Journal of Magnetism and Magnetic Materials 374 (2015) 376–380

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Journal of Magnetism and Magnetic Materials

journal homepage: www.elsevier.com/locate/jmmm

Structural, electrical and magnetic characteristics of nickel substituted

cobalt ferrite nano particles, synthesized by self combustion method
Uday Bhasker Sontu n, Vijayakumar Yelasani, Venkata Ramana Reddy Musugu
Department of Physics, University College of Science, Osmania University, Hyderabad, Telangana State, PIN: 500007, India

art ic l e i nf o a b s t r a c t

Article history: Nickel-substituted cobalt ferrite nano-particles are synthesized using a self-combustion method.
Received 22 December 2013 Aqueous metal nitrates and citric acid form the precursors. No external oxidizing agents are used to
Received in revised form change the pH of the precursors; this resulted in a more environment friendly synthesis. Structural,
24 July 2014
magnetic and electrical characteristics of the nano ferrites are verified using X-ray diffractometer (XRD),
Available online 27 August 2014
VSM and impedance analyzer respectively. Phase formation, particle size, lattice parameter, X-ray
Keywords: density, saturation magnetization, coercivity, dielectric constant and electrical activation energy as
Self-combustion function of nickel substitution in cobalt ferrite are studied. It is shown here that the magnetic and
Nickel and cobalt ferrite electrical properties can be tuned by varying the nickel concentration.
Nano-magnetic properties
& 2014 Elsevier B.V. All rights reserved.
Inverse and mixed spinel phase
Dielectric constant
Activation energy

1. Introduction containing 32 O2  , 8 Ni2 þ /Co2 þ and 16 Fe3 þ ions. The lattice of

oxygen ions contains 64 tetrahedral and 32 octahedral vacancy
Nano-ferrites have drawn wide spread attention in the past few sites. 24 cations are distributed into these sites. The eight Ni2 þ
decades due to their technological importance. Applications of /Co2 þ and eight Fe3 þ cations occupy half of the octahedral sites
ferrites are in as diverse fields as catalysts [1], micro-wave devices and the other eight Fe3 þ ions occupy eight of the 64 tetrahedral
[2], high frequency transformer core, antenna material sand sites [13,14]. This forms the inverse spinel structure. In the mixed
magnetically-guided drug delivery devices [3–8]. Preparation spinel structures the number of Fe3 þ ions at octahedral sites
methods [9,10], doping and substitutions play a crucial role in increase, while that of the Fe3 þ ions at tetrahedral sites decrease
controlling the properties of ferrites. Among these magnetic because some divalent metal ions(Ni2 þ /Co2 þ ) enter into
materials, spinel-type ferrite nanoparticles, MFe2O4 (M ¼Mn, Co, tetrahedral sites.
Ni, Zn, Mg, Fe, etc.), have gained great interest because of their In this study we report an environmentally benign synthesis for
good electromagnetic performance and wide range of applications Co1  xNixFe2O4 nano particles. The ferrite powders are prepared by
in diverse fields. Soft magnetic properties, high electrical resis- the sol–gel self-combustion synthesis method. This method is
tance, low eddy-current loss, high permeability at high frequencies simple and results in stoichiometrically good compounds. There
make nickel ferrite technologically important material. Nickel- are several reports on use of this method of preparation with
based mixed ferrites are also investigated extensively [11,12]. precursor solution changed to pH values 7, 9, 10 and 11 [34]. Here
Cobalt ferrite with mixed spinel structure has high coercivity we are reporting the self-combustion method without altering the
and lower resistivity. Bulk nickel ferrite has inverse spinel struc- pH value of the precursor solution. Structural, electrical and
ture. Nickel substitution into cobalt ferrites allows us to tune the magnetic characterization studies are done on the prepared ferrite
magnetic and electrical properties of ferrites as per the desired nano-particles. This method of preparation is more environment
application. Ni–Co–Fe alloys are reported to be magnetostrictive friendly as it produces lesser amount of pollutant gases during the
and used as magneto resistance sensors. These can also be used synthesis.
for thin film magnetic heads for high-density recording [34].
The spinel structure is face-centered cubic with each unit cell
2. Experimental

