International Journal of Nanoscience Vol. 10, No. 3 (2011) 515520 c # World Scientic Publishing Company . DOI: 10.

1142/S0219581X11008289

BIREFRINGENCE AND MAGNETO-OPTICAL PROPERTIES IN OLEIC ACID COATED Fe3 O4 NANOPARTICLES: APPLICATION FOR OPTICAL SWITCH
SI-HUA XIA*, JUN WANG*,z,, ZHANG-XIAN LUy and FEIYAN ZHANG* *Faculty of Science, Ningbo University Ningbo, 315211, Zhejiang, China yJunior College, Wanli University Ningbo, 315100, Zhejiang, China zwjnaf@ustc.edu Received 4 November 2010 Accepted 16 January 2011
We report magneto-optical properties in a kerosene colloidal suspension of oleic acid coated Fe3 O4 nanoparticles ($14 nm). The magnetic colloids (uids) show birefringence under a magnetic eld. Systematical studies of the ono switch times upon application of the ono magnetic eld with varied experimental parameters indicate that the switch response time depends strongly on the strength of the magnetic eld and the concentration of the magnetic nanoparticles in the uid. The data can be explained in terms of the formation of magnetic nanoparticle chains under a magnetic eld. The important magneto-optical properties of the magnetic uids allow us to design a tunable optical switch. Keywords: Magnetic uids; birefringence; magneto-optical properties; optical switch.

1. Introduction
Colloids have been important in both fundamental and applied research because of their interesting physical properties.13 Localization of light in a disordered medium has been a topic of intense research during the last few decades.46 Magnetic colloids consist of superparamagnetic particles dispersed in a nonmagnetic uid. Like other colloidal systems, the rheological properties of magnetorheological suspensions are intimately tied to the microscopic structure and interparticle forces.7 Some signicative works have been done on the fundamental properties of magnetic colloids and the variety of its properties
Corresponding

when magnetic eld was applied on it.812 Magnetic colloids can be easily manipulated with an external magnetic eld and thus are exciting systems for both fundamental and applied research.1316 In the past decade, magneto-optical eects of magnetic colloids have attracted much attention due to their potential applications in the construction of various functional devices such as magnetic eld sensors,1719 tunable gratings,2022 optical lters,23,24 modulators,25 and switches.15,26 The physical mechanism responsible for the interesting magneto-optical eects is the formation of magnetic particle chains or columns in magnetic colloids under magnetic elds applied either parallel or perpendicular to magnetic

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colloid lms.22,25 The magnetic chains or columns of micrometer size lead to the modications of the refractive index and transmittance of magnetic colloids.27,28 It is generally believed that these modications are caused by a geometrical shadowing eect.29,30 That is, the cross section opaque to the incident light increases upon application of a magnetic eld. The magnetic response time of the colloidal lms depends not only on the properties of the magnetic colloidal lms (e.g., the concentration of magnetic particles, viscosity of the carrier liquid, thickness of the lm, etc.) but also on the strength, direction, and sweep rate of the applied magnetic eld.15,26 In this paper, we report magneto-optical properties in kerosene colloidal suspensions of oleic acid coated Fe3 O4 nanoparticles ($14 nm). The magnetic uids show birefringence under a magnetic eld. The magnetic colloids used in our experiments have excellent long-term stability with no permanent agglomerations even after prolonged application of strong magnetic elds. Systematic studies of the ono switch times upon application of the ono magnetic eld in varied experimental parameters indicate that the switch response time depends strongly on the experimental parameters such as the strength of the magnetic eld and the concentration of the magnetic nanoparticles in the uids. We tentatively explain the data in terms of the formation of magnetic nanoparticle chains under a magnetic eld. The important magnetooptical properties of the magnetic uid allow us to design a tunable optical switch.

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Fig. 1. (a) Experimental setup for birefringence and relaxation time measurements. (b) Schematic diagram of ferrouid lms.

the middle of the second glass is about 2 mm 2 . The measurement system includes polarizer, analyzer, pinhole, detector, and personal computer. A schematic plot of the setup is shown in Fig. 1(a).

