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Abstract
Monodisperse iron oxide nanoparticles with 5–20 nm can be synthesized by an inexpensive and simple ultrasonic-assisted method at low
temperature. This is based on the decomposition of iron pentacarbonyl in cis–trans decalin. The high energy emitted by ultrasonic irradiation at a
short time can promote the crystallization process simultaneously. At low temperature, these crystalline nucleuses can grow to monodisperse
nanoparticles. Effects of ultrasonic treatment, the concentration of surfactant and the refluxing time on the size and size distribution of iron oxide
nanoparticles were investigated. The morphology and crystal structure of iron oxide nanoparticles obtained at different conditions were
characterized by high-resolution transmission electron microscope, X-ray diffraction and selected area electron diffraction.
© 2006 Elsevier B.V. All rights reserved.
3.1. Effect of surfactant concentration on size and size distribution of 3.2. Effect of refluxing time on iron oxide nanoparticles
iron oxide nanoparticles
Fig. 3 shows TEM images of iron oxide nanoparticles obtained with
The concentration of surfactant has a drastic effect on the size oleic acid:Fe(CO)5 ratio of 3:1 at 190 °C for a refluxing time that varies
distribution of iron oxide nanoparticles in this work as shown in Fig. 2. from 30, 60 and 90 min. The average sizes of iron oxide nanoparticles
The obtained iron oxide nanoparticles in Fig. 2a, b and c correspond to are 10, 15 and 20 nm, which correspond with XRD patterns (Fig. 3d).
the molar ratio (oleic acid to Fe(CO)5) of 1:1, 3:1 and 6:1, respectively. The diffraction peaks are attributed to the (220), (311), (400), (422),
The average sizes are 9.5 ± 1.2 nm, 9.6 ± 0.2 nm and 5.4 ± 0.1 nm, (511) and (440) planes of cubic γ-Fe2O3, the smaller the size of the
respectively. We find that higher concentration of oleic acid can get nanoparticles, the broader of the peaks. It appears that the larger
smaller size and narrower size distribution of iron oxide nanoparticles nanoparticles have relatively higher crystallinity.
as reported in Ref. [9]. When the molar ratio is 1:1, only polydispersed
nanoparticles can be observed, which suggests that, at low concentra- 3.3. Effect of ultrasonic irradiation on iron oxide nanoparticles
tion, oleic acid is ineffective at stabilizing the iron oxide particles.
When the ratio reaches 3:1, monodisperse nanoparticles are obtained as Many researchers have investigated the effect of ultrasound on
shown in Fig. 2b, but the size is not smaller than that obtained at 1:1, chemical reactions and have suggested some proposed explanations,
the reason is that the size is an average statistic value from 300 such as the “hot spot” explanation [18], the “electrical explanation”
2206 G.Q. Zhang et al. / Materials Letters 61 (2007) 2204–2207
Fig. 2. TEM images of iron oxide nanocrystals obtained from different concentrations of oleic acid. From (a) to (c) the molar ratio of oleic acid to Fe(CO)5 is 1:1, 3:1
and 6:1, respectively. The ultrasonic irradiation time is 10 min, refluxing time is 30 min.
[22], and a proposed model based on plasma discharge [23]. Most parameters of the processed medium. Thus, we believe that acoustic
theories imply that the harsh conditions generated upon bubble collapse cavitation holds much promise for controlled change in the
lead to the formation of free radicals, mechanical shocks, high shear microstructure of powders obtained under solvothermal conditions.
gradients, and very rapid and efficient mixing in multiphase systems. Ultrasonic irradiation has been successfully used to promote the
When an ultrasonic wave passes through a liquid medium, a large crystallization of many metal oxide nanocrystals in solution [24–26].
number of microbubbles form, grow, and collapse in the very short time Fig. 4 shows TEM images for iron oxide prepared with and without
of a few microseconds, an effect that is called ultrasonic cavitation. ultrasonic irradiation. We can obtain very good crystalline iron oxide
Sonochemical theory calculations and the corresponding experiments nanocrystals with average grain size of 15.8 ± 0.7 nm and a narrower
suggest that ultrasonic cavitation can generate local temperatures as size distribution of σ = 4.4% with ultrasonic irradiation (Fig. 4a). Only
high as 5000 K and local pressures as high as 100 MPa, with heating amorphous iron oxide colloidal can be obtained without ultrasonic
and cooling rates greater than 109 K/s, which is a very extreme irradiation as shown in Fig. 4b. In the present work, the process of
environment [18]. This considerably changes the physicochemical nucleation, crystallization and growth was segregated. The nucleation
process occurred at 190 °C when Fe(CO)5 decomposed. The reported
temperature for crystallization of iron oxide nanoparticles is about
220–250 °C [5,6,17], so the crystallization process could not occur at
190 °C. But the solution temperature would increase from 190 °C to
225 °C (even higher in local parts) after ultrasonic irradiation for
10 min. The local high temperature could promote the crystallization of
the iron oxide nucleus. After crystallization, the growth proceeded at
190 °C when the solution was refluxed at this temperature.
Fig. 3. Iron oxide nanoparticles obtained at different refluxing time. From (a) to
(c), TEM images of iron oxide nanoparticles prepared by refluxing in cis–trans
decalin for 30 min, 60 min and 90 min, respectively. (d) is XRD patterns for iron
oxide particles shown in (a) to (c). The molar ratio of oleic acid to Fe(CO)5 is Fig. 4. TEM images of iron oxide obtained under different reaction conditions.
3:1, ultrasonic irradiation time is 10 min. With (a) and without (b) ultrasonic irradiation.
G.Q. Zhang et al. / Materials Letters 61 (2007) 2204–2207 2207
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