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Effect of sintering temperature on micro structural and impedance

spectroscopic properties of Ni0.5Zn0.5Fe2O4 nano ferrite

Conference Paper  in  AIP Conference Proceedings · July 2017

DOI: 10.1063/1.4990188

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Effect of sintering temperature on micro structural and impedance spectroscopic
properties of Ni0.5Zn0.5Fe2O4 nano ferrite
Davuluri Venkatesh, K. V. Ramesh, and C. V. S. S. Sastry

Citation: AIP Conference Proceedings 1859, 020035 (2017); doi: 10.1063/1.4990188

View online: http://dx.doi.org/10.1063/1.4990188
View Table of Contents: http://aip.scitation.org/toc/apc/1859/1
Published by the American Institute of Physics
 Effect of Sintering Temperature on Micro Structural and
Impedance Spectroscopic Properties of Ni0.5Zn0.5Fe2O4nano
Ferrite

Davuluri Venkatesh1 , K V Ramesh1* and C V S S Sastry2

1
Center for Materials Research, Department of Physics, GITAM Institute of Science, GITAM University,
Rushikonda, Visakhapatnam, Andhra Pradesh-530045, India
2
Government Degree College, Chodavaram, Visakhapatnam, Andhra Pradesh, India
*
Corresponding author: kvramesh11@gmail.com

Abstract. Ni-Zn nanoferrite Ni0.5Zn0.5Fe2O4 is prepared by citrate gel auto combustion method and sintered at various
temperatures 800, 900, 1000, 1100 and 1200 0C. The room temperature x-ray diffraction conforms that the single phase
spinel structure is formed. Crystallite size and density were increased with increasing of sintering temperature. From
Raman spectroscopy all sintered samples are single phase with cubic spinel structure belong to Fd3m space group. From
surface morphology studies it is clearly observed that the particle size increased with increasing of sintering temperature.
Impedance spectroscopy revel that increasing of conductivity is due to grain resistance is decreased with increasing of
sintering temperature. Cole-Cole plots are studied from impedance data. The electrical modulus analysis shows that non-
Debye nature of Ni0.5Zn0.5Fe2O4 ferrite.

Keywords: Ni-Zn ferrite, Auto combustion, Impedance spectroscopy.

INTRODUCTION
The spinel structured nano crystalline Ni-Zn ferrite having chemical formula Ni0.5Zn0.5Fe2O4 is most versatile
magnetic material for electronic devices, inductors, magnetic media, and high frequency applications. Due to their
high resistivity, saturation magnetization, low eddy current losses and high Curie temperature [1-3]. The spinel
structured Ni-Zn ferrites have both tetrahedral (A) and Octahedral (B) Sites with Molecular formula [Fe 3+ Zn2+]A
[Ni2+ Fe3+]B O4 Where Zn2+ ions prefer to occupy tetrahedral (A) site, Ni2+ ions prefer to occupy octahedral (B) site
and Fe3+ ions occupy both A and B sites. The cation distribution of A and B site depends on the method of
preparation, stoichiometric composition, concentration of impurity and ionic radii [4-5]. There are different methods
for preparation of Ni-Zn ferrites. Such as Solid state reaction [6], high energy ball milling [7], co-precipitation
method [8], hydrothermal synthesis [9], sol gel method [10], citrate gel auto combustion method [11].
Ni0.5Zn0.5Fe2O4 is well established in conventional ceramic method but it needs high calcination
temperature. Applying of high temperatures for long time some constituent elements like zinc volatilization may
take place. This may results to formation of Fe2+ ions, which may cause to increase of electron hoping mechanism
and decreasing of resistivity [12] and also this type of preparation techniques have homogeneity of particles is very
less. Synthesis of nano particle in auto combustion methods, no need of high temperature and most of the particles
are formed in uniform size. Preparing of nano ferrites in below 2000C temperature Citrate gel auto combustion
method is promising. In our previous report [13] we reported that cation distribution, microstrain and magnetic
properties of Ni0.5Zn0.5Fe2O4 ferrite sintered at various sintering temperatures. In this present communication our

International Conference on Functional Materials, Characterization, Solid State Physics, Power, Thermal and Combustion Energy
AIP Conf. Proc. 1859, 020035-1–020035-6; doi: 10.1063/1.4990188
Published by AIP Publishing. 978-0-7354-1533-1/$30.00

020035-1
interest is to study effect of grain size on Structural, electrical and Impedance spectroscopic properties of
Ni0.5Zn0.5Fe2O4 system synthesized via citrate gel auto combustion method and sintered at different sintering
temperatures (800, 900, 1000, 1100, 1200 0C).

