure. The magnetic measurements indicate that the coercivity decreases, and the magnetization increases by increasing the Mn content.
& 2012 Elsevier B.V. All rights reserved.
Keywords:
Ferrite
Magnetic properties
X-ray diffraction
Cation distribution
1. Introduction
Ferrites are the magnetic ceramics commonly used in the
production of electronic components [14]. Among different
types of ferrites, MgZn ferrites represent an important class of
soft-magnetic materials, which are widely used in computer
memory and logic devices, cores of transformers, recording heads,
antenna rods, loading coils and microwave devices, and so forth.
As compared to other ferrites, they are preferable because of their
high resistivity and low eddy current losses [5].
Recently, nanoparticle ferrites with a high surface to volume
ratio have received much attention due to their useful, electrical
and magnetic properties used in magnetic uid, information
storage and medical diagnostics [6,7]. These types of nanoparticles can be produced by different wet chemical methods, such as
the co-precipitation [8], hydrothermal synthesis [9], micro-emulsion synthesis [7] and sol gel method [10]. In addition, various dry
methods, including grinding [11], mechanical alloying [12] and
thermal plasma methods [13] have been employed. Besides these
methods, several attempts have been made using auto-ignited
combustion reactions [14,15]. Among them, the glycinenitrate
process (GNP) is a simple, inexpensive and self-sustaining combustion synthesis technique, containing metal nitrates as oxidizers and glycine as fuel.
Corresponding author.
E-mail address: shokrollahi@sutech.ac.ir (H. Shokrollahi).
0304-8853/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jmmm.2012.06.009
3742
H. Mohseni et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 37413747
affect the saturation magnetization. It would be worth mentioning that as compared with the literature in this eld [2224], this
paper has paid special attention to the synthesis of MnMgZn
ferrite by the GNP method.
3.1. FESEM
H. Mohseni et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 37413747
iA h
2
2
Mg20:5x
a Mnbx Zn0:5g Fe1 a b g
iB
3743
O4
Table 1
Lists crystallite size (D), chemical composition, lattice parameter (a), site occupancy, site coordinations and oxygen positional parameter (3/8, 3/8, 3/8) (u).
Sample
P1
P2
P3
P4
P5
P6
Chemical composition
O4
O4
O4
O4
D (nm)
35.5
42.1
48.1
54.9
67.8
65.1
a (nm)
8.388
8.403
8.423
8.437
8.449
8.465
Site occupancy
A-site
B-site
A-site
B-site
0.814
0.824
0.795
0.812
0.833
0.822
0.745
0.728
0.717
0.710
0.727
0.723
1.000
1.000
1.000
1.000
1.000
1.000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.6250
0.6250
0.6250
0.6250
0.6250
0.6250
0.3832
0.3833
0.3795
0.3812
0.3818
0.3827
Rwp (%)
Rp (%)
8.60
8.14
7.05
7.09
6.53
7.36
5.91
5.80
5.22
5.10
4.82
5.51
3744
H. Mohseni et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 37413747
H. Mohseni et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 37413747
3745
layer and the spin-glass properties at the surface can explain the
decrease of the saturation magnetization as the particle size
decreases [39]. The dead magnetic layer originates from the
demagnetization of the surface spin, causing the surface spins to
be disordered or misaligned. This phenomenon weakens the
total magnetization of the nanoparticles [39]. Basically, two
mechanisms have been suggested to explain the origin of spin
canting: one is the surface (or interface) effect, and the other is
the nite- size effect. Variations in coordination numbers and
distances of surface cations could result in a distribution of net
exchange elds. Also, organic molecules bonded to the particles
act as pinning centers for the spins at the surface.
(ii) Cation distribution: In the present work, by assuming 5 mB for
Fe(III) (L0, S5/2, J5/2), and 5 mB for Mn(II) (L0, S 5/2,
J5/2) [35], the net magnetic moment (m/molecule) 9MAMB9
is theoretically calculated, and the results are presented in Fig. 7.
It is obvious that the magnetization of tetrahedral (MA)
decreases; whereas the magnetization of octahedral (MB)
and the net magnetization increase for the samples with
It appears that the substitution of magnetic Mn has strengthened the ferrimagnetic interactions in the system causing an
increase of magnetic order with increasing its concentration (x).
Since, because the occupancy of magnetic Mn increases with x on
both tetrahedral and octahedral sites, the net magnetization
increases relatively signicantly. The synthesis method can affect
strongly the particle size and cation distribution. These parameters change the magnetic properties like saturation magnetization and coercivity. For this reason, it is clear that, a magnetic
powder obtained by GNP method may be have different magnetic
properties as compared with other methods [20,21].
3746
H. Mohseni et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 37413747
Table 2
Magnetic parameters as a function of Mn content in Mg-Mn-Zn Ferrite
Sample
MS(emu/g)7 0.01
HC(Oe)7 0.01
Mr(emu/g)7 0.01
Hmax(kOe)
P1
P2
P3
P4
P5
P6
48.59
53.98
55.14
58.27
59.74
65.25
67.71
64.89
63.47
60.13
57.35
52.39
7.46
7.9
8.08
8.45
8.5
8.86
13.6
13.5
13.9
13.7
13.7
13.6
Fig. 7. Variation of the sublattice and net magnetic moments at room temperature
with Mn concentration.
(l0), magneto-crystalline anisotropy and/or lattice-spin coupling. For this reason, the reduction in magnetic coercivity from
67.7 to 52.4 Oe Table 2 can be contributed only to the increase in
the particle size (Hc a D 1) and/or the decrease in the saturation
magnetization (Hc a MS 1) [40].
4. Conclusions
In this paper, MnMgZn ferrite powders were synthesized by
the glycinenitrate process. The data obtained from XRD, FESEM,
FTIR and VSM revealed that:
1. The nanocrystalline MnMgZn ferrite shows the absorption
bands near 600 and 400 cm 1, respectively. The high frequency band around 600 cm 1 is attributed to the tetrahedral
complexes and the band near 400 cm 1 corresponds to the
octahedral complexes.
2. To calculate the average crystallite size from the broadening of
the XRD peaks of samples and other micro-structural properties, the Rietveld renement of XRD pattern was applied.
3. As the Mn content increases, the lattice parameter due to its
high ionic radius and incomplete-symmetry electronic
conguration.
4. As the Mn content increases, the crystallite size increases as a
result of site preferences, enthalpy formation, electronic conguration and bond energy.
5. Cation site preferences have also caused a large variation in
the magnetic ion concentration over the two sublattices giving
rise to signicant change in the strength of sublattice magnetic
moments.
6. The saturation magnetization increases due to an increase in
the particle size and an increase in the difference in the
saturation magnetization of two sub-lattices.
7. As the Mn content increases, the magnetic coercivity decreases
as a result of an increase in the saturation magnetization and
the particle size. Furthermore, Mg2 (2S2 2P6) and Mn2 (3d5)
do not have contribution in angular momentum and magnetocrystalline anisotropy.
