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Physica B 363 (2005) 225231


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CoZn ferrite nanoparticles for ferrouid preparation:


Study on magnetic properties
R. Arulmurugana,, G. Vaidyanathana, S. Sendhilnathanb, B. Jeyadevanc
a
Department of Physics, Pondicherry Engineering College, Pondicherry 605 014, India
Department of Physics, Sri Manakula Vinayagar Engineering College, Pondicherry 605 107, India
c
Graduate School of Environmental Studies, Tohoku University, Sendai 980-8579, Japan

Received 10 December 2004; received in revised form 9 March 2005; accepted 17 March 2005

Abstract
CoZn substituted nanoferrites having stoichiometric composition Co1xZnxFe2O4 with x ranging from 0.1 to 0.5
were prepared by chemical coprecipitation method. The precipitated particles were used for the preparation of
ferrouid. Ferrouids having Co0.5Zn0.5Fe2O4 particles could be used for the energy conversion application utilizing the
magnetically induced convection for thermal dissipation. The nal estimated cation contents, agreed with the initial
degree of substitution. The powder samples were characterized by XRD, TEM, VSM and Mossbauer studies. The
precipitated particles showed single-phase fcc spinel structure for all compositions of zinc. The magnetic parameters
such as Ms, Hc, Mr, Tc and particle size were found to decrease with the increase in zinc substitution. In the case of
particles with higher zinc concentration, both ferrimagnetic nanoparticles and particles exhibiting superparamagnetic
behavior were present. The ne particles were suitably dispersed in heptane using oleic acid as the surfactant. Volatile
nature of the carrier chosen helped in altering the number concentration of the magnetic particles in a ferrouid.
r 2005 Elsevier B.V. All rights reserved.
PACS: 75.50.Mm; 75.75.+a; 75.75.Tt; 87.64.pj
Keywords: Chemical coprecipitation method; CoZn ferrite; Nanoferrites; Magnetic uid; Temperature-sensitive ferrouid

1. Introduction

Corresponding author. Tel.: +91 413 655281;


fax: +91 413 0655101.
E-mail address: arulphysics@rediffmail.com
(R. Arulmurugan).

A number of solution-based preparation techniques are available for the preparation of ne


particles (which show novel properties when
compared to their properties in the bulk) with
desirable size and magnetic properties. For the
preparation of ferrouid, chemical coprecipitation

0921-4526/$ - see front matter r 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2005.03.025

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R. Arulmurugan et al. / Physica B 363 (2005) 225231

technique has been widely used. Thermomagnetic


energy conversion using ferrouid proposed during the early stage of the magnetic uid research,
can be realized only by synthesizing uids having
large pyromagnetic coefcient. The behavior of
magnetic colloidal uids in power transformer has
been experimentally studied [1]. Only close to the
Curie temperature, the adiabatic magnetization
can cause a considerable change in uid temperature. Ferrouids can be effectively used up to a
maximum temperature of around 150 1C, without
losing much of the stability. In order to reduce the
Curie temperature close to the operating range
(around 150 1C, considering the boiling point of
the carrier and the stability of the uid at elevated
temperature) and to prepare a temperature-sensitive ferrouid, Mn0.5Zn0.5Fe2O4 particles are used.
But in the case of colloids containing magnetically
hard particles, magnetoviscosity of the uid can
signicantly affect the thermal dissipation [2].
Hence in order to prepare ferrouid for thermomagnetic energy conversion and to use the
magnetically induced convection for thermal dissipation CoZn substituted ferrite nanoparticles
(to strike a compromise between magnetically hard
particles and low Curie temperature material) can
be used. Many interesting studies on CoZn
ferrites in the bulk crystalline form prepared by
the usual ceramic technique [3,4] and Co0.2Zn0.8Fe2O4 ne particles prepared by chemical coprecipitation method followed by sintering [5] have
been found in the literature. Recently, intensive
work on synthesis and characterization of cobalt
ferrite nanoparticles by various techniques having
different particle size and magnetic properties were
carried out. Cobalt ferrite nanoparticles are used
in magnetic uids, information storage system,
medical diagnostics, etc., [610]. Jeyadevan et al.
[11,12] successfully prepared (by coprecipitation
method), nearly monodispersed single-domain
cobalt ferrite particles having a maximum value
of Hc which could be used for high-density
recording media. Morais et al. [13] reported the
possibility of controlling the nanoparticles using
different stirring speeds, with no apparent change
of the standard deviation. Temperature-sensitive
magnetic uid having Co0.3Zn0.7Fe2O4 particles
for the study of heat convection [14] and diester-