EXPERIMENTAL
The nano Ni0.5Zn0.5Fe2O4ferrite system was prepared by citrate gel auto combustion method. In this method all
high purity chemicals such as Nickel nitrate, (Ni (NO3)2.6H2O), Zinc nitrate (Zn (NO3)2.6 H2O), Ferric nitrate (Fe
(NO3)2.9 H2O), and Citric acid (C6H8O7) were used. All nitrates were weighed accordingly and dissolved in double
distilled deionized water as per stoichiometry. The raw nitrate solution mixture was kept on a magnetic stirrer with
hot plate and applies continuous stirring to get homogeneity. Temperature was maintained at 65 oC for few minutes
after that the chelating agent citric acid was mixed into the nitrate solution. Now by increase the temperature viscous
gel was formed and it finally becomes powder. The obtained powder was mixed with binder polyvinyl alcohol and
pressed into pellets 10mm diameter and 3mm thickness by applying pressure of 5 tons/inch 2. The samples were
sintered at 800oC, 900oC, 1000oC, 1100oC, and 1200oC in air for 4 hours. In sintering process the oxide layer is
formed to reduce this oxide layer the pellets were polished. For electrical contact silver paste was applied on both
sides of pellets and heated at2000C for one hour.
The room temperature powder X-ray diffraction data was carried out by using of Pan-Analytical X’pertPRO
diffraction meter with CuKα (=1.5406 A0).The crystal structure, crystallite size are estimated from standard
relations. The room temperature Raman data of all sintered samples made on by using of Horiba Scientific Lab Ram
HR Raman spectrometer with excitation wavelength of 532 nm. The surface morphology studies of all sintered
pellets were performed on ZEISS Scanning electron micro scope with accelerating voltage 10 kV. And also
impedance data of all sintered samples were performed on PSM-1735 Newton 4thLtd. In frequency range (1 Hz to 10
MHz).

RESULTS AND DISCUSSIONS

The X-ray diffractrograms of Ni0.5Zn0.5Fe2O4 ferrite sintered at various temperatures such as 800 oC, 900oC,
1000oC, 1100oC, and 1200oC were shown in figure 1. From figure1 which is indicating that all samples exhibiting
single phase spinel cubic structure. The experimental lattice parameter was calculated by using of standard relation
[13].
ܽ௘௫௣ ൌ ݀௛௞௟ ξሺ݄ଶ ൅ ݇ ଶ ൅ ݈ ଶ ሻ

Where ܽ௘௫௣ is experimental lattice parameter, ݀௛௞௟ is interplanar spacing.

The crystallite size of most intense peak (311) of Ni0.5Zn0.5Fe2O4 ferrite was calculated by using the Debye-
Scherer relation [13] as given below.
ଷଵଵୀ బǤవλ
βి౥౩θ

Where λ is wavelength, β is full width at half maximum (FWHM) and is θ angle of diffraction. The crystallite
sizes of all sintered samples were increased with increasing of sintering temperature and the density of samples is
also increased with increasing of sintering temperature. The obtained crystallite size, lattice parameter and density of
the sample sintered at different temperatures are reported in table 1.
Raman spectroscopy is used to study the vibrational spectra of spinel ferrite materials. The cubic spinel
Ni0.5Zn0.5Fe2O4 nanoferrite belongs to Fd3m space group with eight formula (8MIIFe2IIIO4) units per unit cell. The
unit cell containing 56 atoms and the smallest Braves cell consists of 14 atoms. Therefore 42 vibrational modes are
possible [14]. According to group theory the optical phonon distribution is [15]

T= A1g(R)+Eg(R)+T1g+3T2g(R)+2A2u+2Eu+5T1u(IR)+2T2u

Where R and IR are Raman and Infrared activity modes respectively, 5T 1umodes are infrared active mode, other
five (A1g+Eg+T1g+3T2g) modes are Raman active modes. These modes are composed to the motion of O ions and
both tetrahedral and octahedral site ions [16-17]. The room temperature Raman data of Ni0.5Zn0.5Fe2O4ferrite
sintered at 800oC, 900oC, 1000oC, 1100oC, and 1200oC were carried in the frequency range 200 cm-1 to 1000 cm-1.