H. Mohseni et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 37413747
Acknowledgements
The authors wish to thank the Department of Chemistry at
Shiraz University for FTIR measurements.
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E.N. Peleka, Hydrothermally prepared nanocrystalline MnZn ferrites: synthesis and characterization, Microporous and Mesoporous Materials 114 (2008)
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Synthesis and morphological study of chromium substituted ZnMn ferrites
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[12] S. Dasgupta, K.B. Kim, J. Ellrich, J. Eckert, I. Manna, Mechano-chemical
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[13] A.B. Nawale, N.S. Kanhe, K.R. Patil, S.V. Bhoraskar, V.L. Mathe, A.K. Das,
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[14] A.C.F.M. Costa, E. Tortella, M.R. Morelli, R.H.G.A. Kiminami, Synthesis, microstructure and magnetic properties of NiZn ferrites, Journal of Magnetism
and Magnetic Materials 256 (2003) 174182.
[15] C.-C. Hwang, J.-S. Tsai, T.-H. Huang, C.-H. Peng, S.-Y. Chen, Combustion
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[16] J.-S.T.Chyi-Ching Hwang, Ting-Han Huang, Combustion synthesis of NiZn
ferrite by using glycine and metal nitratesinvestigations of precursor
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[17] L.A. Chick, L.R. Pederson, G.D. Maupin, J.L. Bates, L.E. Thomas, G.J. Exarhos,
Glycine-nitrate combustion synthesis of oxide ceramic powders, Materials
Letters 10 (1990) 612.
3747
O R I G I N A L PA P E R
Received: 16 June 2012 / Accepted: 5 September 2012 / Published online: 18 October 2012
Springer Science+Business Media, LLC 2012
1 Introduction
NiZn ferrite (Ni1x Znx Fe2 O4 ) is the most versatile ferrite
from the viewpoint of its large number of applications, due
to its high value of magnetic permeability, high electrical
resistivity, high Curie temperature, and low power loss at
high frequencies [13]. Ni0.64 Zn0.36 Fe2 O4 ferrite is one of
the NiZn ferrite compositions which is well known for its
high electrical resistivity (
= 6200 cm) [4] and its high
saturation magnetization (Ms
= 78 emu/g) [5].
These ferrites are usually prepared by the solid state reaction method (SSRM) for large scale production because
of its easy manufacturing process [2]. Nevertheless, this
method has some serious limitations in the production of
fine powders [6]. Long heating schedules and high temperatures result in the large particle nature of the powders.
Thus, a subsequent grinding or milling operation must be
involved in the process to achieve a specific particle size
distribution, which leads to contamination [2, 7]. As a consequence, these powders usually present undesirable characteristics [7]. Also, in NiZn ferrite, the volatilization of
zinc at high temperatures results in the formation of Fe2+
ions, which increases electron hopping and reduces resistivity [8].
478
2 Experimental Method
Nanocrystalline Ni0.64 Zn0.36 Fe2 O4 ferrite was synthesized
by the auto-combustion synthesis method using glycine as
a fuel and nitrates as oxidants. The stoichiometric quantities of the water solutions of reagent grade Fe(NO3 )3 9H2 O,
Ni(NO3 )2 6H2 O and Zn(NO3 )2 6H2 O were mixed with two
moles of glycine for one mole of metal in a large beaker. The
mixed solution was then evaporated on a water bath. A thick
formed gel was kept on a hot plate to start combustion reaction at a temperature of 200 C. Ni0.64 Zn0.36 Fe2 O4 ferrite was also synthesized via solid state reaction method by
heating the stoichiometric amount of Fe2 O3 , ZnO and NiO
at 1250 C for 2 h. In order to reduce the synthesized ferrite particle size, the calcined powders were milled for 3 h
at a milling rate of 200 rpm with a ball-powder weight ratio
of 10:1.
Shimadzu XRD-6000
X-ray, Cu K
Secondary monochromator
Graphite
Instrument power
40 kV, 40 mA
Detector
Scintillation counter
Receiving slit
0.3 mm
Divergence slit
1 mm
Scattering slit
1 mm
Scan mode
/2
Step size
0.02 (2)
1.2 s
Angular range
1090
Temperature
25 C
479
Weight fraction
(wt.%)
Crystallite size
(nm)
Lattice strain
(%)
Lattice parameter
(nm)
GNP
89.63 0.44
47.29 0.64
0.838180 0.000046
SSRM
100
340 18
0.838887 0.000013
Milled SSRM
100
22.79 0.40
0.1575 0.0062
0.838389 0.000086
480
Fig. 3 SEM (a) and TEM micrograph (b) of the Ni0.64 Zn0.36 Fe2 O4 powders prepared by the GNP method
481
Table 3 Magnetization (Ms ) and coercivity (Hc ) of the NiZn ferrite
powders obtained by the different synthesis methods
Fig. 4 HRTEM image and the corresponding electron diffraction pattern of a nanocrystalline Ni0.64 Zn0.36 Fe2 O4 powder particle prepared
by the GNP method
Synthesis method
Ms (emu/g)
GNP
73.47
SSRM
80.54
Milled SSRM
73.88
Hc (Oe)
53.97
6.41
220.5
482
Table 4 Comparison of the particle size and magnetic properties of the as-synthesized NiZn ferrite powders prepared by the different wet
chemical methods
Sample
Ni0.5 Zn0.5 Fe2 O4
Ni0.20 Zn0.44 Fe2.36 O4
Ms (emu/g)
Hc (Oe)
Techniques
References
5.4
[29]
25.9
[13]
20
GNP method
[17]
26
50
[18]
34
35
[30]
44.24
52.12
2025
Combustion method
[23]
53.5
100150
Solvothermal method
[31]
73.47
53.97
200
GNP method
This study
data have been previously reported by other authors. Referring to Table 4, the saturation magnetization of the ferrite
powders processed in this study is higher than that reported
for the as-prepared ferrite powders processed by other wet
chemical methods. This result can be attributed to the particle size effect. As shown in Table 4, the saturation magnetization decreases as the particle size is decreased in such
a way a lower saturation magnetization corresponds to a
smaller particle size.
4 Conclusion
Nanocrystalline Ni0.64 Zn0.36 Fe2 O4 ferrite powders with
high purity have been successfully synthesized by the
glycine-nitrate autocombustion, which was confirmed by the
XRD studies. The same ferrite powder also has been prepared by the solid state reaction method. The as-synthesized
ferrite powders prepared by this method indicate the preferable magnetic properties. However, due to the undesirable
particle size, the subsequent milling process is unavoidable,
which leads to a decrease in saturation magnetization (73.88
emu/g) and an increase in coercivity (220.5 Oe). On the
other hand, nanocrystalline Ni0.64 Zn0.36 Fe2 O4 ferrite powders with the average particle size of 200 nm, coercivity
of 53.97 Oe, and saturation magnetization of 73 emu/g is
obtained by the GNP method. In addition to a desirable
particle size, the magnetic properties of the as-synthesized
GNP powders are relatively comparable to those measured
for the same milled ferrite powders prepared by the solid
state reaction method and, in most cases, even better that
those reported for as-synthesize NiZn ferrite powders prepared by other wet chemical methods. Consequently, the
as-synthesized GNP powder without an additional process
can be used for practical applications.