Nickel-substituted cobalt Ferrite (Co1  xNixFe2O4/x ¼0, 0.25, 0.5,

n
Corresponding author. 0.75and 1.0) nano-particles are prepared by sol–gel auto-
E-mail address: [email protected] (U.B. Sontu). combustion method. All of the chemicals used are of analytical

http://dx.doi.org/10.1016/j.jmmm.2014.08.072
0304-8853/& 2014 Elsevier B.V. All rights reserved.
 U.B. Sontu et al. / Journal of Magnetism and Magnetic Materials 374 (2015) 376–380 377

grade and used without further purification. The aqueous solu- ‘a’ is calculated using the relation
tions of Fe(NO3)3  9H2O, Ni(NO3)2  6H2O and Co(NO3)3  6H2O are qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 2 2
taken in stoichiometric ratio, form the precursor material. Citric a ¼ d ðh þ k þl Þ ð1Þ
acid in 2:1 M ratio to the metal ions is used as chelating agent and
fuel for self-combustion. For preparing the sample powders, Where,d'is the inter planar distance and (hkl)are Miller indices.
aqueous ferric nitrate solution taken in a beaker is placed on a The correction to the lattice parameter is done employing the
hot plate with magnetic stirrer. The solution temperature is Nelson–Riley scheme. The Nelson–Riley function NR¼ 1/2(cos2θ/
maintained at 80 1C and stirred for about half an hour. Nickel sinθ þ cos2θ/θ) is plotted against the lattice constants, calculated
nitrate solution, cobalt nitrate solution and citric acid solution are from single reflection peaks, and is extrapolated to θ ¼901.
added one after the other, with a gap of half an hour to the ferric The X-ray density (the theoretical density) ρx was calculated
nitrate solution. The complex solution of metal nitrate and citric using the relation
acid is stirred further for evaporation of water molecules and 8M
gelation of the solution. The viscous gel is transferred to a ρx ¼ ð2Þ
N A a3
porcelain dish. The temperature of the dish is maintained at about
200 1C for half an hour in the open air. The gel starts combusting where M is the molar mass of the ferrite, ‘a’ is the lattice
and the combustion continues for half an hour. After combustion a parameter, and NA is Avogadro's number.
puffy solid remains. Before using for characterization, the puffy The particle size ‘D’ was determined using Debye–Scherer
solid is grinded to powder and sintered at 600 1C for 2 h with a formula [17].
heating rate of 10 1C per minute. 0:9λ
The structural characterization is done with X-ray diffractometer D¼ ð3Þ
β cos θ
(XRD) on the sintered powders. XRD is done using Phillips X'Pert
diffractometer for the diffraction angle (2θ) ranging from 101 to 801 where λ is the wavelength of the Cu Kα (1.5406 Å), β is the full-
with a step size of 0.021. A continuous scan with step time of 0.15 s width at half-maximum (FWHM) of the (3 1 1) peak in radians,
is performed. The measurements are taken at 25 1C with Cu as and θ is the Bragg's angle.
anode material and the Kα radiation of wave length 1.5406 Å as The tabulated particle size, as in Table 1, indicates that the
the incident/diffracting wave. Particle size is calculated using variation in the chemical content of the sample does not affect
Debye–Scherer formula. Lattice parameter, X-ray density is deter- the particle size of the formed sample. The particle sizes of the
mined for these powders. These powders are pelletized with samples fall in a very small range from 38 nm to 50 nm. The nano-
PVA binder and 4 t pressure. The pellets are heat treated for 2 h ferrites prepared at considerably low temperatures of about 200 1C
at 350 1C and further at 600 1C for 1 h for the removal of water and sintered at 600 1C for just 2 h are showing good crystallinity
and carbon compounds. Heating rate is maintained at 10 1C per and agreeing well with JCPDS data. As the ionic radius of Ni2 þ is
minute. Samples are allowed to cool to room temperature within smaller (0.74 Å) than that of Co2 þ (0.78 Å), we see that the (3 1 1)
the furnace. Magnetic characterization is carried out on the solid peak position is continuously shifting towards lower angles
samples with Lake Shore Cryotronics VSM (Vibrating Sample Mag- suggesting the reduction in the ‘d’ spacing. The lattice parameter
neto meter). Magnetic field is swept in the range from  5000 kOe to
5000 kOe at room temperature. Temperature dependent DC con- x=0
900
ductivity is measured on the pelletized samples with a Model 196, x=0.25
Keithley digital multimeter. The samples are silver coated for a good x=0.50
x=0.75
contact and heat treated before the conductivity studies. AC con- x=1.00
Intensity in AU

600
ductivity measurements of the ferrite samples are performed in the
frequency range from 100 Hz to 20 MHz at room temperature using
Wayne Kerr 6500B series, precision impedance analyzer. The instru-
300
ment is calibrated for wire capacitance compensation before usage.
The sample testing is done for an applied voltage of 1.00 V signals
without any bias voltage.
0

20 30 40 50 60 70
3. Results and discussion
2θ
3.1. Structural characterization Fig. 1. XRD of Co1  xNixFe2O4.