based ferrouid having Co0.7Zn0.3Fe2O4 nanoparticles were reported [15]. In spite of the development of a variety of solution-based preparation
techniques, production of CoZn substituted
ferrite nanoparticles with desirable size and
magnetic properties is still a challenge. Here we
report synthesis of Co(1x)Zn(x)Fe2O4 nanoparticles (with x varying from 0.1 to 0.5) by coprecipitation method, preparation of ferrouid having
CoZn ferrites, and their characterization and
magnetic properties.

2. Experimental
2.1. Synthesis of Co1xZnxFe2O4 nanoparticles and
ferrofluid
Ultrane particles of Co1xZnxFe2O4 with x
varying from 0.1 to 0.5 were prepared by
coprecipitation method. Initial molar proportion
of salts (Me2+)/(Fe3+) was 0.5, where
Me2 Co2 Zn2 . The molarity of the coprecipitating agent (NaOH) used was 0.66 mol/l.
The mixed solutions of CoCl2, ZnSO4 and FeCl3
in their respective stoichiometry at 80 1C were
added to the boiling solution of NaOH in 10 s
under constant stirring. Nanoferrites are formed
by conversion of metal salts into hydroxides,
which takes place immediately, followed by
transformation of hydroxides into ferrites. For
the transformation of hydroxides into spinel ferrite
(dehydration and atomic rearrangement involved
in the conversion of intermediate hydroxide phase
into ferrite) it was required to maintain a
temperature of 95 1C for 1 h. The size of the
precipitated particles was controlled by xing the
coprecipitation step. For all values of zinc
substitution, the stirring speed was kept constant,
around 3000 rpm. The volume of the nal solution
in the reaction vessel is adjusted so as to keep
[M/OH] ratio to be of the order of 0.2
M Co2 Zn2 Fe3 0:15 mol=l. Further
details on the preparation of ne particles are
discussed elsewhere [16]. After precipitation the
pH of the solution was found to be around 12.0.
Particles were collected and separated using
magnetic separation at this stage. The separated

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R. Arulmurugan et al. / Physica B 363 (2005) 225231

2.2. Characterization
X-ray characterization of the prepared powder
samples was carried out using Rigaku X-ray
diffractometer having Cu Ka radiation. The shape
and morphology of the ne particles were analyzed
using high-resolution transmission electron microscopy (HRTEM-Hitachi HF 2000). Estimation of
Co2+, Mn2+ and Zn2+ in the nal product was
carried out using double beam atomic absorption
spectrometer (GBC-902). The Fe3+ ions were
estimated by using UV visible spectrophotometer
(Shimadzu UV-1601). The concentration of
Fe3+ ion was estimated by measuring the absorbance at 510 nm using the spectrophotometer
[16,17]. The room temperature magnetization
measurements up to a maximum eld of 10 kOe
and temperature dependence of magnetization at
5.0 kOe were carried out using a vibrational
sample magnetometer (VSM Tamakawa model
TM-VSM1230-HHHS). Mossbauer spectra were
taken (Wissel Instrument) at room temperature
with 57Co source in rhodium matrix, operated in
constant acceleration mode. For tting the data
Normos least-squares tting programme was used.
The magnetization of the uid samples were
carried out using pulse eld technique. The
saturation magnetization of the uid samples
were estimated from the M vs. 1/H plot. The
instrument was calibrated using a uid sample of

known magnetization (252 G) supplied by Liquids


Research Ltd. The calibration constant used
was 0.165.