The glycine-nitrate process reported in this paper is technically simple and cost effective because initial materials are
very cheap and the method does not require any complex
equipment. The method is versatile and can be utilized to
synthesize different ferrite powders.
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4. Akther Hossain, A.K.M., Mahmud, S.T., Seki, M., Kawai, T.,
Tabata, H.: Structural, electrical transport, and magnetic properties
of Ni1x Znx Fe2 O4 . J. Magn. Magn. Mater. 312, 210219 (2007)
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effective dopant on the microstructure development and magnetic
properties of Ni0.64 Zn0.36 Fe2 O4 soft ferrites. Mater. Charact. 59,
638641 (2008)
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R.H.G.A.: Synthesis, microstructure and magnetic properties
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temperature. J. Appl. Phys. 95, 63926395 (2004)
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thermal-plastic polyurethane (TPU)-bonded NiZn-ferrites prepared by combustion synthesis method. Mater. Sci. Eng. B 117,
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Cullity, B.D., Graham, C.D.: Introduction to Magnetic Materials,
2nd edn. Wiley, Hoboken (2009)
Smith, W.F., Hashemi, J.: Foundations of Materials Science and
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Abstract Ultrafine particles of Co1x Lix Fe2 O4 (x = 0, 0.2) samples are prepared
by glycinenitrate combustion route. X-ray diffraction and transmission electron
microscopy studies show that the samples have cubic spinel structure and average
crystallite sizes of x = 0 and 0.2 are 36 and 44 nm respectively. Vibrating sample
magnetometer studies revealed the ferromagnetic nature of the samples. Li-doped
CoFe2 O4 sample showed higher values of coercive field, remanent magnetization
and saturation magnetization compared to pure CoF2 O4 indicating the enhancement
of magnetic interactions. Mssbauer spectra at 77 K exhibited two broad sextets
indicating that Fe3+ ions occupy both tetrahedral and octahedral sites. From these
studies, it is concluded that Co1x Lix Fe2 O4 (x = 0, 0.2) samples exhibit an inverse
spinel structure. At room temperature, two sextets are superimposed on a very broad
228
1 Introduction
Ferrites are useful materials in many applications such as magnetic devices, microwave absorbers, chemical sensors, catalysts, and biomedical applications [16].
In order to control properties, size and shape of the particles and their distribution
are very critical. CoFe2 O4 is the cubic spinel with space group Fd3m . The cationic
distribution is described by the chemical formula: (Fe1x Cox )[Fe1+x Co1x ]O4 . i. e.
(A)[B/ B// ]O4 , ( ) and [ ] denote the tetrahedral A and octahedral B sites respectively.
When x = 0, structure is fully inverse, otherwise the degree of inversion changes
leading to the metastable properties. In order to understand the cationic distribution,
it is necessary to know the thermal history of the sample. When CoFe2 O4 is doped
with other elements such as Mg, Ni, Cu, Zn, Li etc, there is effect on cationic
distribution at tetrahedral and octahedral sites.
Bulk CoFe2 O4 is ferrimagnetic below the Curie temperature (Tc = 860 K) [5]. At
room temperature, it has saturation magnetization (Ms ) of 80 emu/g and coercivity
(Hc ) of (110) kOe [16]. It has easy magnetization axis along [100] with magnetic
saturation (3.95 B ) per formula unit at 5 K and 3.35 B at 300 K [7]. From a
molecular field model, there are six exchange parameters between tetrahedral Fe3+
2+
(A), octahedral Fe3+ (B/ ) and Co
(B// ) when x = 0. It leads to antiferromagnetic
exchange constants J = 20 K JAA , JAB , JAB / , JB / B / , JB / B // except for JB // B //
+40 K. When x = 0, there is no Co2+ ions at the A site. In view of this, expected value
of saturation magnetization is 3 B by considering all the A moments parallel to one
another and antiparallel to the B moments. This 3 B is less than the experimentally
measured value of 3.95 B . The higher measured value could be due to contribution
from orbital moments [5]. In this work, synthesis, magnetic and Mssbauer studies
of Li doped CoFe2 O4 ultrafine particles are presented.
2 Experimental section
Li-doped CoFe2 O4 samples (Co1 x Lix Fe2 O4 , x = 0, 0.2) are prepared by glycine
nitrate combustion route. According to the stoichiometric composition of
Co1 x Lix Fe2 O4 (x = 0, 0.2) specified amounts of lithium acetate, ferric nitrate, cobalt
acetate and glycine in equimolar ratio of metal ions and glycine are dissolved in
minimum quantity of dilute nitric acid. At this stage, the metal acetates are converted
to metal nitrates. The solution is heated on a hot plate at 250 C for 30 min. Initially it
undergoes dehydration at 80 C forming a viscous gel followed by decomposition of
glycine with the evolution of large amount of gases. The powder obtained is calcined
at 575 C for 30 min to remove all the traces of carbonaceous impurities.
X-ray diffraction measurements are carried on the combustion-synthesized powder for phase confirmation and crystallite size estimation using a Philips X-ray
diffractometer (Model-1718) with Ni filtered Cu-K radiation. The average crystallite
229
80
x = 0.0
x = 0.2
60
M (emu/g)
40
20
0
-20
-40
-60
-80
-20
-15
-10
-5
10
15
20
H (kOe)
size has been calculated from the line broadening using the Scherrers relation.
Morphology of particles (size and shape) is determined from Scanning Electron
Microscope (SEM, model JSM-840A) on pellet sample as well as Transmission Electron Microscope (TEM, JEOL 2000 FX microscope) on powder sample. Magnetization measurements are carried out using Vibrating Sample Magnetometer (VSM).
Mssbauer spectra were recorded using a commercial spectrometer operating in
constant acceleration mode at room and liquid nitrogen temperatures. Magnetic
hyperfine fields (Hhf ), quadrupole splitting () and isomer shift () values are calculated with a WIN-NORMOS fit program.
