International Journal of Theoretical and Applied Science 3(2): 10-12(2011) ISSN No.

(Print) : 0975-1718
ISSN No. (Online) : 2249-3247

Micro-Structural Studies of Gadolinium Doped Cobalt Ferrites

P. Kumar, J. Chand, Satish Verma, M. Singh
Department of Physics, Himachal Pradesh University, Shimla, (HP)

(Received 19 October, 2011, Accepted 8 November, 2011)

ABSTRACT : CoFe2-xGdx O4; x = 0, 0.1, 0.15, and 0.2 were prepared using coprecipitation method. All the samples
were sintered at 500ÚC. The structure has been studied using XRD, TEM and EDAX. Effect of Gd doping on
crystal structure has also been studied and discussed. The particle size has been estimated using Scherrer
equation. All the peaks in XRD patterns are narrow which means that particles are in nano range. The structure
3+
inferred from the XRD is cubic. Gd being larger in size prefers octahedral site.
Keywords: Micro-structural; Ferrites; Coprecipitation.

I. INTRODUCTION are among the most widely used magnetic materials having
low cost, high performance for high frequency applications.
Control and understanding of matter at dimensions of Spinel ferrites are cubic close packed cage of oxygen ions
roughly 1-100 nm has generated a lot of interest in recent occupying the tetrahedral (A) and octahedral (B) interstitial
years. These materials have many astonishing properties in sites, which interact with each other through the
contrast to their bulk counterparts. The different properties superexchange interactions (JAB) and the intra-exchange
of these novel materials are ascribed to their characteristic (JAA, JBB). All these interactions are negative and hence
structural features in between the isolated bulk macroscopic attractive. The order of magnitude of these interactions is
and atoms the materials. These typical properties of nano |JAB| >|JAA| >|JBB|, when A and B are totally magnetic. A
sized materials is due to quantum size effects and the large selective magnetic dilution is very important in ferrites [5].
surface area of magnetic nanoparticles surprisingly change Small amounts of rare earths can be used for this purpose
some of the magnetic properties and also exhibit leading to control electrical , dielectric and magnetic
superparamagnetism among other phenomena. It has been properties of ferrites. The properties of ferrites are very
confirmed that the refinement of the grain size is an effective sensitive to the processing techniques. The various
way of reducing the noise [1]. In general; spinels are processing techniques, which are used for the synthesis of
classified as normal, inverse, and mixed. It has been reported spinel ferrite powders, include microwave refluxing,
that the presence of nonmagnetic ions reduces the magnetic hydrothermal, sol gel, co-precipitation and spray pyrolysis.
interactions between the two interstitial sites, causes Cobalt ferrites prepared by different methods have different
decrease in hyperfine magnetic fields, and hence changes magnetic properties.
the magnetic and electronic properties. These effects are
A molecule of spinel ferrite can be written as DT2O4,
particularly apparent in the Mossbauer studies. For all the where D is divalent ion and T is trivalent ion. The both the
magnetic nanoparticles there is a critical size dimension (Dsp) cations can occupy either tetrahedral (A) site or the
below which it will be superparamagnetic with no hysteresis octahedral [B] site. Hence the cation distribution can be
and no remanence. So the useful particle size should be in expressed as (D1– T) [DT 1-] O4. Here  is known as
the range Dsp< D < Dsd where Dsd is single domain size [2]. degree of inversion. If = 1, the structure is called inverse
Cobalt ferrite is a ferrimagnetic oxide which have large spinel and if  = 0 it is normal spinel. For 0 <  > 1 the
magneto crystalline anisotropy, high coercivity, moderate spinel structure is referred to as mixed.
saturation magnetization, high chemical stability and high Many researchers have studied rare earth doped cobalt
mechanical hardness. Nano scale cobalt ferrite fabrication ferrites using different methods. Gadolinium-doped CoFe2O4
has interested many researchers because of its physical nanoparticles are discussed by Jianhong Peng et al [6] and
properties such as magneto-optical and superparamagnetism. R.P. Pant et al [7].
These interesting physical properties are result of strong
quantum confinement effect which is not the case with bulk Jianhong Peng et al [6] showed that doping cobalt
material [3, 4]. Synthesis of nanoparticles, especially spinel ferrites with gadolinium have a strong influence on saturation
ferrites, characterized by a low size distribution is important magnetization and coercivity. Ben Tahar et al [8] found a
due to their remarkable electrical and magnetic properties significant increase in saturation magnetization of cobalt
and wide practical applications in information storage ferrites by doping with Gd3+ and Sm3+ .
systems, ferro-fluid technology, magneto-caloric refrigeration Jing Jiang et al showed that properties of ferrites are
and magnetic diagnostics. They are also used in radio 3+
strongly affected by La content [6]. The saturation
frequency circuits, high quality filters, rod antennas, magnetization decrease, while coercivity increases with
transformer cores, high speed digital tapes. Cobalt ferrites increasing the La3+ content.
 Kumar, Chand, Verma and Singh 11
From above discussion it is clear that cobalt ferrites
are very useful and it is of interest to investigate the effect
of rare earth ions on the properties of cobalt ferrites. Our
interest is to modulate the properties of cobalt ferrites. Our
work is to produce lanthanum and gadolinium doped cobalt
ferrites which have high resistivity and are single phase.
Our work will be intended to synthesize nano particles with
desired properties like magnetic moment, high permeability,
resistivity, high dielectric constant, low dielectric loss.
Fig. 1. XRD patterns of nano-crystalline CoGdx Fe2-xO 4
II. MATERIAL AND METHODS for x = 0, 0.10, 0.15.

