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5 authors, including:
Ayyappan Sathya
John Philip
SEE PROFILE
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NANOTECHNOLOGY
doi:10.1088/0957-4484/17/23/023
1. Introduction
Tailoring of magnetic nanocrystals of well-defined size, shape
and self-assembly has been a topic of intensive research [15]
because of the enormous scope for applications of these
materials in storage media [6, 7], biomedical devices [8, 9],
optical devices, sensors [10] and magnetic fluids [1113]. In
addition, magnetic colloids have been found to be a model
system for fundamental studies of phenomena such as the
interaction between particles and molecules [14]. Inspired
by the potential applications of magnetic nanoparticles, in
recent years, several studies were focused on enlarging the
coercivity [15, 16] and transition temperatures [1720]. The
maghemite ( -Fe2 O3 ) to haematite ( -Fe2 O3 ) phase transition
studies in the nanosize regime attracted much attention due
1 Author to whom any correspondence should be addressed.
0957-4484/06/235851+07$30.00
5851
G Gnanaprakash et al
2. Experimental section
2.1. Chemicals
For the synthesis of magnetite nanoparticles, FeSO4 7H2 O,
FeCl3 6H2 O, 25% aqueous NH3 , NaOH, ethanol, oleic acid,
35% HCl, H2 SO4 , hexane and acetone procured from E-Merck
were used. All the chemicals were GR grade (except the
hexane) and used without any further purification. The water
used in all the experiments was triply distilled and filtered with
a 0.22 m size filter. The conductivity of the water used is
below 0.2 S cm1 .
2.2. Synthesis
Magnetite nanoparticles were prepared by precipitating iron
salts with ammonium hydroxide (process 1) and sodium
hydroxide (process 2). The iron salts used were freshly
prepared with 0.8 M FeCl3 6H2 O and 0.4 M FeSO4 7H2 O in an
acidic medium of HCl and H2 SO4 , respectively. The iron salt
solutions were mixed at 1:1 ratio with constant stirring. On
vigorous stirring, the solution pH was increased rapidly, by the
addition of one of the alkalis, which leads to a black coloured
solution. After 30 min of digestion time, 5 ml oleic acid was
added to the above solution to coat the magnetite nanoparticles.
At this stage, the pH of the solution was adjusted to 9 at a
constant temperature of 70 C. The same pH, temperature
and stirring speed were maintained for 30 min to finish the
5852
Ethanol/water ratio
0 : 100
Intensity (a.u)
20 : 80
40: 60
60 : 40
40
50
60
70
80
90
100
110
2 (degree)
r =
2V
kB T ln(S)
(1)
G Gnanaprakash et al
50
Distribution (%)
40
30
20
20 nm
10
0
2
10
12
14
Figure 2. The TEM image of sample S4 (left) and the size distribution (right).
S1
S2
S3
S4
60:40
40:60
20:80
0:100
2.3
3.3
4.8
6.5
Saturation
magnetization
(emu g1 )
6.23
14.57
18.36
26.27
Sample
Average
particle size
(nm)
100
2.3 nm
80
60
6.5 nm
40
0
100
200
300
400
500
600
700
800
Temperature ( 0 C)
25
25 0C
A1
25 C
4.8 nm
15
16
S3
Magnetization (emu/g)
Magnetization (emu/g)
24
8
0
-8
-16
-24
600 0C
5
700 0C
-5
0.7
-0.3
-15
-32
-8
-6
-4
-2
-0.8
-8
-25
-8
700 0C
0.2
-6
-4
-2
-6
-4
-2
Intensity (a.u)
600 C
450 C
350 C
0
250 C
25 C
20
30
40
50
60
70
80
90
100
110
300
214
116
024
113
110
750 C
Intensity (a.u)
012
104
(b)
018
2 (deg)
700 C
250 C
440
511
422
400
311
220
211
111
210
600 C
25 C
20
30
40
50
60
70
80
90
100
110
2 (deg)
G Gnanaprakash et al
Intensity (a.u)
6.5 nm
4.8 nm
2.3 nm
20
30
40
50
60
70
80
90
100
110
2 (deg)
Figure 7. XRD patterns of S1 (2.3 nm), S3 (4.8 nm) and S4 (6.5 nm)
samples treated at 600 C.
8
6.5 nm
0
Magnetization (emu/g)
600 C
4.8 nm
2.3 nm
-4
-8
-8000
-6000
-4000
-2000
2000
4000
6000
8000
Field (Oe)
4. Conclusions
In summary, we have been able to tailor magnetic nanoparticles
in the size range of 27 nm by changing the dielectric constant
of the solvent and the alkali addition rates. An enhancement
in the temperature of the phase transition from cubic -Fe2 O3
to rhombohedral -Fe2 O3 is observed for magnetite samples
prepared with NaOH. The enhancement in the phase transition
temperature by about 150 C for 5 nm size particles seems to be
Acknowledgments
We thank Dr K S Viswanathan for the atomic absorption
spectrometry, Mr S Mahadevan for the XRD investigations.
We also thank Dr Vasudeva Rao and Mr P Kalyanasundaram
for support and encouragement.
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