230
(b) x = 0.2
(a) x = 0.0
-10
-5
0
Velocity (mm/s)
10
Table 1 The hyperfine values (Hhf ), isomer shift (), quadrupole splitting (), linewidth ( ) and
areas in percentage of tetrahedral and octahedral sites of Fe3+ ions at liquid nitrogen temperature
for Co1 x Lix Fe2 O4
Phases
Iron sites
Isomer shift
() mm/s
Quadrupole
splitting
(EQ ) mm/s
Hyperfine
splitting
(Hf )104 Oe
Width
( ) mm/s
Area (%)
CoFe2 O4
Sextet 1
Sextet 2
Sextet 1
Sextet 2
0.38
0.49
0.36
0.48
0.00
0.03
0.00
0.03
47.72
50.54
46.54
49.08
0.44
0.46
0.51
0.50
62
38
63.6
36.3
231
(b) x = 0.2
(a) x = 0.0
-10
-5
0
Velocity (mm/s)
10
Table 2 The hyperfine values (Hhf ), isomer shift (), quadrupole splitting (), linewidth ( ) and
areas in percentage of tetrahedral and octahedral sites of Fe3+ ions at room temperature for
Co1 x Lix Fe2 O4
Phases
Iron sites
Isomer shift
() mm/s
Quadrupole
splitting
(EQ ) mm/s
Hyperfine
splitting
(Hf )104 Oe
Width
( )mm/s
CoFe2 O4
Sextet 1
Sextet 2
Sextet 3
Doublet
Sextet 1
Sextet 2
Sextet 3
Doublet
0.30
0.40
0.51
1.08
0.40
0.29
0.55
0.94
0.00
0.08
0.00
0.60
0.04
0.00
0.02
0.76
49.36
52.00
46.01
51.69
49.45
45.77
0.44
0.30
0.64
0.42
0.43
0.43
0.83
0.58
232
Figure 2 shows the Mssbauer spectra of Co1 x Lix Fe2 O4 (x = 0, 0.2) at liquid
nitrogen temperature and the derived hyperfine interaction parameters are given
in Table 1. The x = 0.0 sample (pure CoFe2 O4 ) has two sextets (Zeeman patterns)
indicating that CoFe2 O4 has inverse spinel structure. The values of these parameters
are different from those reported ones for the bulk samples indicating the ultrafine
nature of these particles. Linewidths ( ) for tetrahedral and octahedral sites of pure
CoFe2 O4 are 0.44 and 0.46 mm/s respectively and of Li-doped CoFe2 O4 are 0.51
and 0.50 mm/s respectively. These values are larger than the reported bulk value in
CoFe2 O4 (0.35 mm/s) [6]. Areas in relative percentage in tetrahedral and octahedral
sites are 62% and 38% respectively in CoFe2 O4 . It means that the formula of
composition will be (Co0.8 Fe1.2 )[Co0.2 Fe0.8 ]O4 . While, areas in relative percentage in
tetrahedral and octahedral sites are 64% and 36% respectively in Li (x = 0.2) doped
CoFe2 O4 . It corresponds to the formula of composition: (Co0.7 Fe1.3 )[Co0.3 Fe0.7 ]O4 .
Figure 3 shows the room temperature Mssbauer spectra of Co1 x Lix Fe2 O4 (x =
0.0, 0.2). The sextet peaks are more asymmetric compared to that in liquid nitrogen
temperature and also an additional unresolved broad contribution is seen clearly in
the spectrum and the parameters are given in Table 2. Due to the nano-nature of
some of the particles, it is possible to observe the partially collapsed spectrum due
to the shorter spin relaxation time of ferric ions. Similar complex spectra have been
reported for nano crystalline spinel ferrites in the literature [11].
4 Conclusions
Ultrafine particles of Co1 x Lix Fe2 O4 (x = 0, 0.2) are prepared by glycinenitrate
combustion method. The enhancement in Ms and Hc on Li-doping is due to the
presence of Co2+ in order to compensate charge balance in the Li-doped sample.
Room temperature Mssbauer studies have indicated the presence of nano particles
(spin relaxation effects) in addition to the larger particles exhibiting partially inverted
spinel structure. However, the spectra at 77 K, spin relaxation has sufficiently slowed
down to observe the characteristic spectra assigned to the iron ions occupying both
the tetrahedral and octahedral lattice sites in spinel ferrites.
References
1. Gajbhiye, N.S., Bhattacharyya, S., Balaji, G., Ningthoujam, R.S., Das, R.K., Basak, S.,
Weissmller, J.: Mssbauer and magnetic studies of MFe2 O4 (M = Co, Ni) nanoparticles.
Hyperfine Interact. 165, 153159 (2005)
2. Xu, Z.C.: Magnetic anisotropy and Mssbauer spectra in disordered lithiumzinc ferrites.
J. Appl. Phys. 93, 47464749 (2003)
3. Gajbhiye, N.S., Ningthoujam, R.S., Weissmller, J.: Mssbauer study of nanocrystalline
-Fe3x Cox N system. Hyperfine Interact. 156, 5156 (2004)
4. Kikukawa, N., Takemori, M., Nagano, Y., Sugasawa, M., Kobayashi, S.: Synthesis and magnetic
properties of nanostructured spinel ferrites using a glycinenitrate process. J. Magn. Magn.
Mater. 284, 206214 (2004)
5. Cullity, B.D.: Introduction to Magnetic Materials. Addison-Wesley, London (1972)
6. Ngo, A.T., Bonville, P., Pileni, M.P.: Spin canting and size effects in nanoparticles of nonstoichiometric cobalt ferrite. J. Appl. Phys. 89, 33703376 (2001)
7. Teillet, J., Bouree, F., Krishnan, R.: Magnetic structure of CoFe2 O4 . J. Magn. Magn. Mater. 123,
9396 (2003)
233
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Rapid communication
Department of Applied Chemistry, Chung Cheng Institute of Technology, National Defence University, Number 190, Sanyuan First Street,
Tashi Jen, Taoyuan 33509, Taiwan
b
Department of Materials Science and Engineering, National Chao Tung University, Hsinchu 300, Taiwan
Received 30 August 2004; received in revised form 26 October 2004; accepted 28 October 2004
Abstract
In this study, Ni0.5Zn0.5Fe2O4 powder was synthesized via an exothermic reaction between nitrates [Ni(NO3)2 6H2O,
Zn(NO3)2 6H2O, Fe(NO3)3 9H2O, and NH4NO3] and glycine [NH2CH2COOH]. By adjusting the glycine-to-nitrates ratio, the
oxygen balance (OB) values of the reactant mixtures can be varied in which the combustion phenomena is altered and thereby the assynthesized products with different characteristics are obtained. An interpretation based on the measurement of maximum
combustion temperature (Tc) and the amounts of gas evolved during reaction for various OB values has been proposed regarding the
nature of combustion and its correlation with the characteristics of as-synthesized products. After instrumental analyses, it is shown
that the as-synthesized powders are nanoscale crystallites with a large specic surface area and they inherit a superparamagnetic
behavior.
r 2004 Elsevier Inc. All rights reserved.
