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Synthesis, characterization and magnetic properties of CaFe2O4 nanoparticles

by solution combustion method

Article · February 2015

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 International journal of advanced scientific and technical research Issue 5 volume 1, January-February 2015
Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954

Synthesis, characterization and magnetic properties of

CaFe2O4 nanoparticles by solution combustion method

P. Shankar#1, Bhavyashri2, R.S. Raveendra3, A. Jayasheelan4 C.S. Prakash5,

B.M. Nagabhushana6, H. Nagabhushana7, B. Daruka Prasad8
1
Department of Physics, Sai Vidya Institute of Technology, Bengaluru - 560 064, India
1
Visveswaraya Technological University, Belagavi-590 014, India
2
Department of Physics, A.C.S. College of Engineering, Bengaluru -560 074, India
3
Department of Chemistry, Sai Vidya Institute of Technology, Bengaluru-560 064, India
4
Department of physics, Maharani’s science college for women Bengaluru-560 001, India
5
Department of Physics, SJC Institute of Technology, Chikkaballapura- 562 101, India
6
Department of Chemistry, M.S. Ramaiah Institute of Technology, Bengaluru - 560054, India
7
C.N.R. Rao Centre for Advanced Material Research, Tumkur University, Tumkur-572 103, India
8
Department of Physics, B.M.S. Institute of Technology, Bengaluru - 560 064, India

ABSTRACT

In the current paper we focused on the synthesis and characterization of solution combustion
derived CaFe2O4 nanoparticles prepared by using Fe(NO3)3 as oxidizer and glycine as fuel at the
temperature of 500C. The prepared sample was calcined at 900C for 2 hours. The
characterizations of sample were analyzed with powder X-ray diffraction (PXRD), scanning
electron microscopy (SEM), Fourier Transform infrared spectroscopy (FT-IR) and ultraviolet
visible spectroscopy (UV-Vis). PXRD results show that the CaFe2O4 nanoparticles crystallizes
and phase is formed at 900 C and the phase is identified to be orthorhombic CaFe2O4. (Matched
with ICDD card number 72-1199) with space group Pnam (62) and cell parameters a=9.23000 Å
b=10.70500 Å and c=3.02400 Å. The average crystallite size is ~ 16-20 nm which is calculated
by Debye-Scherer’s formula. SEM micrographs points to the formation of spherical like
structure. The FT-IR spectrum confirms the M-O bond formation and purity of the product. The
sample calcinated at 900 ºC exhibited mixed characteristics of paramagnetic and ferromagnetic
properties.

Key words: Combustion, Orthorhombic, Debye- Scherer, spherical

# Corresponding Author: Tel: +91 9740145249 (M)

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International journal of advanced scientific and technical research Issue 5 volume 1, January-February 2015
Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954

INTRODUCTION

Recently magnetic nanoparticles of spinel ferrites were focused by many researchers

because of their interesting electrical and magnetic properties. Spinel type oxides with the
general formula AB2O4[1]. Ferrites are iron based oxides with technologically fascinating
magnetic properties, making them a prominent category in magnetic materials. The ferrite
particles in nano-regime with significant change of physical properties provide more advantages
over the bulk ferrites. The structural and electromagnetic properties are thus in fact size
dependent and highly sensitive to the method of preparation as well. In the nano regime ferrites
were found to have undergone changes in magnetic properties due to super paramagnetism and
surface spin effects until the stable magnetism occurs below the blocking temperature [2, 4]. The
CaFe2O4 type structure includes edge and corner sharing BO6 octahedral, constituting a very
distinctive network similar to the one formed in perovskite related compounds. This structural
network suggests that interesting physical properties may exist in the CaFe2O4 type compounds,
where the B-site atoms are transition metal magnetic elements, such as high-TC
superconductivity in cuprates, quantum magnetic characters in ruthenates, strongly correlated
features in manganates [5].

In comparison with other ferrites such as MnFe2O4, NiFe2O4, ZnFe2O4, CoFe2O4 and
CuFe2O4, calcium ferrite has a significant advantage; it is biocompatible and eco-friendly due to
the presence of Ca2+ instead of heavy metals [6]. The prototype CaFe2O4 crystallizes in an
orthorhombic structure with lattice constants a = 9.217Å, b = 10.702Å, and c = 3.018Å, (space
group: Pnam), (# 62, Z = 4) made up of distorted FeO6 octahedra sharing edges and corners, and
eight-fold coordinated calcium atoms TN=160 K the magnetic moments of Fe3+ (S=5/2) order
antiferromagnetically. The structure, magnetic and thermodynamic properties of CaFe2O4 have
been studied in number of experimental works, however, there are scarce data on the electronic,
transport and optical properties [7].

