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Precipitation Temp On Size
Precipitation Temp On Size
Abstract
Magnetic nanoparticles of cobalt ferrite (CoFe2O4) have been synthesized in a homogeneous aqueous solution
without any template and subsequent heat treatment. The average particle size could be varied in the range of
2–14 nm by controlling coprecipitation temperature of Co2+ and Fe3+ ions in alkaline solution although the size
distribution is pretty wide. As the precipitation temperature increased in the range of 20–80 C, the average particle
size also increased. However, there is a considerable change in XRD crystallinity and the average size of the
nanoparticles at the precipitation temperature between 40 C and 60 C. While the nanoparticles prepared at the
temperature below 40 C show superparamagnetic relaxation at room temperature with blocking temperatures between
75 and 200 K, the samples prepared at the temperature higher than 60 C consist of both superparamagnetic and
.
ferrimagnetic nanoparticles that result in magnetic coercivity at room temperature. Mossbauer spectra of the samples
also confirmed their magnetic properties and wide size distribution in each sample. The analysis of the spectra gave a
rough estimation of the ratio of superparamagnetic and ferromagnetic nanoparticles in each sample at various
temperatures.
r 2003 Elsevier B.V. All rights reserved.
.
Keywords: Cobalt ferrite; Nanoparticles; Superparamagnetism; Size distribution; XRD; Mossbauer; SQUID
0921-4526/03/$ - see front matter r 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0921-4526(03)00322-3
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600
(311)
500
(440)
400
Intensity (a.u.)
(511)
(220)
(400)
300
(222)
(422)
D
200
C
100
B
A
0
30 40 50 60 70
2θ (degree)
Fig. 1. XRD patterns of CoFe2O4 nanoparticles prepared at various temperatures: 20 C(A), 40 C(B), 60 C(C), 80 C(D).
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60
400
50
Intensity (a.u.)
40 300
Intensity (a.u.)
30
200
20
10 100
0
0
25 30 35 40 45 25 30 35 40 45
(a) 2θ (b) 2θ
Fig. 2. The fitted XRD peaks of reflection (2 2 0), (3 1 1), (2 2 2) and (4 0 0) for CoFe2O4 nanoparticles prepared at 20 C(a) and
80 C(b). The (2 2 2) reflection in (a) was neglected due to too small contribution.
Table 1
.
Summaries of some properties of CoFe2O4 nanoparticles derived from XRD, TEM, magnetic measurements and Mossbauer spectra
Samples Precipitation Lattice DXRD (nm) DTEM (nm) Magnetization at Hc (Oe) TB (K)a TB (K)b
temperature ( C) (
parameter (A) 10 kOe (emu/g) at 300 K
sample C, the reflections of (3 1 1), (4 0 0) and and 58.3 emu/g for the samples C and D,
(4 4 0) planes are clearly seen. From the assigned d respectively. The value for sample D is close to
values, the lattice parameter a was also estimated the saturation magnetization of bulk cobalt ferrite,
as 8.171 and 8.358 A ( for the samples prepared at known as 65 emu/g [13]. And the magnetization
20 C and 40 C, respectively. These values are curves show hysteresis with the coercivities (Hc) of
smaller than those of the samples prepared at 60 C 39 and 193 Oe at 300 K for the samples C and D,
and 80 C, which is close to that of bulk cobalt respectively. These values are much smaller than
ferrite. This indicates that there are more defect that of the bulk ferrite, 980 Oe [13]. Although the
sites in these nanoparticles than in the samples C critical size of cobalt ferrite showing superpar-
and D. amagnetic relaxation at room temperature is not
The room temperature magnetizations for ap- theoretically known, it has been known that
plied magnetic field are shown in Fig. 5. The CoFe2O4 in the size range of 10–30 nm shows no
magnetizations for the samples A and B are very superparamagnetic relaxation up to room tem-
weak and are not saturated at the field of 10 kOe. perature [14,15]. It can be inferred that the critical
They did not show any coercivity at this tempera- size of CoFe2O4 for superparamagnetic relaxation
ture. This is characteristic of superparamagnetism. at room temperature lies roughly between 4 and
The magnetizations of the samples C and D are 9 nm from our results. Fig. 6 shows the tem-
much higher and tend to be saturated at a high perature dependences of magnetization for
field. The magnetization values at 10 kOe are 36.0 those samples measured at the zero-field-cooled
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(a) (b)
Fig. 3. TEM micrographs of CoFe2O4 nanoparticles prepared at 40 C(a) and 60 C(b).
