Indian Journal of Pure & Applied Physics

Vol. 48, August 2010, pp. 581-585

Effect of preparative conditions on magnetic properties of

CoFe2O4 nanoparticles*
Kinnari Parekh
Department of Physics, Indian Institute of Technology Gandhinagar, Chandkheda, Ahmedabad
E-mail: pkinnarih@[Link]
Received 24 September 2009, revised 29 January 2010; accepted 16 April 2010

Nanomagnetic particles of CoFe2O4 have been synthesized using chemical co-precipitation technique followed by
annealing, characterized and investigated by powder XRD and magnetic measurement tools. All samples of nano ferrites
synthesized at different annealing temperatures show single phase cubic spinel structure with particle size changes from 9.5
to 21 nm. The virgin curve of magnetic measurement exhibits superparamagnetic behaviour at room temperature which
changes to ‘S’ shape with increasing annealing temperature indicating change in soft magnet to pinning-type magnet. The
coercivity of the nano-cobalt ferrite particles has been found to increase with increase in annealing temperature.
Keywords: Magnetic nanoparticles, Superparamagnetic, Co ferrite

1 Introduction enormous application potentials of nanoparticles, the

Magnetic particles in nano-regime is an interesting demand of their manufacturing rises despite of
field of study because of its wide tunable applications persisting difficulties in larger-scale production.
as well as basic research understanding of the fastest The high coercivity fields revealed for magnetic
growing areas of researches in the field of nanoparticles system makes these materials
nanotechnology1,2. Their properties are significantly interesting for applications in the field of high-density
modified in comparison with those of the bulk magnetic media. So far, many elemental nanoparticles
counterpart. Some new magnetic properties and (Ni, Co, Fe) have been studied9,10, while studies on
phenomena, such as superparamagnetism, spin ferrite-based systems are still few in number. One
canting and core/shell structure, are characteristics of reason is that to obtain isolated ferrite nanoparticles is
only nanoscale magnetic materials. These properties often a crucial problem due to difficult control of the
depend on a number of factors such as composition, particle shape and size distribution11. Promising
shape, size, surface morphology, anisotropy and candidates are cobalt ferrite composites because of
interparticle interactions. Magnetic properties are high coercivity fields (Hc) and saturated
sensitive to microstructure and structure parameters, magnetization (Ms) values12,13.
which, themselves, strongly depend on the In the present paper the synthesis route of
preparation method used. Consequently, different production of nanoscale magnetic particles has been
methods of preparation of nanosize powders comprise studied. Fabrication, characterization and selected
of bottom-up approach via sol-gel3, micro emulsion, magnetic characteristics of well-defined CoFe2O4
hydrothermal4, chemical co-precipitation5-7 or top- nanoparticles have been presented. The effect of
down approach like ball milling8 and high preparative conditions on structural and magnetic
temperature sintering. Each technique has their own properties of CoFe2O4 particles prepared by chemical
merits and demerits in terms of tunable micro and co-precipitation technique followed by annealing in
macro scale structural and magnetic properties. air is studied. It is observed that saturation
However, to produce nanoparticles with desired magnetization and anisotropy constant of the material
properties within short processing time at low increase systematically with increasing annealing
temperature synthesis is a challenging task. Due to temperature.
_________ 2 Experimental Details
*Paper presented at one-day workshop on Synthesis and
Characterization of Nanostructured Materials (SCNM-08)
Cobalt ferrite particles have been synthesized using
organized by Applied Physics Department, M S University of chemical co-precipitation route. All chemicals were of
Baroda, Vadodara on March 30, 2008. AR grade and used as such without further
582 INDIAN J PURE & APPL PHYS, VOL 48, AUGUST 2010