Combustion synthesis has emerged as an important technique for the synthesis and
processing of advanced ceramics (structural and functional), catalysts, composites, alloys,
intermetallics and nanomaterials. In this method, the exothermicity of the redox (reduction–
oxidation or electron transfer) chemical reaction is used to produce useful materials. Combustion
synthesis processes are characterized by high-temperatures, fast heating rates and short reaction
times. These features make Combustion synthesis an attractive method for the manufacture of
technologically useful materials at lower costs compared to conventional ceramic processes [8,
9]. Nanocrystalline ferrites pursue wide applications in cutting edge areas such as high-density
information storage, in heat transfer devices, spintronics devices, magnetic hyperthermia,
biosensors, magnetic resonance imaging, microwave devices and ferrofluid technology. CaFe2O4
have considerable application in information storage devices, magnetic bulk cores, magnetic
fluids, microwave absorbers, catalysts and medical diagnostics [1-3].

MATERIALS AND METHODS

Commercially pure ferric nitrate (Fe(NO3)3, AR 99 % Nice), Calcium nitrate hexa

hydrate (Ca(NO3)2 6.H2O AR 99 % Aldrich), Glycine (C2H5NO2) AR 99 % Merck), were used
as such without further purification.

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International journal of advanced scientific and technical research Issue 5 volume 1, January-February 2015
Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954

SYNTHESIS OF CALCIUM FERRITE NANOPARTICLES

To synthesize CaFe2O4 nanoparticles solution combustion synthesis method was used

[10]. The stoichiometry of the redox mixture for combustion is calculated based on the total
oxidizing and reducing valencies of the oxidizer and the fuel using the concept of propellant
chemistry. Fe(NO3)3, Ca(NO3)2 6 H2O were used as oxidizer and C2H5NO2 as fuel. Precursor
mixture was magnetically stirred well in a crystalline dish for about 30 min with distilled water
to get homogeneous mixture, then it was introduced into the pre-heated muffle furnace at 500
10 C. The solution was boiled. The resulted viscous liquid gets auto ignited, which rapidly
proceeded throughout the entire volume forming a rich brownish powdered product. The overall
reaction can be written as,

18 Fe(NO3)3 + 9 Ca(NO3)2 + 40 C2H5NO2 → 9 CaFe2O4 + 56 N2 + 80 CO2 + 100 H2O --- (1)

CHARACTERIZATION TECHNIQUES

Solution combustion derived product was characterized by PXRD. Powder X- ray

diffraction patterns were collected on a Shimadzu XRD-700 X-ray Diffractometer with CuKα
radiation with diffraction angle range 2θ = 20º to 80º operating at 40 kV and 30mA. Product was
morphologically characterized by SEM analysis which was performed on a JSM-6490 electron
scanning microscope. The FT-IR studies have been performed on a Perkin Elmer Spectrometer
(Spectrum 1000) with KBr pellet technique in the range of 400-4000 cm-1. To calculate optical
energy band gap, UV-Vis spectrum was recorded using ElicoSL-210 UV-Vis spectrophotometer.
Magnetization data were collected for CaFe2O4 as a function of applied field of 100 G from 405
to 550 °C using a Guays Balance.

RESULT AND DISCUSSIONS

PXRD studies for phase formation and crystallite size:

The formation of nanocrystalline phase of prepared sample was confirmed by PXRD
measurements. The PXRD of as-formed sample show the amorphous nature of product. Whereas
the sample calcinated at 900C confirms the crystallinity of the sample with orthorhombic
CaFe2O4 (matched with ICDD card number 72-1199 with space group Pnam (62)) and cell
parameters a=9.23000 Å, b=10.70500 Å, and c=3.02400 Å. All the diffraction peaks can be
indexed to (2 2 0), (3 2 0), (0 4 0), (1 3 1) (3 1 1), (3 3 1), (4 0 1), (5 2 0), (2 6 0), (6 0 0), (1 7 0),
(0 2 2), and (0 4 2) reflections. The broadening of the reflections clearly indicates the inherent
nature of nanocrystals. Fig.1 shows the powder X-ray diffraction patterns of sample calcined at
900 C. Crystal packing diagram is shown in Fig. 2. The crystallite size is calculated from the
full width at half maximum (FWHM ()) of the diffraction peaks using Debye- Scherer’s method
[11] using the following equation,