(220)
(311)
(400)
(311)
(422)
(511)
(400) (440) (440)
(a) (b)
Fig. 4. Selected area electron diffraction patterns of the sample B(a) and sample C(b).
condition. While there are maximum magnetiza- superparamagnetic relaxation starts to appear,
tions below room temperature for the samples A below room temperature, the samples C and D
and B, the magnetizations for the samples C and D have them above room temperature. The ave-
are continuously increased up to room tempera- rage blocking temperatures (TB) for the sam-
ture. This means that while the samples A and B ples A and B can be estimated as 75 and
have the blocking temperatures, at which the 210 K, respectively, from the temperatures of the
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5 0.4
4
3 B
Magnetization (emu/g)
M agnetization (em u/g)
0.3
2 A B
1
0 0.2
-1
-2
0.1
-3
A
-4
-5 0.0
-10000 -5000 0 5000 10000
50 100 150 200 250 300
Applied Field (Oe) Temperature (K)
6
60
D
5
Magnetization (emu/g)
M agnetization (em u/g)
40
C 4
20
D
0 3
-20 2
-40 1
C
-60 0
maximum magnetizations. For the sample B, it the larger particles is much greater than the
seems to be consisted of apparently two compo- smaller particles.
nents that gives two different blocking tempera- .
We have measured 57Fe Mossbauer spectra of
tures since there is a shoulder at around 80 K in the all samples prepared here at various temperatures
temperature-dependent magnetization curve. It is in order to study the superparamagnetic nature
interesting that the magnetic properties of the and the size distribution. Fig. 7 shows the spectra
samples A and B are considerably different, measured at room temperature. As shown in
despite their sizes and crystallinities are not much magnetization measurement there is clear differ-
different as shown in XRD and TEM. This ence between the spectra of the samples prepared
difference might be explained by the difference of at 20 C and 40 C and those prepared at 60 C and
size distribution in two samples. If the sample B 80 C. While the formers show a quadrupole
has a wider size distribution than the sample A doublet which is due to superparamagnetic relaxa-
has, even though the average particle size is not tion, the latters have a complex hyperfine structure
much different from that of the sample A, the in which a quadrupole doublet is superimposed on
total magnetization will be dominated by the a magnetically split sextet as shown in the fitted
larger particles because the magnetization of curve. This indicates that the samples C and D can
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0
0
D D
5
5
C
10
C
Absorption (a.u.)
10
Absorption (a.u.)
B
15
15 B
A
20 20
A
25 25
30 30
-10 -5 0 5 10 -10 -5 0 5 10
Velocity (mm/sec) Velocity (mm/sec)
.
Fig. 7. Mossbauer spectra of CoFe2O4 nanoparticles measured .
Fig. 8. Mossbauer spectra of CoFe2O4 nanoparticles measured
at room temperature. The spectra are denoted as indicated in at 125 K.
text.
superparamagnetic components in those samples netic fraction for the samples A and B occurs at
at various temperatures. The results are shown in narrow temperature range, the change for the
Fig. 11. While the change of the superparamag- samples C and D occurs at wider temperature
range. This implies that the size distribution in the
samples A and B is narrower than in the samples C
and D. This was confirmed from the TEM images
0
of Fig. 3.
The blocking temperature can be also defined as
350 K
a temperature at which the magnetically split and
unsplit components represent 50% each of the
5
.
Mossbauer spectral area. From Fig. 11, the
blocking temperatures can be estimated as about
Absorption (a.u.)
120
A
100
B
C
80 D
Fraction (%)
60
40
20
Temperature (K)
.
Fig. 11. Thermal variation of the superparamagnetic fraction in CoFe2O4 nanoparticles derived from the Mossbauer spectra.
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magnetization since the superparamagnetic relaxa- of 3.3 nm in diameter showed the blocking
tion is a dynamic process and the measuring time .
temperature of 85 K from Mossbauer spectra
scales of both methods are completely different. [18]. This value is roughly consistent with those
Indeed, Zhang et al. have shown that TB of some .
of the samples A and B estimated from Mossbauer
magnetic nanoparticles estimated from tempera- spectra.
ture-dependent magnetization decay is much lower
.
than that from Mossbauer data [16,17]. However,
TB from a magnetization measurement is strongly 4. Conclusion
dependent upon the applied field and it will shift to
higher value under higher magnetic field. The TB We have prepared CoFe2O4 nanoparticles in
that was estimated from the magnetization decay aqueous solutions at various temperatures by
in field-free condition by Zhang et al. can be coprecipitation method without any template.
therefore different from that estimated from the The average particle sizes of the ferrites, estimated
magnetization maximum which, here we obtained, from XRD line broadening, were 2.0, 2.4, 9.2 and
was measured under the applied magnetic field 13.8 nm when the precipitation temperatures are
(100 G). Zhang et al. have also obtained two 20 C, 40 C, 60 C and 80 C, respectively. As the
different TB values for Co-ferrite nanoparticles precipitation temperature increased, the average
with similar sizes of 8.5–9 nm: one was 151 K from sizes increased. However, there was a transition in
magnetization decay [16] and the other was about size and crystallinity at the temperature between
300 K from magnetization maximum [4]. The 40 C and 60 C. The field-dependent and tempera-
.
latter is closer to that (394 K) from Mossbauer ture-dependent magnetization measurements and
data [16]. Therefore, the blocking temperatures .