Spinel structure of annealed powders of nickel-substituted

cobalt ferrite (Co1  xNixFe2O4 / x¼ 0, 0.25, 0.5, 0.75, 1.0) nano- Table 1
particles prepared by sol–gel auto-combustion has been confirmed Physical properties of cobalt and nickel-substituted cobalt ferrites.
by the XRD. Fig. 1 shows the XRD of (Co1  xNixFe2O4 / x¼ 0, 0.25,
Particle size Lattice 2θ of (3 1 1) X-ray density
0.5, 0.75, 1.0). Nickel-rich ferrite nano powders show extra peaks Sample
(nm) parameter (Å) peak (Kg/M3)
of Fe2O3. These extra peaks may be because of the combustion
taking place in an oxygen-rich environment and small percentage CoFe2 O4 35.24 8.416 35.5 5229.53
of the sample is not reduced from Fe2O3 to Fe3O4. Nickel is less Co0.75
Nio.25Fe2 49.34 8.407 35.41 5244.12
oxidizing than cobalt and so this is found to be common, in
O4
particular for nickel-rich samples prepared at low sintering tem- Coo.5 Nio.5Fe2
38.02 8.380 35.26 5286.99
peratures. Similar reports are found in the literature [15,16]. All the O4
diffraction peaks of ferrite samples are indexed on the basis of the Coo.25
face centered cubic unit cell (JCPDS no. 00-022-1086 for CoFe2O4 Nio.75Fe2 49.52 8.374 35.12 5303.41
O4
and JCPDS no.00-044-1485 for NiFe2O4). All the samples are found NiFe2 O4 38.12 8.347 35.01 5354.19
to have Fd-3 m space group symmetry. The cubic lattice parameter
378 U.B. Sontu et al. / Journal of Magnetism and Magnetic Materials 374 (2015) 376–380

100
8.43

Lattice parameter in A0
90

Partice size in nm
80
70 8.40
60
50
40 8.37
30
20
10 8.34
0 0.25 0.50 0.75 1.0 0 0.25 0.50 0.75 1.0
Composition x Composition x
(311) pea position in degrees

35.6

X-Ray density in kg/m3

5340
35.4

35.2 5280

35.0 5220
0 0.25 0.50 0.75 1.0 0 0.25 0.50 0.75 1.0
Composition x Composition x
Fig. 2. Variation of (a) particle size ,(b) lattice parameter, (c) (3 1 1) peak position and (d) X-ray density with Nickel concentration(x) in Cobalt Ferrite.

‘a’ of this cubic spinel ferrite is calculated from the available peaks 80
of the XRD and Nelson–Riley function is used to get the corrected
60 x=1
value of the lattice parameter. The lattice parameter value
decreases from 8.416 Å for cobalt ferrite to 8.347 Å for nickel 40
x=0.75
ferrite with increasing substitution of Ni for Co. X-ray density of x=0.5
M in emu/gm

the sample is also calculated and shown in Table 1. X-ray density 20 x=0.25
shows a continuous increase from the cobalt ferrite to nickel x=0
0
ferrite as expected, due to the smaller radius of nickel atom in
comparison to the cobalt atom. The graphs corresponding to -20
particle size variation, lattice parameter variation, X-ray density
variations with the nickel substitution are shown in Fig.2. -40

-60
3.2. Magnetic characterization
-80
Ferrites are anti-ferromagnetic in nature, a super-exchange -6000 -4000 -2000 0 2000 4000 6000
interaction between magnetic cations mediated by oxygen atoms Applied field in Oe
binds all the cations of similar site location (octahedral ‘B’ site) to Fig. 3. M–H Loops of the samples Co1  xNixFe2O4.
one direction. Similarly for the cations of the other site (tetrahe-
dral ‘A’ site) into the opposite direction. Total magnetic moment of
the cell is generally the difference between net magnetic moment Ms is the saturation magnetization;
because of ‘B’ site cations ‘MB’ and magnetic moment because of MM s
cations at ‘A’ site ‘MA’. Theoretical values of magnetic moment per nB ¼ ð5Þ
mB N A
formula unit for inverse spinel cobalt and nickel ferrites are 3mb
and 2mb, respectively. where mB  nB is unit cell magnetic moment, NA is Avogadro's
Co1  xNixFe2O4 samples at room temperature have been char- number, mB is Bohr magneton, M is the molecular weight of the
acterized for their magnetic properties. The maximal applied composition and Ms is the saturation magnetization;
magnetic field is low (5000 Oe) in comparison to that required K ¼ μ0 H c M s =2 ð6Þ
(20,000–30,000 Oe) [26] for complete magnetic saturation in the
case of cobalt ferrites. From Fig. 3 it is evident that all the samples where K is magneto crystalline anisotropy constant, m0 is vacuum
are exhibiting hysteresis. Sample x¼ 1.0 (pure nickel ferrite) is permeability and Hc is the coercivity.
getting completely saturated for the applied field and other The reported values of the bulk saturation magnetization for
samples have not attained their saturation values in the applied cobalt and nickel ferrite in the inverse spinel state are 80.8 and
field range. 55 emu/g[26,27], respectively. The saturation magnetization
Squareness (S), unit cell magnetic moment (nB, in Bohr mag- values for our pure cobalt and nickel ferrite samples determined
netons) and anisotropy constant (K) are calculated using the from our findings are 60.5 and 25 emu/g (Table 2). From Fig. 3 we
relations: see that the tail of magnetization curve does not saturate for cobalt
containing samples. This is evident from the M–H loops in Fig. 3.
S ¼ M r =M s ð4Þ
The unsaturated magnetization is due to the insufficient magni-
where S is the squareness, Mr is the remanent magnetization and tude of the applied field.
 U.B. Sontu et al. / Journal of Magnetism and Magnetic Materials 374 (2015) 376–380 379