3. Results and discussion


The structure of the particles was analyzed using
a X-ray diffractometer. The patterns were analyzed using Powder X software [18]. The analysis
conrms the formation of single-phase fcc spinel
structure for all the samples. The indexed X-ray
diffraction patterns are shown in Fig. 1. The broad
XRD lines indicate that the particles are of
nanosize range. In addition, the estimated nal
cation contents of the prepared samples agree with
the initial stoichiometry. The nal cation contents
estimated for different values of zinc substitution,
and the particle size calculated from the (3 1 1)
plane using DebyeScherrer formula are given in

(311)

3000
2000

Co0.9Zn0.1Fe2O4

(311)

2250

Co0.8Zn0.2Fe2O4

1500
(220)

750

(511)(440)
(422)

(400)

(220)

1000
0

(511) (440)
(422)

(400)

0
Intensity (a.u.)

particles were washed several times with distilled


water followed by acetone and dried at room
temperature.
The pH of the solution was reduced to E10.5 as
coating of surfactant takes place only at pH value
1011. Oleic acid was used as the surfactant. Oleic
acid was converted to sodium oleate after heating
with NaOH solution at a pH of 10. The sodium
oleate solution was transferred to the reaction
vessel and stirred for nearly 3 h. Coating of
surfactant was carried out at 80 1C. To coagulate
the oleic acid coated particles, dilute HNO3 was
added. After decantation, the product was washed
a number of times with distilled water to remove
soluble impurities. After removing the excess water
by acetone washing, the coated particles were
dispersed in heptane.

227

(311)

2250

Co0.7Zn0.3Fe2O4

1500
(220)

750
0

(511) (440)
(422)

(400)

(311)

3000
2000
1000
0

Co0.6Zn0.4Fe2O4
(220)

(311)

3000

(511)(440)
(422)

(400)

Co0.5Zn0.5Fe2O4

2000
(220)

1000

(400)

(511)(440)
(422)

0
20

30

40

50

60

70

2 theta
Fig. 1. X-ray diffraction pattern of Co(1x)ZnxFe2O4 powders
with x varying from 0.1 to 0.5.

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228

3.1. Magnetization measurements of fine particles

5 kOe) to the temperature axis. This is due to the


appearance of nonlinear tail. The change in
magnetic properties such as Ms, Hc, Mr and Tc is
due to the inuence of the cationic stoichiometry
and their occupancy, in the specic sites. In the
cubic system of ferrimagnetic spinels, the magnetic
order is mainly due to a super exchange interaction
mechanism occurring between the metal ions in the
A and B sublattices. The substitution of nonmagnetic ion such as Zn, which has a preferential
A site occupancy, results in the reduction of the
exchange interaction between A and B sites. In
addition, formation of dead layer on the surface,
existence of random canting of particle surface
spins, nonsaturation effects due to random distribution of particle size, deviation from the
normal cation distribution etc., also result in
the reduction of magnetic properties of nanosized
particles. The decrease in specic magnetization
and Curie temperature with the increase in

The room temperature magnetization measurements were carried out by vibrating sample
magnetometer. Fig. 3 shows the room temperature
hysteresis loop of the prepared powder samples.
The coercivity is found to be maximum when the
partial substitution of zinc with cobalt ferrite is
minimum. The variation of the coercivity and
remanence with Zn concentration are shown in
Fig. 4. Upon increasing the zinc substitution, the
saturation magnetization, remanence, coercivity
and Curie temperature were found to decrease.
The Curie temperature was obtained by extrapolating the linear section of the temperaturedependent magnetization curve (recorded at

Fig. 2. Transmission electron micrograph of (a) Co0.9Zn0.1Fe2O4 and (b) Co0.5Zn0.5Fe2O4.

Table 1. The particle size (D311) decreases from 12


to 8 nm when the partial substitution of zinc
increases (x 0:1 to 0.5).
The shape and morphology of the particles were
examined by direct observation using high-resolution transmission electron microscopy. The transmission electron micrograph of the prepared
samples are given in Fig. 2. Direct observation of
the lattice image reveals that the particles are
approximately spherical in shape and ne particles
with higher zinc concentration are agglomerated.
In other words, the decrease in particle size led to
agglomeration of magnetic ne particles. Because
of the small size, single-domain particles experience a magnetic moment proportional to
their volume and get permanently magnetized.
Hence ne particles of size less than 10 nm are
agglomerated.