020035-2
Figure 2 shows the Raman spectra of the sintered samples indicating the characteristic peaks at 221, 246, 355, 452
with shoulder at 650 cm-1. The Raman mode at 650 cm-1 was more promising at 12000C sintering temperature as it is
increasing from 8000C. This indicates the formation of mixed spinel ferrite is prominent at 1200 0C temperature.
[311]
Intensity (arb.units)

[220] [511] [440]

[400]

Intensity (a.u)
[222] [422] 0 0
1200 C 1200 C
0
1100 C 0
1100 C
0 0
1000 C 1000 C

0
900 C
0
900 C

0 0
800 C 800 C

300 400 500 600 700 800

Raman Shift (Cm-1)

20 30 40 50 60 70
Glancing angle (2T)

FIGURE 1. X-Ray Diffractograms of Ni0.5Zn0.5Fe2O4 FIGURE 2. Raman spectra of Ni0.5Zn0.5Fe2O4 ferrite

sintered at 8000C, 9000C, 10000C, 11000C, and 12000C. sintered at 800oC, 900oC, 1000oC, 1100oC, and 1200oC with
excitation wavelength of 532 nm.
Study of Micro structure is very important to understand the electrical properties of polycrystalline ferrites. The
scanning electron microscopic (SEM) images of Ni0.5Zn0.5Fe2O4 ferrite sintered at different sintering temperatures
was shown in figure 3. From SEM images it is very clear that grain size is increased with increasing of sintering
temperature. The grain size is reported in the table 1. From SEM images it was observed that sintered samples
contain grooves, pores, layers, cracks and sheet like patterns having some small aggregations within the available
resolution. The observed sheet like structures gradually decreases to increasing of sintering temperature which leads
to increase in grain size with increasing of sintering temperature. The grain size of all sintered samples measured by
linear intercept method [18] and it was found to be linearly increases with increasing of sintering temperature and
the obtained values in the range of 100nm-500nm. The obtained grain size values are very smaller than those
reported in conventionally synthesized ferrites [19]. The observed smaller grain size values of sintered pellets can be
explained on the basis of open and closed pores in the microstructure. Open pores are more effective at pinning than
closed pores to restrict the growth of grain [20].

Table 1. Variation of Density, Crystallite size, Lattice Parameter, Grain Size, Relaxation time, Grain resistance, Grain
capacitance of Ni0.5Zn0.5Fe2O4 ferrite samples with sintering temperatures.
Sintering Lattice Grain Grain
Density Crystallite Grain Relaxation
temperature parameter resistance Capacitance
(gm/cm3) size (nm) size (nm) time (τ) msec
(0C) (Å) (Rg) KΩ (Cg) nf
800 3.35 32 8.391 117 43.6 22500 1.93
900 3.41 34 8.393 162 43.6 16800 2.6
1000 3.7 35 8.392 207 18.9 3240 5.82
1100 3.82 37 8.392 321 7.56 327 23.1
1200 4.01 39 8.394 508 2.81 47.7 58.8

(a) (b) (c) (d) (e)

FIGURE 3.(a-e) SEM images of Ni0.5Zn0.5Fe2O4 sintered at (a) 800oC, (b) 900oC, (c) 1000oC, (d) 1100oC, and (e) 1200oC.

020035-3
 Complex impedance spectroscopy is very important tool to understand the electrical properties of poly
crystalline spinel type materials [21]. This is used to find grain, grain boundary resistance and relaxation time etc. In
general polycrystalline ferrites have contributions from grain and grain boundary effects with two semi circles and
high frequency side corresponding to grain resistance. Low frequency region belong grain boundary resistance. The
complex impedance spectra of poly crystalline ferrites can be calculated by using the standard relation [21].

ோ
Z* = Z'+iZ" =
ሺଵା୧ωτሻ
ோ ωோ మ ஼
Z' = and Z" =
ଵାሺனୖେሻమ ଵାሺωୖେሻమ

Where Z' is real part of impedance, Z" is imaginary part of impedance, ω is angular frequency, and τ is
relaxation time (τ=RC). The variation of frequency (log f) with real part of impedance (Z') indicates that the
magnitude of Z' decreases that increasing frequency and sintering temperature were shown in figure 4(a). The Z'
values merge to high frequency region due to release of space charge with rise of sintering temperature [22] this may
be due to change in a.c conductivity in high frequency region. The variation of frequency with imaginary part of
impedance Z" is shown in figure 4(b). The curves in graph exhibit relaxation frequency fmax. These curves are
shifted towards high frequency region with increase of frequency and sintering temperature. This indicates that the
decrease of relaxation time τ. Then the domination space charge polarization occurred [23]. The room temperature
Cole-Cole plots of Z' and Z" was shown in figure 4(c). The impedance behavior of the samples is explained by using
an equivalent circuit as shown in figure 4(d). From figure 4(a) single semicircular arc was observed in high
frequency region which is corresponds to grain contribution C g = 1/Rgωg where Cg and Rg capacitance and resistance
of the grain. The values of Cg and Rg are reported in table 1. The relaxation time and grain resistance were decreased
with increasing of sintering temperature.
25.0M
350.0k 800 150.0k 800 150.0k
300.0k 900 10.0M 14.0M 800
120.0k
900 900 120.0k
20.0M 250.0k 1000 1000 1000 90.0k
1100 90.0k 12.0M
8.0M 1100