Mossbauer spectra measured at various tempera-
estimated from magnetization measurement and tures showed that the cobalt ferrites nanoparticles
.
Mossbauer spectra for the same sample cannot be prepared at the temperature lower than 40 C are
in principle same due to different time scale if they entirely superparamagnetic at room temperature
are measured under the same field-free condition. with TB of around 80 K and those, prepared at
However, they, estimated from magnetiza- temperatures higher than 60 C, consisted of
tion measurement under an applied field and superparamagnetic and ferromagnetic components
.
Mossbauer spectra under field-free condition, can with TB higher than 400 K. For the latter, the
be apparently similar depending on the strength of fraction of superparamagnetic components de-
applied field even though the quantitative predic- creased as the precipitation temperature increased
tion may not be possible. In our cases, the TBs, with the increased particle size.
measured from both methods, are roughly close
together as shown in Table 1.
.
For the sample B, the Mossbauer spectrum at
125 K shown in Fig. 8 is consisted of mainly a Acknowledgements
quadrupole doublet with a very small portion of
split sextet. It means that most of the particles are This work was supported by Korea Research
superparamagnetic at this temperature. This is Foundation Grant (KRF-2001-015-DP0365).
consistent with the above argument from the
temperature dependence of magnetization for
sample B if the blocking temperatures from References
.
Mossbauer data and the magnetization measure-
ment are similar to each other as mentioned above. [1] A.K. Giri, K. Pellerin, W. Pongsaksawad, M. Sorescu,
Therefore the average particle size of the sample B S. Majetich, IEEE Trans. Magn. 36 (2000) 3029.
[2] A.K. Giri, E.M. Kirkpatrick, P. Moongkhamklang,
is close to that of the sample A despite of some S.A. Majetich, Appl. Phys. Lett. 80 (2002) 2341.
larger particles included in it. Slawska-Waniewska [3] N. Moumen, P. Veillet, M.P. Pileni, J. Magn. Magn.
et al. reported that the cobalt ferrite nanoparticles Mater. 149 (1995) 67.
ARTICLE IN PRESS
[4] C. Liu, B. Zou, A.J. Rondinone, Z.J. Zhang, J. Am. Chem. [11] JCPDS data base 22-1086.
Soc. 122 (2000) 6263. [12] L.B. Azaroff, The Powder Methods, McGraw-Hill, New
[5] V. Pillai, D.O. Shah, J. Magn. Magn. Mater. 163 (1996) York, 1958.
243. [13] G. Bate, in: E.P. Wohlfarth (Ed.), Ferromagnetic Materi-
[6] Y. Ahn, E.J. Choi, S. Kim, H.N. Ok, Mater. Lett. 50 als, Vol. 2, North-Holland, Amsterdam, 1980, p. 431.
(2001) 47. [14] H.R. Rechenberg, F.A. Tourinho, Hyperfine Interactions
[7] S.R. Ahmed, P. Kofinas, Mater. Res. Soc. Symp. Proc. 661 67 (1991) 627.
(2001) KK 10.10.1. [15] K. Haneda, A.H. Morrish, J. Appl. Phys. 63 (1988)
[8] T. Pannaparayil, S. Komarneni, IEEE Trans. Magn. 25 4258.
(1989) 4233. [16] A.J. Rondinone, A.C.S. Samia, Z.J. Zhang, Appl. Phys.
[9] P.C. Morais, V.K. Garg, A.C. Oliveira, L.P. Silva, R.B. Lett. 76 (2000) 3624.
Azevedo, A.M.L. Silva, E.C.D. Lima, J. Magn. Magn. [17] A.J. Rondinone, C. Liu, Z.J. Zhang, J. Phys. Chem. B 105
Mater. 225 (2001) 37. (2001) 7967.
[10] M. Rajendran, R.C. Pullar, A.K. Bhattacharya, D. Das, !
[18] A. Slawska-Waniewska, P. Didukh, J.M. Greneche,
S.N. Chintalapudi, C.K. Majumdar, J. Magn. Magn. P.C. Fannin, J. Magn. Magn. Mater. 215–216 (2000)
Mater. 232 (2001) 71. 227.