Table 2 8
Magnetic properties of cobalt and nickel-substituted cobalt ferrite.

Co1  xNixFe2O4 Hc Mr Ms S squareness nB K (Anisotropy

(Oe) emu/g) (emu/g) (Mr/Ms) (mb) constant)
(erg/cm3)

x-0 1305 36 60.5 0.59 2.54 0.05 6

log ρ
0.25 1080 28.5 49 0.58 2.06 0.033
0.5 855 20 40 0.5 1.68 0.022
0.75 685 20.8 40 0.52 1.68 0.017
1 305 10.8 25 0.43 1.05 0.005 x=0.00
x=0.25
x=0.50
4 x=0.75
Table 3
x=1.00
Activation energies of cobalt and nickel-substituted cobalt ferrites.

Composition (x) 0 0.25 0.5 0.75 1.0

1.6 2.4 3.2
Activation energy (eV) 0.549 0.551 0.556 0.643 0.788
1000/T

Table 2 gives the data derived from the M–H loops. Cobalt Fig. 4. Log(ρ) v/s 1/T for Co1  xNixFe2O4.

ferrite(x ¼0) has shown a magnetic moment of 60.5 emu/g with a

magnetic moment of 2.54mb per unit cell, even at low applied
magnetic field. Rather high magnetic value at low fields may be 0.85
because of mixed spinel nature of the nano ferrites instead of the
0.80
inverse spinel structure for cobalt rich ferrites. The decrease in
saturation magnetization at higher nickel contents is directly
Activation energy in eV
0.75
related to the lower magnetic moment ions (2mb) (Ni2 þ ions)
replacing higher magnetic moment ions (3mb) (Co2 þ ions) at the 0.70
octahedral site. This affects the net magnetic moment per cell
which in turn decreases Ms with the increase of nickel content. 0.65

Very low saturation magnetization (Ms) of the sample x ¼1, maybe

0.60
because of the presence of impurity α-Fe2O3 phase [28] as a result
of high rate of sintering (about 10 1C/min). The saturation magne- 0.55
tization also depends on other factors like that of preparation
method [30], sintering temperature [29] and nano-particle size 0.50
0.00 0.25 0.50 0.75 1.00 1.25
[18,26] (Table 3).
Composition (x)
The decrease in coercivity and remanence may be attributed to
the reduction in magneto crystalline anisotropy with increasing Fig. 5. Variation of Activation energy with Nickel composition in Co1  xNixFe2O4.
the Ni content. Nickel ferrite has lower magnetic anisotropy
(  0.7  105 erg/cm3) than Cobalt ferrite (2.6  106 erg/cm3). samples. Polaron is a deformation in the crystal lattice because
Therefore nickel addition to the cobalt ferrite reduces the mag- of electron–lattice interaction. This polaron shifts to an adjacent
netic anisotropy of the sample. From these observations it may be lattice site which has the same element in a different ionization
concluded that as the Ni composition (x) is increasing from 0 to state, as explained in Verwey mechanism [21]. The existence of
1 in the cobalt ferrite the coercivity is found to decrease gradually. polaron hopping is discussed by Kinger and Mott et al. [22,23]. The
This means that the ferrite material becomes softer as regards to hopping mechanism in this case can be given as Fe3 þ þe  -Fe2 þ ,
its magnetic properties. Also in nickel-rich compounds x¼ 0.75 due to electron hopping for Fe ions at octahedral site and hole
and x ¼1.0, the presence of hematite (α-Fe2O3) impurity phase hopping for Co, Ni ions as (Ni/Co) 2 þ þhole-(Ni/Co)3 þ . As the
may also be a reason for reduced remanence [28]. hole mobility is less in comparison with that of electrons, electron
conductivity dominates over hole conductivity. Octahedral ‘B’ site
3.3. Electrical characterization cations only contribute in the hopping process as the B–B site
distance is 0.292 Å whereas it is 0.357 Å for A–A site hopping.
To study the temperature dependent DC conductivity the Even at ‘B’ site, the hopping between similar atoms requires less
samples are silver coated for a good metallic contact. The con- energy than between dissimilar atoms [24]. In ferrites the net
ductivity study is performed in the temperature range of 300– charge carrier concentration remains almost constant throughout
600 K. The following Arrhenius equation. (7) is used for the DC the temperature range [25], but the hopping frequency of charge
conductivity of ferrites. carriers increases with temperature. This leads to increase in the
conductivity of ferrites with the temperature.
ρ ¼ ρ0 xeΔE=kT ð7Þ
As Ni2 þ substitution increases in the sample, the number of
here ΔE is the activation energy, ‘k’ is the Boltzmann constant and Co ions at ‘B’ sites in the sample is reduced. As Ni2 þ has higher
2þ

