Yan 2009
Yan 2009
Yan 2009
Hao Yan, Jian-cheng Zhang, Chen-xia You, Zhen-wei Song, Ben-wei Yu, and Yue Shen
School of Materials Science and Engineering, Shanghai University, Shanghai 200072, China
(Received 2008-04-11)
Abstract: Fe3O4 magnetic nanoparticles were synthesized by the hydrothermal method, and the influences of the surfactant sodium
bis(2-ethylhexyl) sulfosuccinate (AOT) on the particles were investigated. The structure, morphology, and magnetic properties of the
products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infra-
red spectroscopy (FT-IR), and vibrating sample magnetometer (VSM). It is confirmed that the as-prepared nanoparticles have been
modified by using the surfactant during the synthesis process. The amount of the surfactant has an effect on the size, the dispersal,
and the magnetic properties of the particles. Besides, the mechanisms of the influences were also discussed.
Key words: surfactant; magnetite nanoparticle; hydrothermal; particle size; dispersion; magnetism
[This study was financially supported by the National Natural Science Foundation of China (No.90206017), Systems Biology Re-
search Foundation of Shanghai University, Innovation Program of Shanghai Municipal Education Commission (No.08YZ08), and
Shanghai City Committee of Science and Technology (No.08520741600, 0572nm016, 07JC14058).]
were precipitated by centrifugation, washed, and dried force, magnetic force, and the reacting force of the
in air. double electronic layer. The preceding two affinities
All the as-prepared samples (A, B, C, and D) have among the particles must be counteracted by the later
the same experimental conditions except the different repulsive force to make the particles exist stably in the
molar ratios of AOT to Fe3+. The ratios of samples A, solvent. But this kind of repulsive force is very small.
B, C, and D are 0, 0.2, 0.5, and 1, respectively. Generally, in order to make the particles disperse well
in the solvent, the nanoparticles should be given sur-
The X-ray diffraction (XRD) data were collected at face modification to make them absorb one layer of
room temperature using a Rigaku D/max 2200 V polymer on the surface. Thus, the space hindrance re-
X-ray diffractometer with high-intensity Cu KĮ radia- pulsive force from the polymer can conquer the affini-
tion (Ȝ=0.154056 nm). For measuring the diameters of ties between the particles. At the same time, the rim
magnetite nanoparticles, the TEM images were taken angle and the wetting property of the nanoparticles
using FEI Tecnai 20 transmission electron microscopy. with other mediums can be improved by the surface
The IR spectrum was recorded using Avatar 370 modification of the particles, and then the dispersal
FT-IR (Thermo Nicolet, America). The magnetic property will be better. In this experiment, AOT was
properties of the nanoparticles were measured using used as the surfactant to make the Fe3O4 nanoparticles
an EG&G Princeton Applied Research Vibrating disperse well in the solvent.
Sample Magnetometer (VSM) at room temperature.
crystallite sizes of the powder samples were calculated Fig. 4 shows the hysteresis loops of the
using the strongest phases of the diffraction plane (311) as-synthesized samples A, B, C, and D measured at
in Fig. 3. The results, listed in Table 1, show that the room temperature. The results indicate that all the par-
average particle size decreases with the increase in the ticles are likely superparamagnetic at room tempera-
molar ratio (AOT/Fe3+). The hydrothermal approach ture since the remanence of the particles is zero and
used here is one of the solution-phase methods, which the coercivity is almost negligible in the absence of an
involves nucleation and growth from the homogene- external magnetic field. The reason for the nanoparti-
ous solution [17]. Since the particle synthesis from a cles having superparamagnetic property is explained
homogeneous solution involves nucleation and growth, as follows: the characteristic physical lengths related
it is essential to make the particles grow to a specific to magnetism (such as the size of the single magnetic
size and then to arrest the growth. One of the strate- domain and the critical size of superparamagnetism)
gies is to form micelles to arrest the growth after nu- are approximately 1-100 nm. When the particle size is
cleation and constrain the particle size [18]. In this ar- corresponding to or smaller than the characteristic
ticle, AOT was used as the surfactant (in samples B, C, physical length, the particles will show abnormal
and D), which may form micelles on the surface of the magnetic properties. Since the critical size of super-
particles after nucleation, thereby prohibiting further paramagnetism for Fe3O4 at room temperature is 16
growth in a way. The ability of the micelles to arrest nm and the average diameter of the as-prepared sam-
the growth of the particles becomes stronger by in- ple is about 11 nm, the Fe3O4 particles exhibit super-
creasing the amount of the surfactant, so the average paramagnetism.
particle size decreases, finally leading to the homoge- From Table 2, it can be seen that the specific satu-
neous dispersal of them. ration magnetizations (ıs) of samples B, C, and D are
Table 1. Estimated average particle diameter according to smaller than that of the Fe3O4 bulk material (ıs=88
the Scherrer’s formula Am2kg1). According to the report of Ref. [19], the
Sam- Molar ratio of 2T / FWHM/ Average decrease in ıs results from the noncollinear structure
ple AOT to Fe3+ (q) (q) diameter/nm of the surfactant on the surface of the particles. Mean-
A 0.00 35.4 0.30 27.5 while, ıs decreases with decreasing the particle size in
B 0.23 35.4 0.46 17.9 the range of 10-30 nm (see Fig. 4 and Table 2). So the
C 0.56 35.4 0.67 12.2 decrease in ıs here is most likely attributed to the ex-
D 1.13 35.4 0.68 12.1 istence of the surfactant on the surface of the Fe3O4
nanoparticles and their much smaller sizes.
Fig. 4. Hysteresis loops of the magnetic Fe3O4 nanoparticles of samples A (a), B (b), C (c), and D (d) measured at room
temperature.
H. Yan et al., Surface modification of Fe3O4 nanoparticles and their magnetic properties 229