Table 1
Summary of the results obtained from the powder and uid samples
Sample composition

Co0.90Zn0.10Fe1.96O4
Co0.81Zn0.20Fe1.98O4
Co0.70Zn0.31Fe1.96O4
Co0.61Zn0.41Fe1.96O4
Co0.51Zn0.50Fe1.95O4

D(3 1 1) (nm)

12.0
11.1
9.7
8.8
8.4

Magnetic parameters measured at room


temperature for the powder samples in a eld of
10 kOe
Ms (emu/g)

Mr (emu/g)

Hc (Oe)

54.1
50.7
48.8
42.8
39.6

10.60
4.84
2.35
0.80
0.50

223.0
76.2
33.5
11.6
9.8

Estimated
Curie
temperature
(1C)

Saturation
magnetization
of the uid
samples (G)

415
373
352
285
267

180
150
137
125
110

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partial substitution of zinc with cobalt are shown


in Fig. 5.
The saturation magnetization was found to
decrease from 54.1 to 39.6 emu/g when the
concentration of zinc was increased from 0.1 to
0.5. The value of saturation magnetization measured at 10 kOe for Co0.9Zn0.1Fe2O4 (54.1 emu/g
for 11.1 nm size particle) was close to the value of
CoFe2O4 (58.3 emu/g for 13.8 nm size particle
precipitated at 80 1C) reported by Kim et al. [6].
But it is interesting to note that the coercivity
(223 Oe) obtained is high when compared to the
coercivity of cobalt ferrite (193 Oe) reported by
Kim et al. [6]. The saturation magnetization and
coercivity values obtained (58.3 emu/g, 223 Oe) are
much smaller than that of bulk CoFe2O4 (65 emu/
g, 980 Oe) [19]. The reduction in the magnetic
property may be due to the partial substitution on
nonmagnetic zinc x 0:1, due to size effect or
due to the presence of superparamagnetic particles. From Fig. 4. it is clear that there is a sharp
decrease in the coercivity (from 223 to 33.5 Oe)
and remanence (from 10.6 to 2.35 emu/g) when the
value of x is varied form 0.1 to 0.3. Further
increase in zinc substitution also results in the
decrease of remanence and coercivity, 0.5 emu/g
and 9.8 Oe, respectively, for Co0.5Zn0.5Fe2O4.
Summary of the results obtained from magnetization measurements of the powder samples are
given in Table 2.
Mossbauer spectra for the representative
samples (x 0:1, 0.3 and 0.5) have been recorded.

(a)

Magnetization (emu/g)

(b)
(c)

30

30

60
10

10

Field (Oe)
Fig. 3. Room temperature magnetization curve of (a)
Co0.9Zn0.1Fe2O4, (b) Co0.7Zn0.3Fe2O4 and (c) Co0.5Zn0.5Fe2O4.

Coercivity - Hc (Oe)

Coercivity - Hc
Remanence - Mr

200

10
8

150
6
100

50
0
0.0

Remanence - Mr (emu/g)

12

250

0
0.1

0.2

0.3

0.4

0.5

Zinc Concentration

Curie temperature -Tc (C)

Fig. 4. Variation of the coercivity and remanence with Zn


concentration.

56

420
400

Tc

54

380

Ms

52
50

360

48
46

340
320

44

300

42

280

40

260

38
0.1

0.2

0.3

0.4

0.5

Specific Magnetisation - Ms (emu/g)

60

229

Zinc Concentration
Fig. 5. Variation of saturation magnetization and Curie temperature with Zn concentration.

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1.010
1.005
1.000
0.995
0.990
0.985
0.980
0.975
0.970

Co0.9Zn0.1Fe2O4

10.0 7.5 5.0 2.5 0.0

Relative transmission
Relative transmission

5.0

7.5 10.0

1.01
Co0.7Zn0.3Fe2O4
1.00
1.00
1.00
0.99
0.98
0.98
0.97
0.97
10.0 7.5 5.0 2.5 0.0 2.5 5.0 7.5 10.0
Velocity (mm/s)

(b)
1.010
1.005
1.000
0.995
0.990
0.985
0.980
0.975
0.970

Co0.5Zn0.5Fe2O4

10.0 7.5 5.0 2.5 0.0


(c)

2.5

Velocity (mm/s)

(a)