…… (2)

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International journal of advanced scientific and technical research Issue 5 volume 1, January-February 2015
Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954

Where‘d’ is the average crystalline dimension perpendicular to the reflecting phases, ‘λ’ is the X-
ray wavelength, ‘k’ is Scherer’s constant (0.92), ‘β’ is the full width at half maximum (FWHM)
intensity of a Bragg reflection excluding instrumental broadening and ‘’ is the Bragg’s angle.
The calculated average crystallite size of the sample is found to be 16 -20 nm. The lattice and the
structural parameters of the CaFe2O4 nanoparticles are summarized in Fig-1. Packing diagram is
as shown in Fig-2.

(040)
(320)

(170)
(401)

(042)
(131)
(311)
Intesity (a.u.)

(331)

(520)

(022)
(600)
(260)
(220)

PDF No:72-1199

20 30 40 50 60 70 80
2 (Degree)
Fig 1: PXRD

Fig 2: packing diagram

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International journal of advanced scientific and technical research Issue 5 volume 1, January-February 2015
Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954

FT-IR spectroscopic studies

Fig. 3 represents FT-IR spectrum of the sample recorded to define the irrational
frequency of Metal–Oxygen and other bonds related to impurities present in the CaFe2O4. It can
be seen that no major impurity peaks were observed. Strong absorption bands at 468 cm-1 can be
assigned to the stretching vibration of Fe3+ in the octahedral site of spinal structure [12].

100
Transmittance (a.u.)

90

80

70

60 (468)

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)

Fig 3: FT-IR spectrum

UV-Vis spectroscopy studies
In order to determine the optical property, the UV-Vis absorption spectrum was recorded.
The sample shows a strong absorption peak (λmax) at 224 nm at the UV region. Fig. 4 shows the
UV-Vis absorption spectrum of sample calcined at 900 C. This can be attributed to photo
excitation of electron from valence band to conduction band.

(224)
Absorbance (a.u.)

220 240 260 280 300 320

Wavelength (nm)

Fig 4: UV-Vis spectrum

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International journal of advanced scientific and technical research Issue 5 volume 1, January-February 2015
Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954

Morphological analysis

Fig. 5 shows SEM micrographs of CaFe2O4 nanoparticles. Micrographs reveals that the
particles are spherically agglomerated having uniform size and distribution. Agglomerization
may be due to the magnetic dipole interaction between ferrite particles [13]. The particles are
having large number of voids due to the release of gaseous products.

Fig 5(a-c): SEM micrographs at different magnifications

Magnetic property

Magneto-structural correlations are one of the main foci of studying low-dimensional

magnetic materials. The reciprocal of susceptibility increases as the temperature increases [14,
15]. The graph for ferrite shows the susceptibility tending to infinity as the temperature moves
closer to or above the Curie temperature. The high temperature susceptibilities of the three
compounds were fit to the Curie–Weiss expression. The Curie constant values fall within the
expected range. The Weiss constant suggests the exchange between the described
antiferromagnetic chains is barely significant within experimental error.

17

As prepared
16 Calcinated compound

15

14
(1/ )

13

12

11

10 Curie Temperature = 513 C

400 420 440 460 480 500 520 540

Temperature (C)

Fig 6: Plot of reciprocal of susceptibility V/s temperature

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International journal of advanced scientific and technical research Issue 5 volume 1, January-February 2015
Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954

CONCLUSION

CaFe2O4 nanoparticles were successfully prepared by the simple solution combustion

method using ferric nitrate and calcium nitrate as oxidizer and glycine as fuel. Synthesized
product is well matched with ICDD card number 72-1199 and having orthorhombic structure.
Magnetic properties like variation reciprocal of susceptibility with temperature are analyzed
using Guays Balance. This work may be extended to study the electrical properties like AC
conductivity and DC conductivity and magnetic properties like hysteresis loop analysis for
obtaining the resourceful properties of CaFe2O4.

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