Keywords: Combustion synthesis; Nanocrystalline; Oxygen balance; Nitrates; Glycine
1. Introduction
In the past decade, a solution combustion method has
been narrated and utilized to synthesize simple and
mixed metal oxides [19]. With this method, the heating
and evaporation of desired nitrate solution employing
an organic compound (usually glycine, urea, or citric
acid, etc.) can result in self-ring to generate heat by
exothermic reaction. This liberated heat is used to
synthesize the ceramic oxide powders. Together, this
method has advantages of applying inexpensive raw
materials, maintaining a relatively simple, quick and
straightforward preparation process, and achieving a
ne powder with high homogeneity. Recently, a wide
range of technological applications has made homoCorresponding author. Fax: +886 3 389 2494.
ARTICLE IN PRESS
C.-C. Hwang et al. / Journal of Solid State Chemistry 178 (2005) 382389
simplied) as follows:
0:5NiNO3 2 6H2 Oc 0:5ZnNO3 2 6H2 Oc
2FeNO3 3 9H2 Oc cNH2 CH2 COOHc
kNH4 NO3c
!
4 k N2g 10
O2g
2
4
2
11
7
1
14 c k moles of gas produced :
4
2
According to the denition of oxygen balance (OB)
employed in the eld of propellants and explosives
described in Ref. [12], it is appropriate to express OB
value in terms of the weight percent of excessive oxygen
required versus the formula weight of the mixture.
AWoxygen
9c
OB%
k 100%;
(2)
20
2
FWmixture
where AWoxygen and FWmixture are the atomic weight of
oxygen and the formula weight of the mixture,
respectively. From Eqs. (1) and (2), OB value of the
reactant mixture can be adjusted by varying the values
of C and k; as illustrated below:
1. OBo0 (fuel-rich), when C4 40
9 4:44 and k 0:
Obtaining oxygen from atmosphere is required for
combustion between glycine and metal nitrates.
2. OB 0 (stoichiometric), when C 4.44 and k 0:
The oxygen content of metal nitrates can react
completely in oxidizing glycine equivalently.
3. OB40 (fuel-lean), when C 4.44 and k40: There is
an excess amount of oxygen in the reactant mixture
caused by the addition of NH4NO3.
383
2. Experimental
2.1. Sample synthesis
Ni0.5Zn0.5Fe2O4 powder was synthesized by an
amount of 25 g per batch. After considering both
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C.-C. Hwang et al. / Journal of Solid State Chemistry 178 (2005) 382389
384
DH r DH p
;
cp
(3)
Table 1
Entropy of formation and specic heat for the combustion synthesis of NiZn ferrite
Compound
DHf1 (kJ/mol)
Ni(NO3)2(c)
Zn(NO3)2(c)
Fe(NO3)3(aq)a
NH2CH2COOH(c)
NH4NO3(c)
Ni0.5Zn0.5Fe2O4(c)b
CO2(g)
H2O(g)
N2(g)
O2(g)
428
482
671
528
365
1041
395
243
cp (kJ/mol K)
Notes
0.148
0.061
0.051
0.024
0.039
The enthalpy of formation of Fe(NO3)3(aq) was used because that of Fe(NO3)3 (c) was not available.
Due to a lack of thermodynamic data for Ni0.5Zn0.5Fe2O4, the average enthalpy and specic heat of Fe3O4(c) (DH 0f 1117 kJ=mol;
cp 0:147 kJ=mol K) and CuFe2O4(c) (DH 0f 965 kJ=mol; cp 0:149 kJ=mol K) were used [9] because these compounds are isostructure and these
divalence metallic radii (Fe2+, Ni2+, Cu2+, and Zn2+) are nearly the same [19].
b
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C.-C. Hwang et al. / Journal of Solid State Chemistry 178 (2005) 382389
385
OB (%)
-16
-14
-12
-10
-8
-6
-4
-2
10
2800
Temperature (C)
2400
Un-ignitable
SCS
SHS
60
2000
50
1600
40
1200
30
70
800
20
-16
-14
-12
-10
-8
-6
-4
-2
= 6.92
6.44
6.00
5.66
5.33
5.00 4.73
=0
10
OB (%)
4.44
4.44
4.44
0.66
2.21
4.18
4.44
4.44
12.55
6.76
= 4.44
=0
Fig. 2. Theoretical adiabatic ame temperature (Tad) and amount of produced gas, and maximum combustion temperature (Tc) achieved for
different reaction nature as a function of OB value. (&) Tad, (X) Tc, and (K) amount of produced gas (SCS smoldering combustion synthesis;
SHS self-propagating high-temperature synthesis).
Tc=1250C
1400
Temperature (C)
1200
1200
Tc=995C
1000
1000
(a) OB=0
Tc=700C
800
800
(b) OB=+5%
600
600
(c) OB=-8%
400
400
Shoulder
200
Temperature (C)
1400
200
0
0
10
15
20
0
10
15
0
20
10
15
20
25
Time (sec)
Fig. 3. Typical temperaturetime histories during combustion for dried reactant mixtures with (a) OB 0, (b) OB +5%, and (c) OB 8%:
ARTICLE IN PRESS
C.-C. Hwang et al. / Journal of Solid State Chemistry 178 (2005) 382389
386
(c) OB=-8%
Table 2
Effect of OB value on characteristics of as-synthesized powders
spinel ferrite
Fe2O3
OB (%)
Crystallite
sizea (nm)
Surface area
(m2/g)
Carbon content
(wt%)
8 (fuel-rich)
0 (stoichiometric)
+5 (fuel-lean)
27.8
34.5
25.3
39.1
30.2
44.5
9.25
1.53
2.15
a
Crystallite size of the as-synthesized Ni0.5Zn0.5Fe2O4 powders
calculated from the line broadening of the (311) XRD peak by
Scherrer formula.
30
35
40
45
50
2 (Degree)
(440)
(422)
(222)
(400)
(a) OB=0%
(220)
25
(333)/(511)
(311)
(b) OB=+5%
55
60
65
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C.-C. Hwang et al. / Journal of Solid State Chemistry 178 (2005) 382389
387
Fig. 6. TEM images of as-synthesized powders with corresponding diffraction patterns for (a) OB 0 and (b) OB 5% (Taken under the same
operation conditions for both specimens).
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C.-C. Hwang et al. / Journal of Solid State Chemistry 178 (2005) 382389
388
were estimated to be
2025 nm for the OB +5%
product and
3540 nm for OB 0 one, in terms of
which they are about the same sizes as the ones
estimated by using XRD method. In addition, diffraction patterns indicate that the OB 0 product has a
higher degree of crystallinity than do the OB +5%
one. (The TEM photograph of the as-synthesized
product with OB 8% is similar to the one using
OB +5%, but not shown here).