Gd-Co ferrite of composition CoGd0.1Fe1.9 O4 was Table 1. Particle size for CoFe2-xGdx O4; for x = 0, 0.1,
prepared by the co-precipitation method. The materials used 0.15, and 0.2 nano particles.
were cobalt nitrate (97% Merck, India), iron nitrate (98% Composition (CoFe2-xGdx O4) Particle size(nm)
Merck, India), gadolinium nitrate (Merck, Germany) and
X=0 49.84
sodium hydroxide (96% Merck, India). One molar solution
of these materials was made with distilled water. Sodium X = 0.05 42.56
hydroxide (70 ml) was taken from one molar solution in X = 0.1 35.01
approximately 1760 ml of distilled water to have the
X = 0.15 31.09
concentration of 0.37 mol/l and heated to boiling. Cobalt
When some Fe ions are substituted by Gd3+ ions, the
3+
nitrate, gadolinium nitrate and iron (III) nitrate were taken
from their molar solution in accurate stoichiometric lattice parameters are changed. The lattice parameters may
proportions. These solutions were poured as quickly as increase or decrease (Table 2) depending upon the result of
two effects. The large size of Gd3+ tries to increase the
possible into the boiling solution of NaOH under vigorous
lattice parameter and the strain produced by its substitution
stirring produced by the glass mechanical stirrer (500 rpm).
in the cell, tries to decrease it. This has been investigated
Mixing is very important; otherwise segregation of phases by many researchers [10, 11]. This explains the increase in
can take place. After co-precipitation, pH is set to 12.5–13. lattice parameter up to x = 0.15 and decrease in lattice
The beaker was covered to diminish the evaporation of the parameter thereafter for x = 0.20.
solution. Reaction was allowed to continue for 30–40 minute
at temperature 95–100°C under vigorous stirring. The beaker
Table 2. Variation of lattice parameter with dopant
concentration.
was cooled to ambient temperature and particles precipitate.
Total volume was reduced to 500 ml by the aspiration of Composition Lattice Parameter
supernatant. Precipitates were washed with distilled water X = 0.05 8.319 Å
8.329 Å
(900 ml) and centrifuged at 7000 rpm for 10 minutes. The
X = 0.10
residue was dried and powdered. These samples were
sintered in air at 500°C at a heating rate of 350°C/h for 3h X = 0.15 8.332 Å
and were subsequently cooled. These samples were then X = 0.20 8.323 Å
sintered in air at 500°C for 3h and were subsequently cooled.
XRD was taken with XPERT-PRO system.

III. RESULT AND DISCUSSION

Fig. 1 shows the XRD patterns of nano-crystalline
CoGdxFe2-xO4 for x= 0, 0.10, 0.15. Particle size as estimated
from Scherrer equation [9] is listed in Table 1. Particle size
decreases continuously with Gd3+ ions doping.

Fig. 2. TEM of CoFe2-xGdx O4; for x = 0.1

12 Kumar, Chand, Verma and Singh

Fig. 2 shows TEM images of the samples for x = 0.1. IV. CONCLUSIONS
There are no isolated particles and particles prefer to be in
groups and agglomerates of many particles are clearly seen. The lattice parameter increases up to a concentration
This agglomeration shows that particles are attracted towards of X = 0.15 while after that the lattice parameter starts
each other indicating their magnetic character. decreasing. All the gadolinium added does not replace iron
Fig.3 shows the diffraction Tem image. Carefully seen as is clear from the EDAX data. Particle size goes on
the periodic arrangement of the constituents is visible. decreasing with gadolinium doping. All the particles are of
Crystal structure of the prepared ferrites is inferred from uniform size. The magnetic character of the particles is clear
this figure. from the agglomerates which are formed due to the attraction
among themselves. The diffraction Tem image shows the
periodic arrangements of the constituents. This clearly shows
the crystal structure of the ferrite powder.

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Fig. 4. EDAX-Energy Dispersive x-ray for CoFe2-xGdx O4;

x = 0.1