T is the temperature in Kelvin scale. Fig. 4 shows the plot of Log(ρ) preference to octahedral site than Co and Fe ions, Ni2 þ occupies the
v 1/T for Co1  x NixFe2O4. The DC electrical conductivity in Ferrites octahedral ‘B’ sites. Variation of activation energy with increase in
is supposed to be having three regions. Impurity region at low the Ni composition in cobalt ferrite is plotted in Fig. 5. Increase in the
temperatures, followed by conductivity due to polaron hopping Ni2 þ concentration increases energy of hopping because the
and the third region is because of magnetic ordering [19,20]. Ni2 þ oxidation tendency is less than that of Cobalt. Higher energies
Impurity conductivity because of impurities and oxygen vacancies of hopping result in higher activation energies. Initially Ni2 þ sub-
are predominant at low temperatures, while the polaron hopping stitution may be taking place only for the cobalt ions at ‘B’ sites. Lesser
starts at about 340 K and extends to about 550 K for all the oxidation tendency of Ni2 þ would increase activation energy but a
380 U.B. Sontu et al. / Journal of Magnetism and Magnetic Materials 374 (2015) 376–380

100 in nickel substitution is continuously reducing the dielectric

90 properties. Pure nickel ferrite dielectric constant value is less than
that of pure cobalt ferrite.
80
x=0
70 x=0.25
x=0.50 4. Conclusions
60 x=0.75
50 x=1.00
ε'

Nickel substituted cobalt ferrite nano particles have been synthe-

40 sized using a self-combustion method at considerably low tempera-
30 tures (200 1C), without adding ammonia to the precursor solution.
20
Nickel substitution into the cobalt ferrite allow us to tune the
magnetic and electrical properties of the ferrite material from the
10
hard magnetic and lower resistivity cobalt ferrite to soft magnetic
0 and high resistivity nickel ferrites. Comparing the various composi-
1 2 3 4 5 6 7 8 tions of nickel substituted cobalt ferrites, the compound with a
composition of x¼0.25 shows high dielectric constant and low
Log f
activation energy and pure nickel ferrite with impure phase shows
Fig. 6. Variation Dielectric constant with log(f). lowest dielectric constant and highest activation energy.

reduced ‘B–B’ distance, due to smaller radius of Ni2 þ is reducing the

Acknowledgments
hopping energy. This keeps the net change in the activation energy to
be small. The same behavior is observed for x¼0.25 and 0.50
One of the author, S. UdayBhasker would like to thank Dr.
compositions. As the Ni2 þ substitution further increases, the Fe3 þ
Manivel Raja, Scientist, DMRL, Hyderabad., Telangana State., INDIA,
ions also get displaced from octahedral site to tetrahedral site leading
for initial VSM recordings and R.K.Kotnala from NPL New Delhi
to a more inverse spinel formation. Reduced Fe3 þ content at
India for VSM. M.V.R.R. thanks UGC, New Delhi for providing
octahedral sites decreases further the contribution of the electron
financial assistance in the form of project [UGC-MRP, F.No.41-907/
hopping. So for high Ni concentrations the activation energies are
2012 (sr)].
increased considerably. We can also propose that the small impurity
phase in the samples with higher Ni concentration may also be
responsible for reduced hopping frequency and increased activation References
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