purification. The starting materials used were iron intensity of (220) and (440) peaks is high in as
chloride hexahydrate i.e. FeCl3.6H2O ([Link] chem) precipitated particles compared to the annealing of
(2 mM, 99.9%) and cobalt chloride hexahydrate paricles at 800°C. This corresponds to the CoO and
CoCl2.6H2O (MERCK) (1 mM, 99.9%). Aqueous Co2O3 phases when compared with standard patterns
solutions of cobalt and iron chlorides were prepared from JCPDS software. However, the percentage
in stoichiometric proportion (1:2) by dissolving in 100 contribution of both oxide phases is very small
ml distilled water. At room temperature, under compared to pure CoFe2O4 phase. These secondary
constant stirring aqueous salt solutions were added oxide phases disappear after annealing. The intensity
into basic ion solution composed of NaOH (8 mM). of all the peaks increases with increasing annealing
With vigorous stirring the mixed colloidal solution temperature indicating growth of particle size.
was then heated to 60°C for half an hour at 10.5 pH. Crystallite size was calculated using full width half
After cooling down to room temperature, several maximum (FWHM) of the strongest reflections, (311)
water wash were given followed by acetone wash. plane and Scherrer’s formalism. This indicates that
The black particles were collected by magnetic 9.5 nm particles corresponding to the as precipitated
sedimentation. These particles were dried at normal sample has grown to 21 nm after annealing at 800ºC
temperature and kept in a furnace for annealing. The for 30 min.
annealing temperature was varied from 200 to 800°C.
The samples were collected at temperature interval of 3.2 Magnetic characterization
200°C. The annealing time of 30 min was used for The field dependent magnetization measurement of
each temperature. CoFe2O4 nanoparticles treated under different
Nanomagnetic particles of CoFe2O4 were conditions is shown in Fig. 2. The magnetic response
characterized using powder X-ray diffractometer of the sample is normalized with its gram weight
Model X’Pert Highscore Plus equipped with taken for the measurement. It is seen from the figure
proportional counter and Cu kα source. The XRD that material possess hysteresis loop at room
patterns were measured in angular range of 25 to 65 temperature and the loop becomes wider and wider
degree in Bragg-Brentano geometry. The EG and G with increasing annealing temperature, deviating from
model PAR155 vibrating sample magnetometer was its superparamagnetic (SP) nature with annealing.
used to measured the hysteresis loop at room This deviation from SP to ‘S’ shape hysteretic nature
temperature. is clearly seen from the extended zoom image of the
virgin curve shown in inset of the Fig. 2. Usually
3 Results and Discussion hysteresis loops can be identified by two qualitatively
different kinds of behaviour; nucleation-type and
3.1 Structural characterization
X-ray diffraction pattern of as precipitated and
800°C annealed samples of CoFe2O4 particles is
shown in Fig. 1. Pattern reveals the formation of cubic
spinel structure in both the cases. It is seen that the

Fig. 2 — Magnetic response of CoFe2O4 nanoparticles treated at

Fig. 1 — Powder XRD pattern of CoFe2O4 nanoparticles (as different annealing temperatures as a function of magnetic field
precipitate and 800°C annealed). *represent additional peaks for measured at room temperature. Inset figure shows zoom extended
oxide phase of Co near origin of the virgin curve for the same
 PAREKH: MAGNETIC PROPERTIES OF CoFe2O4 NANOPARTICLES 583

pinning-type14. In the former type magnet, the virgin interaction was included in this theory by introducing
curve is steep and saturation is reached under fields mean field theory for particle interaction. According
much lower than the saturation loop coercive field. to this the internal field Hint acting on each particle
This is due to the fact that domain walls are present in due to interaction with other neighbouring particles is
the virgin state and the walls are free to move so that proportional to the magnetization, i.e.:
the material can be easily saturated. Once the virgin
domain structure has been swept away, the formation Hint=λM′ …(3)
of reversed domains becomes a difficult process and where, λ is the mean field constant (dimensionless)
the demagnetization curve is characterized by a and M' is the magnetization expressed in emu/cc.
substantial coercivity. In a pinning type magnet, on Thus, Eq. (1) is modified by (H+Hint) and can be
the contrary, fields of the order of the saturation loop rewritten as:
coercive field are required to saturate the material also ∞
when one starts from the virgin state. This indicates ⌠  µ( H + H int ) 
that domain wall pinning is the main mechanism M = φM d  L  P ( D ) d ( D) …(4)
responsible for coercivity. In soft materials, ⌡  kBT 
0
nucleation-type effects can be put in evidence by
traversing the loop under controlled magnetization Figure 3 shows the plot of normalized magnetic
rate of change. In the present case the development of response where points are experimental and line is fit
‘S’ shape with annealing indicates the transition of to Eq. (4). The value of domain magnetization thus
soft material to pinning-type magnet with increase in found is 110 emu/cc, median diameter 8.2 nm, size
annealing temperature. distribution 0.31 and λ = 90.
The soft material response of as precipitate From high field response of the curve it is observed
particles can be fitted with Langevin’s theory of that applied field is not enough to saturate the system.
superparamagnetic materials to extract magnetic This is usual characteristic of fine magnetic particles
parameters. The normalized magnetic response of as that it needs very large field to saturate. At high fields
precipitate particles was fitted with modified domain walls are swept away by field pressure and
Langevin’s theory with particle size distribution as the only important magnetization mechanism remain
described in Eq. 1: is the progressive alignment of magnetization to the
∞ field against anisotropy. This is the region of
⌠  M d πD 3 H   approach to saturation. If the distribution of
  Coth   anisotropy axes in the system is isotropic and field is

