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International Journal of Minerals, Metallurgy and Materials

Volume 16, Number 2, April 2009, Page 226 Materials

Surface modification of Fe3O4 nanoparticles and their magnetic properties

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).]

1. Introduction ple have reported the effects of surfactant on Fe3O4


nanoparticles. In this study, the hydrothermal method
Fe3O4 has a cubic inverse spinel structure, where was used to synthesize Fe3O4 nanoparticles by using
oxygen forms a face-cubic-crystal closed packing and sodium bis(2-ethylhexyl) sulfosuccinate (AOT) as the
Fe occupies interstitial tetrahedral sites and octahedral dispersant and hydrazine hydrate (N2H4·H2O) as the
sites [1]. It exhibits unique electric and magnetic reagent for adjusting the pH value of the solution [15],
properties since electrons can transfer between Fe2+ respectively. The influences of the surfactant on the
and Fe3+ ions in the octahedral sites. Nevertheless, size, the dispersal, and the magnetic properties of
magnetic nanoparticles show novel properties that are Fe3O4 nanoparticles were investigated. The results
different from those of the bulk due to their small size showed that the surfactant had great effects on the
and fundamental change in the coordination, symme- growth of the particles.
try, and confinement [2]. They have a wide range of
applications, such as magnetic recording media, ca- 2. Experimental
talysis, medicine transporter, biomedicine, and so on All the reagents were of analytical grade. They
[3-6]. So the synthesis of magnetic nanoparticles has were purchased from China National Medicines
long been pursued for their extensive scientific and (Group) Shanghai Chemical Reagents Company and
technological interest. were used without further purification.
Fe3O4 magnetic nanoparticles have been prepared Typically, the aqueous FeCl3 solution and AOT so-
using many methods such as coprecipitation [7-8], lution were prepared. The N2H4·H2O (50wt%) and
sol-gel [9], sonochemistry [10], colloidal method [11], AOT solution were then added into the FeCl3 solution
nonaqueous route [12-13], gas-phase method [14] etc. at the same time. After magnetic stirring for some
Although there are a large number of reports on the time, the mixture was transferred into the Teflon-lined
synthesis and magnetic properties of Fe3O4 nanoparti- stainless autoclave. The autoclave was put in an oven
cles, there have not been any detailed studies on the at 150qC for 10 h and then slowly cooled to room
size controllability conditions. Furthermore, few peo- temperature naturally. The black Fe3O4 nanoparticles
Corresponding author: Jian-cheng Zhang, E-mail: jchzhang@mail.shu.edu.cn Also available online at www.sciencedirect.com
© 2009 University of Science and Technology Beijing. All rights reserved.
H. Yan et al., Surface modification of Fe3O4 nanoparticles and their magnetic properties 227

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.

3. Results and discussion


Fig. 1 shows the FT-IR spectrum of the
as-synthesized sample D. The peaks around 1047 and
3422 cm1 should be ascribed to the symmetric
stretching vibration of the (CH2)n group and of the
OH group, respectively. The peaks around 1629 and
1399 cm1 assignable to the asymmetric and symmet-
ric stretching vibration of C=O can be obviously
found. So it is demonstrated that the surfactant (AOT)
molecules are chemically bonded to the surface of the Fig. 2. TEM image of the Fe3O4 nanoparticles with the
hydrothermal reaction time of 10 h at 150qC
nanoparticles. The peak at about 577 cm1 is related to
the vibration of the FeO functional group, which Fig. 3 is the XRD spectra of the obtained magnetic
matches well with the characteristic peak of Fe3O4 Fe3O4 nanoparticles from different molar ratios of
[16]. But the peak has slight red shift, and this may be AOT to Fe3+. The curves of (a), (b), (c), and (d) in Fig.
because of the existence of the surfactant on the sur- 3 represent the samples A, B, C, and D, respectively.
face of the particles. The XRD patterns exhibit a group of spinel-type dif-
fraction peaks similar to the reported data (JCPDS
#72-2303), which can be indexed as the face-centered
cubic Fe3O4 structure with a lattice parameter a=0.840
nm. Based on the Scherrer’s formula, the average

Fig. 1. FT-IR spectrum of the as-prepared sample D.

The TEM image of sample D is shown in Fig. 2.


The average particle size is about 11 nm, and the dis-
tribution of the particle diameters is relatively ho-
mogenous. The dispersion of the Fe3O4 nanoparticles
is much better. There are three types of interactions Fig. 3. XRD patterns of the obtained samples A (a), B (b),
among the nanoparticles: London-Van der Waals C (c), and D (d).
228 International Journal of Minerals, Metallurgy and Materials, Vol.16, No.2, Apr 2009

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 A˜m2˜kg1). 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

Table 2. Specific saturation magnetizations (ıs) of samples A, B, C, and D


Sample Molar ratio of AOT to Fe3+ Average diameter/nm Specific saturation magnetization / (A˜m2˜kg1)
A 0.00 27.5 87.7
B 0.23 17.9 72.4
C 0.56 12.2 63.8
D 1.13 12.1 55.8

4. Conclusion properties of magnetite nanoparticles by sol-gel method, J.


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