Z''
200.0k 1100 60.0k
1200
Z"

60.0k 1200 1200 30.0k

150.0k 10.0M
Z'

15.0M 0.0
100.0k 6.0M 30.0k 0 100k 200k 300k

50.0k 8.0M Z'

Z"

0.0
Z"

10.0M
Z'

0.0 4.0M 0 1 2 3 4 5 6 7 8 6.0M

0 1 2 3 4 5 6 7 log f (Hz)
5.0M log f (Hz) 2.0M 4.0M

2.0M
0.0 0.0
0.0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7 8 0.0 5.0M 10.0M 15.0M 20.0M 25.0M

log f (Hz) log f (Hz) Z'

(a) (b) (c) (d)

FIGURE 4.(a-d) Frequency variation real (a), imaginary (b) part of impedance, (c) cole-cole plots of Ni0.5Zn0.5Fe2O4 sintered
at different sintering temperatures and (d) equivalent circuit.

The complex electrical modulus study is introduced to understand the electrical relaxation in ionically and
electrically conducting materials. It is an advantage to suppressing the electrode polarizing effects [24-25]. the
complex electric modulus M* is calculated by using the following standard relation
M* = ‫ ܯ‬′ ൅ ‫ܯ‬′′ = jωC0Z*
ᇱ ′′
Where ‫ ܯ‬ൌ ߱‫ܥ‬଴ ܼԢԢ and ‫ ܯ‬ൌ ߱‫ܥ‬଴ ܼ′ are the real and imaginary parts of the complex electrical modulus
respectively and ‫ܥ‬଴ is the geometrical capacitance ‫ܥ‬଴ ൌ ߝ଴ ‫ܣ‬Τ‫( ݐ‬here A is the surface area of pellet, ߝ଴ is
permittivity of free space and t is thickness of the sample). Figure 5(a) and 5(b) shows that the real and imaginary
part of complex modulus spectra of Ni0.5Zn0.5Fe2O4ferrite sintered at 8000C, 9000C, 10000C, 11000C, and 12000C
temperatures. From figure 5(a) the variation of real part of complex modulus with frequency at room temperature.
Low frequency side the ‫ ܯ‬ᇱ have very low value and it is increased with increasing of frequency and also it saturate
at high frequency region. The dispersion is shifted to high frequency side with increasing of sintering temperature.
From figure 5(b) the variation of imaginary part of complex modulus with frequency at room temperature from
figure which is clearly observed that ‫ܯ‬ᇱᇱ have maximum value in low frequency side and the peak frequency is
shifted with increasing of frequency and sintering temperature. Which indicates that the transition from long range
to short range mobility with increasing of frequency. From figures of Z" and ‫ ܯ‬ᇱᇱ indicates that non-Debye type
relaxation of the sample.

020035-4
 0.0030 0 0
800 C 0.00035 800 C
0 0
900 C 900 C
0.0025 0
1000 C
0
1000 C 0.00030 0
0 1100 C
1100 C 0
0.0020 0 0.00025 1200 C
1200 C

0.0015 0.00020

M"
M'

0.00015
0.0010
0.00010
0.0005
0.00005
0.0000 0.00000

-1 0 1 2 3 4 5 6 7 8 -1 0 1 2 3 4 5 6 7 8

Log f (Hz) Log f (Hz)

(a) (b)
FIGURE 5.(a-b) Variation of (a) real part and (b) imaginary part of complex electrical modulus with frequency at room
temperature of Ni0.5Zn0.5Fe2O4 ferrite.

CONCLUSIONS
Ni0.5Zn0.5Fe2O4 is synthesized by citrate gel auto combustion method and sintered at various temperatures and
conforms that the single phase spinel structure from XRD. Raman spectroscopy of all sintered samples indicated that
are belongs to Fd3m space group. The grain resistance and grain capacitance were reported from impedance data
indicating the non-Debye type relaxation nature of the sample.

ACKNOWLEDGMENTS
The authors are thankful to University Grants Commission, India, for providing financial assistance through
UGC Major Research Project F.No.42-824/2013 (SR) Dt.22-03-2013.

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