Fig. 7 shows the real trace of the hysteresis loops of
the as-synthesized powders (crystallite size: o40 nm)
and the sintered sample (grain size:
1 2 mm). The
hysteresis loops of the as-synthesized ferrites were
characterized to have quite low magnetization values
and they do not reach saturation value even at 15 kOe,
indicating their superparamagnetic nature. However, on
sintering the ferrite at 950 1C/2 h, saturation magnetization was attained (
72 emu/g) at 2.5 kOe. This result is
obviously caused by the dependence of grain size on Ms,
which can be explained through the transition from
mono- to multi-magnetic-domain behavior [25]. As
shown in Figs. 7(b) and (c), the maximum magnetization
attained for powders synthesized with different OB
value was in the order of OB 04OB +5%4OB
8%, whereas the order of coercive force was just
opposite. It is suggested that impurity content or poor
crystallization may affect the magnetic behavior of the
as-synthesized ferrite by reducing the maximum magnetization and increasing the coercive force. (It is worth
noting that the soft-magnetic properties of the sintered
sample are comparable with those obtained by other
80
60
20
4. Conclusions
1. A combustion synthesis method has been used to
prepare nanocrystalline Ni0.5Zn0.5Fe2O4 containing a
considerably large surface area. Utilization of glycine,
metal (Ni, Zn, and Fe) nitrates, ammonium nitrate
joined with mixing the reactants without adding
water and combining a step of thorough dehydration
are the key techniques of this method. Once ignited in
air at room temperature, the reactant mixtures
undergo a combustion process and directly transform
into porous ferrite powders.
2. The combustion reaction is between nitrates and
glycine, in that NO
3 is oxidant and the organic group
is fuel. The reaction mode and the combustion
temperature can be controlled by changing the
oxygen balance (OB) values of the reactant mixtures.
Thus, the properties (such as crystallite size, surface
area, carbon content, etc.) of as-synthesized product
can vary based on OB value.
3. The maximum magnetization and coercive force
of the resulting ferrites show a strong dependence
on OB value. In addition, the as-synthesized powders
(b)
6
0
0
12
16
5.0
Magnetization (emu/g)
Magnetization (emu/g)
40
Magnetization (emu/g)
(a)
-20
-40
-60
(c)
2.5
0.0
-2.5
-5.0
-1.0
-0.5
0.0
0.5
1.0
-80
-15
-10
-5
0
5
Magnetic Field (kOe)
10
15
Fig. 7. (a) Room temperature hysteresis loops of as-synthesized powders made with various OB values and the sintered sample obtained by using the
product of OB 0: (b) A zoom plot showing the rst quadrant of Fig. 7(a). (c) A zoom plot showing the vicinity of the origin in Fig. 7(a). () assynthesized powder for OB 0; (n) as-synthesized powder for OB 5%, (J) as-synthesized powder for OB 8%; and (.) sintered sample.
ARTICLE IN PRESS
C.-C. Hwang et al. / Journal of Solid State Chemistry 178 (2005) 382389
contain a superparamagnetic nature due to their lowranking and unsaturated magnetization value as
compared with those of sintered sample.
Acknowledgment
Support for this research by the National Science
Council of the Republic of China under Grant No. NSC
93-2214-E-014-001 is gratefully acknowledged.
References
[1] L.A. Chick, L.R. Pederson, G.D. Maupin, J.L. Bates, L.E.
Thomas, G.J. Exarhos, Mater. Lett. 10 (1990) 612.
[2] K. Suresh, K.C. Patil, J. Solid State Chem. 99 (1992) 1217.
[3] J.J. Kingsley, L.R. Pederson, Mater. Res. Soc. Symp. Proc. 296
(1993) 361366.
[4] L.E. Shea, J. McKittrick, O.A. Lopez, E. Sluzky, J. Am. Ceram.
Soc. 79 (1996) 32573265.
[5] C.H. Yan, Z.G. Xu, F.X. Cheng, Z.M. Wang, L.D. Sun,
C.S. Liao, J.T. Jia, Solid State Commun. 111 (1999) 287291.
[6] R.D. Purohit, B.P. Sharma, K.T. Pillai, A.K. Tyagi, Mater. Res.
Bull. 36 (2001) 27112721.
[7] Y.P. Fu, C.H. Lin, J. Magn. Magn. Mater. 251 (2002) 7479.
[8] R. Kalai Selvan, C.O. Augustin, L. John Berchmans, R.
Saraswathi, Mater. Res. Bull. 38 (2003) 4154.
[9] R.V. Mangalaraja, S. Ananthakmar, P. Manohar, F.D. Gnanam,
M. Awano, Mater. Sci. Eng. A 367 (2004) 301305.
[10] T.Y. Tsay, K.S. Liu, I.N. Lin, J. Magn. Magn. Mater. 209 (2000)
189192.
389
ARTICLE IN PRESS
Physica B 404 (2009) 39153921
Physica B
journal homepage: www.elsevier.com/locate/physb
Department of Applied Physics, Electronics and Communication Engineering, Islamic University, Kushtia 7003, Bangladesh
Department of Physics, Bangladesh University of Engineering and Technology, Dhaka 1000, Bangladesh
c
Materials Science Division, Atomic Energy Centre, Ramna, Dhaka 1000, Bangladesh
b
a r t i c l e in fo
abstract
Article history:
Received 7 December 2008
Accepted 6 July 2009
Polycrystalline Mg1xZnxFe2O4 (x 0.00.6) ferrites have been prepared using solid-state reaction
technique. The X-ray diffraction analysis revealed that the samples crystallize in a single-phase cubic
spinel structure. The lattice parameter increases linearly with increase in zinc content obeying Vegards
law. The continuous decrease in Curie temperature (Tc) with an increase in Zn content is attributed to
the weakening of AB exchange interaction. Saturation magnetization (Ms) and magnetic moment are
observed to increase up to x 0.4, and thereafter decrease due to the spin canting in B-sites. The initial
permeability is found to increase with the addition of Zn2+ ions but the resonance frequency shifts
towards the lower frequency.
& 2009 Elsevier B.V. All rights reserved.
PACS:
75.50.Gg
Keywords:
MgZn ferrites
Complex permeability
Spin canting
1. Introduction
MgFe2O4 is a partially inverse cubic spinel and it can be
considered as a collinear ferrimagnet whose degree of inversion is
sensitive to the sample preparation history. Magnetic properties
of ferrites strongly depend on their chemical compositions and
additives/substitutions. Small amount of foreign ions in the ferrite
can dramatically change the properties of ferrites. Therefore, most
of the latest ferrite products contain a small amount of additives/
substitutions. Nonmagnetic Zn is a very promising and interesting
candidate among them. The magnetic properties of Zn-substituted
ferrites have attracted considerable attention because of the
importance of these materials for high-frequency applications.
