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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
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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226
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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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
(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.)
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
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
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
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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(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
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
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
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
2.5
Velocity (mm/s)
(a)
2.5
5.0
7.5 10.0
Velocity (mm/s)
(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)
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
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).