2.5

5.0

particles, respectively. The particles which are


greater than 10 nm (for x 0:1 with 11 nm particle
size) have complex hyperne structure in which a
quadrupole doublet is superimposed on magnetically split sextets which corresponds to the
tetrahedral A and octahedral B coordinations of
iron. This is due to the presence of both superparamagnetic and ferrimagnetic particles, which
may be due to the wide size distribution or effect
of preparation. The tted Mossbauer spectrum
of Co0.9Zn0.1Fe2O4 ne particles is shown in
Fig. 6a.
3.2. Magnetization of the fluid samples
The ne particles were used to prepare less
viscous hydrocarbon-(heptane) based ferrouid.
The magnetization measurements of the uid
samples were carried out by pulse eld technique
to a maximum eld of 1000 Oe. The saturation
magnetization of the uid samples were determined from the M vs. 1/H plot. Field vs. reduced
magnetization curves for all the uid samples
prepared are shown in Fig. 7. The saturation
magnetization of the uid samples decreases as the
partial substitution of zinc with cobalt increases
Table 1.

7.5 10.0

Velocity (mm/s)

Fig. 6. Mossbauer spectrum of (a) Co0.9Zn0.1Fe2O4, (b)


Co0.7Zn0.3Fe2O4 and (c) Co0.5Zn0.5Fe2O4 ne particles measured at room temperature.

Fig. 6 shows the spectra recorded at room


temperature. The ne particles with higher zinc
concentration (x 0:3 and 0.5) whose particle size
are less than 10 nm, show only a quadrupole
doublet when tted (Figs. 6b and c). This is due
to the single-domain nature of the particles.
Mossbauer spectra of both the samples were
tted satisfactorily with a single doublet having
a quadrupole splitting of 0.64 and 0.20 mm/s and
Isomer shift of 0.33(70.02) and 0.22(70.01) mm/s
for Co0.5Zn0.5Fe2O4 and Co0.7Zn0.3Fe2O4 ne

(a)

1.0
Reduced Magnetization (M/MS)

Relative transmission

230

(c)

0.8
0.6

(d)

(e)

(b)

0.4
0.2
0.0
200

400

600

800

1000

Field (Oe)
Fig. 7. Field vs. reduced magnetization curve for ferrouids
having (a) Co0.9Zn0.1Fe2O4, (b) Co0.8Zn0.2Fe2O4, (c) Co0.7Zn0.3Fe2O4, (d) Co0.6Zn0.4Fe2O4 and (e)Co0.5Zn0.5Fe2O4 ne
particles.

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231

Table 2
Summary of Mossbauer results obtained for the powder samples at room temperature
Sample

Isomershift (mm/s)

Quadrupole splitting (mm/s)

Hyperne eld (T)

Width (mm/s)

Co(0.5)Zn(0.5)Fe2O4
Co(0.7)Zn(0.3)Fe2O4
Co(0.9)Zn(0.1)Fe2O4

0.33
0.22
0.29
0.31
0.35

0.64
0.20
0.03
0.02
0.94

40.3
44.7

0.78
0.68
0.44
0.44
0.44

(70.02)
(70.01)
[A]
[B]
[C]

4. Conclusion

References

The preparation technique adopted favors the


formation of CoZn substituted ferrite nanoparticles suitable for ferrouid preparation. The ne
particles could be suitably dispersed in any
hydrocarbon-based carrier liquid. The Curie temperature was found to decrease with the increase in
zinc substitution. Hence partial substitution of
zinc with cobalt for x40.5 can bring down the
Curie temperature close to the room temperature.
The low Curie temperature material can be used
for the preparation of temperature-sensitive ferrouid. Mossbauer studies indicate that the particles
with higher zinc substitution are single domain in
nature. The volatile hydrocarbon-based ferrouid
can be transferred to a carrier liquid whose boiling
point is close to the Curie temperature of the
particles and less volatile in nature. This can be
done by carrier exchange technique. Ferrouids
having Co0.5Zn0.5Fe2O4 ne particles (with large
magnetic volume force) can be effectively used for
energy conversion applications.

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Acknowledgements
The authors are thankful to Dr. P.C. Scholten
and Prof. R.V. Mehta for their interest and help
and to Dr. S.W. Charles and Dr. Stephen Wells of
Liquids Research for providing sample uid for
calibration. One of the authors Dr. G. Vaidyanathan gratefully acknowledges CSIR (Ref. no.
03(1001)/04/EMR-II) for the nancial assistance
received through project. The rst author R.
Arulmurugan is also thankful to CSIR for the
award of fellowship (SRF).