Zinc ferrite (ZnFe2O4) possesses a normal spinel structure, i.e.,
2+
2
ions reside on A-sites and Fe3+
(Zn2+)A [Fe3+
2 ]BO4 , where all Zn
ions on B-sites. Therefore, substitution of Mg by Zn in
Mg1xZnxFe2O4 is expected to increase the magnetic moment up
to a certain limit, thereafter it decreases for the canting of spins in
B-sites. The structural and magnetic characteristics of MgFe2O4
with nonmagnetic substances such as Zn2+ [1], Ca2+ [2,3], Ti4+ [4],
Zr4+ [5] and Al3+ [6] have been investigated. Zn- and Cdsubstituted mixed ferrites such as FeZn [7], CuZn [8], NiCd
[9], MgCd [10] and MgZn [11] show canted-spin arrangement
on the octahedral B-sites. In the present study, a series of
Mg1xZnxFe2O4 (x 0.0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) were
Corresponding author. Tel.: +88 01715 157526; fax: +88 07154400.
2. Experimental
The MgZn ferrites of the composition Mg1xZnxFe2O4 (x 0.0,
0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) have been prepared using the solidstate reaction technique at Materials Science Division, Atomic
Energy Centre, Dhaka, Bangladesh. The starting materials were in
the form of AR-grade oxides (Fe2O3, MgO and ZnO) of E. Merck of
Germany. The detailed procedure of sample preparation is
described elsewhere [12,13]. The pellet and toroid-shaped samples were sintered at 1275 1C for 12 h in air and cooled in the
furnace. All the samples were heated slowly in the Thermolyne
high-temperature furnace at the rate of 1 1C/min and kept at the
ring temperature for 12 h. The cooling was done in the furnace at
the same rate of heating. The samples were polished in order to
remove any oxide layer formed during the process of sintering.
The weight and dimensions of the pellets were measured to
determine bulk densities.
Phase analysis was done by X-ray diffraction using a Phillips
(PW3040) X0 Pert PRO X-ray diffractometer. The powder specimens were exposed to CuKa radiation with a primary beam power
of 40 kV and 30 mA with a sampling pitch of 0.021 and time for
each step data collection was 1.0 s. X-ray diffraction patterns
conrmed the spinel phase for all the samples. Frequency
dependence of complex permeability of the toroid-shaped
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3916
8.43
8.42
8.40
8.39
8.38
0.1
0.0
0.3
0.4
Zn content (x)
Mg1-xZnxFe2O4
(440)
(511)
(422)
x = 0.6
(400)
(222)
(220)
(620)
(440)
(511)
(422)
(400)
(311)
(311)
0.2
x = 0.2
x = 0.1
x = 0.4
x = 0.0
20
30
40
50
60
70
0.5
0.6
Mg1-xZnxFe2O4
(222)
(220)
Intensity (a.u)
8.41
a ()
x = 0.3
80 20
30
40
50
2
2
Fig. 1. XRD patterns of Mg1xZnxFe2O4 ferrites.
60
70
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M. Manjurul Haque et al. / Physica B 404 (2009) 39153921
3917
400
5.0
dB
dX
x = 0.0
350
x = 0.1
x = 0.2
300
4.8
x = 0.3
x = 0.5
x = 0.6
'
Density (g-cm-3)
x = 0.4
250
4.6
200
150
4.4
100
50
4.2
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Zn content (x)
Fig. 3. Variation of density with Zn content (x) of Mg1xZnxFe2O4 ferrites.
200
300
400
500
T (C)
Fig. 4. Temperature dependence of real permeability of Mg1xZnxFe2O4 ferrites.
is 8 for the spinel cubic structure. The X-ray density and bulk
density increase signicantly with increase in Zn content. The
atomic weight and density of Mg are 24.31 and 1.74 g cm3,
respectively, while the corresponding values of Zn are 65.37 and
7.14 g cm3, respectively. The bulk density (dB) is less than the
X-ray density (dX). This may be due to the existence of pores,
which were formed and developed during sample preparation or
sintering process.
500
300
y = -667.86x + 473.64
400
Tc (C)
100
200
100
0
0.0
0.1
0.2
0.3
0.4
Zn content (x)
0.5
0.6
0.7
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M. Manjurul Haque et al. / Physica B 404 (2009) 39153921
80
x = 0.2
60
40
x = 0.1
'
20
0.2
x = 0.0
x=
0.1
x=
', ''
3918
''
0.1
10
0.
100
f (MHz)
350
Tc x Tc 0 667:86x
300
x = 0.6
250
x = 0.5
200
', ''
150
Table 1
Data of the lattice parameter (a), bulk density (dB), X-ray density (dX), Curie
temperature (Tc), initial permeability (m0 ) and resonance frequency (fr) of
Mg1xZnxFe2O4 ferrites sintered at 1275 1C.
50
x = 0.4
'
x = 0.3
100
0.6
0.0
0.1
0.2
0.3
0.4
0.5
0.6
4.253
4.378
4.484
4.531
4.625
4.665
4.755
8.384
8.391
8.396
8.401
8.411
8.417
8.420
4.508
4.588
4.676
4.759
4.826
4.911
4.996
460
399
356
285
222
149
49
24
37
68
122
164
224
335
4100
E100
56.234
31.623
14.125
10.000
7.499
0.
''
0.
0.
x=
0
0.1
10
100
f (MHz)
Fig. 6. Complex permeability spectra for Mg1xZnxFe2O4 ferrite system sintered at
1275 1C.
ARTICLE IN PRESS
M. Manjurul Haque et al. / Physica B 404 (2009) 39153921
6000
Molecular weight Ms
mB N
x = 0.3
5000
3919
70
x = 0.4
60
x = 0.5
50
x = 0.2
3000
2000
Ms (emu/g)
4000
x = 0.6
40
Mg1-xZnxFe2O4
x = 0.1
30
1000
x=0.0
20
0
1E-3
0.01
0.1
10
100
f (MHz)
Fig. 7. Frequency dependence of relative quality factor (RQF) of Mg1xZnxFe2O4
ferrites sintered at 1275 1C.
10
0.0
0.1
0.2
0.3
0.4
Zinc content (x)
0.5
0.6
ARTICLE IN PRESS
3920
Table 2
Data of saturation magnetization (Ms), theoretical and experimental magnetic
moment (nB) and YafetKittel angle (aYK).
Zinc content (x)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Ms (emu/g)
27.9
45
57.5
60.8
63.9
54.5
33.8
nB (mB)
aYK
Theoretical
Experimental
1.0
1.9
2.8
3.7
4.6
5.5
6.4
0.985
1.645
2.144
2.311
2.476
2.152
1.359
0
0
0
0
0
32.241
53.141
7
nB(Theoretical)
nB(Experimental)
Magnetic moment ()
0.0
0.2
0.4
0.6
4. Conclusions
The X-ray diffraction conrmed the single-phase cubic spinel
structure of the samples. The lattice parameter increases with
increase in Zn content obeying Vegards law. Curie temperatures
show a decreasing trend with successive addition of zinc ions. This
is due to the fact that the replacement of Fe3+ ions by Zn2+ ions in
the A-sites results in decrease in the strength of AB super
exchange interaction. Saturation magnetization and magnetic
moment are found to increase with Zn content up to xZ0.4. This
is because Zn substitution leads to increased Fe3+ ions on the
B-sites and decreases Fe3+ ions on the A-sites. Decrease in the
magnetic moment after x40.4 indicates the possibility of a noncollinear spin canting effect in the system. An increase in initial
permeability has been observed with increase in zinc content but
the resonance frequency shifts towards the lower frequency.