M / Ms =    6kBT  
large then experimental data are often described by a
 P( D)d ( D) …(1)
  − 6kBT  series of type14 as follows:
  M πD3 H 
⌡ d 
0

where Md is domain magnetization of particles, D is

diameter of particle, kB is Boltzmann constant, Ms is
spontaneous saturation magnetization and P(D)d(D) is
log-normal distribution function given as:
  D 
2
 − ln   
1   D0  
P( D)d ( D) = exp   …(2)
σD 2π  2σ 2 
 
 
Here, ln(D0) is mean of ln (D) and σ is particle size
distribution. Since the Langevin’s theory is applicable
for non-interacting superparamagnetic system, which
Fig. 3 — Normalized magnetic response at room temperature for
is not the case here, as measurement is done on as precipitate CoFe2O4 nanoparticles (points) and line is theory
particle system, the effect of particle-particle generated using Langevin fit for superparamagnetic system
584 INDIAN J PURE & APPL PHYS, VOL 48, AUGUST 2010

Table 1 — Magnetic parameters as a function of annealing

temperature

Annealing Temp. Ms Hc
T (°C) (emu/gm) (Oe)

60 26.0 26.7
200 23.6 23.8
400 46.4 46.7
600 61.0 61.8
800 78.5 79.3

M a b
= 1− − 2 − ... …(5)
Ms Ha Ha

Here, Ha is applied magnetic field and a/Ha describes

the effect of various types of inhomogeneities like
secondary domains around defects and b/Ha2 is the
effect discussed above.
Spontaneous saturation magnetization, Ms, was
found by normalizing the magnetic response with its
gram weight and then from the intercept of the
extrapolating the high field region of the Ms versus
1/H curve. The observed values of magnetization and
coercive field obtained from the Fig. 2 are given in
Table 1. It is seen from Fig. 4 (a) and (b) that Ms and
coercive field Hc, both increase systematically with
increasing annealing temperature. Usually, coercivity
is a function of particle size and in the region of DSP
to DSD coercivity increases with increase in size
whereas from DSD to DMD coercivity decreases5. Here,
DSP is superparamagnetic particle size, DSD is single Fig. 4 — Plot of (a) Saturation magnetization versus annealing
temperature and (b) coercivity as a function of annealing
domain size range and DMD is multi-domain size
temperature
range with DSP<DSD<DMD. It is seen from Fig. 4(b)
that the coercivity increases non-linearly as a function
of annealing temperature. That shows that the particle
size has grown less than single domain size in the
temperature range studied. Increase in further
annealing temperature or time lead to increase in the
size from single domain to multi-domain and as a
result coercivity behaviour may change.
Figure 5 shows the zoom magnetic response for as
precipitate sample. It shows slight hysteresis loop
with constriction towards origin. This loop
constriction indicates magnetically two phase system
which reflects the results of XRD pattern for the
same where the presence of CoO and Co2O3 phase
(which is antiferromagnetic) is observed alongwith
CoFe2O4 spinel phase (which is ferrimagnetic).
Hence two different magnetic phases will respond
differently at origin resulting into constriction in Fig. 5 — Hysteresis loop constriction near origin for as precipitate
hysteresis loop. sample measured at room temperature
 PAREKH: MAGNETIC PROPERTIES OF CoFe2O4 NANOPARTICLES 585

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