ARTICLE IN PRESS
M. Manjurul Haque et al. / Physica B 404 (2009) 39153921
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Physica B
journal homepage: www.elsevier.com/locate/physb
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 28 September 2011
Received in revised form
4 January 2012
Accepted 5 January 2012
Available online 17 January 2012
Nanocrystalline Nickel ferrite (NiFe2O4) and Zn substituted nickel ferrite (NiZnFe2O4) have been
synthesized by the reuxing method. These ferrites were characterized by XRD, TEM, Mossbauer
spectroscopy and VSM in order to study the effect of zinc substitution in nickel ferrite. XRD diffraction
results conrm the spinel structure for the prepared nanocrystalline ferrites with an average crystallite
size of 1416 nm. Lattice parameter was found to increase with the substitution of Zn2 ions from
TEM images conrmed average particle size of about 20 nm and indicates nanocrystal8.40 A to 8.42 A.
line nature of the compounds. A shift in isomeric deviation with the doublet was observed due to the
inuence of Zn substitution in the nickel ferrite. The Zn content has a signicant inuence on the
magnetic behavior and electrical conductivity of NiFe2O4. Saturation magnetization drastically
increased whereas room temperature electrical conductivity decreased due to the addition of Zn
content in NiFe2O4, indicating super magnetic material with lesser coercivity.
& 2012 Elsevier B.V. All rights reserved.
Keywords:
Nickel ferrite
Nickel zinc ferrite
Reux method
Mossbauer spectroscopy
VSM
1. Introduction
Recently, nanocrystalline magnetic materials have been
receiving more attention due to their novel material properties,
which are signicantly different from those of their bulk counterparts. Spinel-type oxides (MFe2O4, where M is a divalent metal)
which include the magnetic ferrites, are often denoted by the
formula AB2O4, where A and B refer to tetrahedral and octahedral
sites, respectively, in the face centered cubic lattice. These
materials are technologically important and have been used in
many applications including magnetic recording media and
magnetic uids for the storage and/or retrieval of information,
magnetic resonance imaging (MRI) enhancement, catalysis, magnetically guided drug delivery, sensors and pigments [1]. Among
all ferrites, NiFe2O4 has been synthesized because it has promising applications like ferro-uids, gas sensor, catalyst, microwave
absorber, information storage devices, magnetic uids, drug
delivery [2]. Nickel ferrite (NiFe2O4) is basically an inverse spinel
ferrite in which the tetrahedral (A) sites are occupied by ferric
ions and the octahedral (B) sites by ferric and nickel ions. Thus,
the compound can be represented as (Fe3 )A[Ni2 Fe3 ]BO2 4. The
magnetic properties and cation distribution are found to be
different in nanocrystalline spinel ferrites, when compared to
0921-4526/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2012.01.081
1105
2. Experimental
Ferric nitrate [Fe(NO3)3 9H2O], nickel nitrate [Ni(NO3)2 6H2O]
and zinc nitrate [Zn(NO3)2 6H2O] with the purity 99.5% were
purchased from Hi-media and used as received. NiFe2O4 and Zn2
substituted NiFe2O4 ferrites have been synthesized by simple
approach of reuxing method. In a typical procedure, specic molar
concentration of nickel nitrate and ferric nitrate as precursors were
mixed in a starch solution and stirred for half an hour for the
synthesis of NiFe2O4. Under reux condition, NaOH was added drop
by drop for 4 h to provide a net negative surface charge to the nuclei
limiting their further growth and aggregation. After reuxing, the
solution was kept overnight and then ltered and dried in hot air
oven at 80 1C for 12 h. Dried sample was treated at different
temperatures 800 1C, 900 1C, 1000 1C, 1100 1C in order to maintain
the stability of compound giving stoichiometric ferrite structure
according to the following reaction,
2Fe3 M2 8OH -Fe2 MOH8 -MFe2 O4 4H2 O:
The nucleation rate is quite high at the beginning of the precipitation process whereas the excess of OH ions provides a net negative
surface charge to the nuclei avoiding aggregation. For synthesis of
Zn2 substituted NiFe2O4 ferrite, specic molar concentration of
nickel nitrate, zinc nitrate and ferric nitrate as precursor were mixed
in a starch solution and stirred for half an hour. Under reux
condition, NaOH was added drop by drop for 4 h. After reuxing,
the solution was kept overnight and then ltered and dried in hot air
oven at 80 1C for 12 h. Finally sample was treated at different
temperatures 800 1C, 900 1C, 1000 1C, 1100 1C resulting into the
Zn2 substituted nanocrystalline NiFe2O4. These ferrites have been
abbreviated as NF for NiFe2O4 and NZF for Zn2 substituted NiFe2O4,
respectively. Ferrites have been characterized by XRD (Philips PW
1730 automatic X-ray diffractometer with Cu-Ka radiation of
l 1.5428 A),
TEM (Hitachi H-7000 operated at 100 kV and
30 mA), Mossbauer spectroscopy (4.2300 K, 5 T) using a commercial oxford cryostat. Magnetic measurement using EG & G PAR model
4500 vibrating sample magnetometer and electrical resistivity measurement using four point probe technique was done to study the
effect of zinc substitution in nickel ferrite.
Fig. 1. XRD pattern of (a) NiFe2O4 and (b) Zn2 substituted NiFe2O4.
1106
Fig. 2. (a) TEM image of NiFe2O4. (b) TEM image of Zn2 substituted NiFe2O4.
Fig. 3. (a) Mossbauer spectra of NiFe2O4. (b) Mossbauer spectra of Zn2 substituted NiFe2O4.
1107
4. Conclusions
The synthesized NiFe2O4 and Zn2 substituted NiFe2O4 ferrites
are crystalline, having average particle size of 20 nm as revealed
by TEM. Lattice parameter was found to increase with the
substitution of Zn2 ions in NiFe2O4. VSM results show that
saturation magnetization of NiFe2O4 drastically increased due to
the addition of Zn2 content indicating super magnetic material
with lesser remanance as supported from its Mossbauer spectroscopy. The substitution of Zn2 in NiFe2O4 lowered the electrical
conductivity due to widening of band gap as a result of size
dependent property.
Acknowledgment
The authors are grateful for the nancial support of University
Grants Commission, New Delhi, India (F No.39-540/2010 SR).
Fig. 4. MH curves for (a) NiFe2O4 and (b) Zn2 substituted NiFe2O4.
Fig. 5. Electrical conductivity of (a) NiFe2O4 and (b) Zn2 substituted NiFe2O4.
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