3. Results and Discussion

To examine the particle crystalline structure and their mean diameter, we performed X-ray diraction for a powder sample. A typical result obtained

2. Experimental
FeSO4 7H2 O (0.01 mol), FeCl3 6H2 O (0.02 mol) were rst dissolved in 60 mL de-ionized water, stirring the above solution vigorously while a sucient volume of ammonia was added to raise the pH and maintain it between 11 and 11.5 for half an hour. After Fe3 O4 nanoparticles precipitated out of the solution, 5 mL of oleic acid was added to the solution to coat the nanoparticles with oleic acid. The solid material was allowed to settle and water was decanted. Then, the magnetic nanoparticles were dried at 65  C for 10 h. Finally, the dried nanoparticles were dispersed into kerosene to form homogeneous magnetic uid. The ferrouids were transported into the glasses, as shown schematically in Fig. 1(b). The thickness of each glass is 0.2 mm and the area of the hole in

Fig. 2. X-ray diraction spectrum of Fe3 O4 nanoparticles used to make ferrouids. The peaks characteristic of the Fe3 O4 spinel structure are marked.

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Fig. 3. Relative transmittance as a function of magnetic eld for the ferrouid samples with the concentrations of (a) 0.8 vol.% and (b) 3 vol.%.

with the Cu K (1.54 ) radiation is presented in Fig. 2. All the diraction peaks can be indexed by the cubic phase of Fe3 O4 , which is in good agreement with the reported spectrum (JCPDS Card No. 19-0629). The full width at half maximum of the (311) peak is found to be 0:5826  . Using the DebyeScherrer equation,31d 0:89= cos , we calculate that d is $14 nm. Figure 3 shows the relative transmittance as a function of magnetic eld for dierent concentrations when  160   is the angle between the external eld and the deexion of polarizer). At a lower concentration (0.8 vol%), the transmittance increases with increasing magnetic eld. We attribute this to the birefringence in the magnetic uid.32 Since a high magnetic eld (0.12 T) is required for the transmittance to reach saturation for this concentration, its applications will be limited. In contrast, for a higher concentration of 3 vol% (Fig. 3), the transmittance acquires a maximum rst (at a lower eld of 0.012 T), and then decreases as we further increase the magnetic eld up to 0.125 T. This suggests that a lower eld is required for the transmittance to reach a maximum when the concentration is higher. In the absence of the magnetic eld, the particles are randomly distributed in the ferrouid as shown in Figs. 4(a) and 5(a). After turning the magnetic eld on, individual nanoparticles will join together through magnetic interaction,33 forming magnetic chains along the eld lines (see Fig. 4(b)). These sparse chains result in anisotropy of the magnetic uid and nally the birefringence, as shown in Fig. 3(a). In the case of the lower concentration of

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Fig. 4. Schematic plots of the proposed nanoparticles aggregation patterns for the 0.8 vol% ferrouid in the eld of (a) H 0 T and (b) H 0:08 T.

0.8 vol%, less chain could be formed under a magnetic eld. Because of the limited amount of nanoparticles, the transmittance increases slowly with increasing magnetic eld. When we increase the concentration of the magnetic uid to 3 vol%, the magnetic nanoparticles at a lower magnetic eld are divided into two parts: magnetic chains and hollow individual particles, as demonstrated in Fig. 5(b). These magnetic chains lead to the enhancement of the transmittance when the magnetic eld increases from 0 to 0.012 T. Dierent from the situation above for the 0.8 vol% ferrouid, there are enough magnetic nanoparticles here to form magnetic chains when we continue to increase the magnetic eld. The hollow individual particles turn into magnetic chains which induce the coarsening of chains (see Fig. 5(c)), and these coarsened chains act like a wall which reduces the transmittance (see in Fig. 3(b)). As discussed above, transmittance is a function of the magnetic eld and also depends on the

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Fig. 6. The dependence of the maximum transmittance on   is the angle between the external eld and the deexion of polarizer, and the concentration of the ferrouid we used is 3 vol%; the intensity of magnetic eld is 0.01 T).

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Fig. 5. Schematic plots of the proposed nanoparticle aggregation patterns for the 3 vol% magnetic uid in the eld of (a) 0 T, (b) 0.01 T, and (c) 0.08 T.

concentration of nanoparticles in the uid. Given the concentration of ferrouid and intensity of magnetic eld, the transmittance also changes when  is changed ( is the angle between the external eld and the deexion of polarizer), as we can see in Fig. 6 (3 vol%, 0.01 T). As indicated by arrow 1, almost no power is received by the detector when

 110  even if the magnetic eld increases to 0.125 T. In contrast, a large value of the transmittance is seen at  160  (indicated by arrow 2). This result indicates that dierent polarization directions of the light can lead to dierent magnitudes of the transmittance, which is the signature of birefringence in the magnetic uid. Figure 7 plots the time-dependent applied magnetic eld and the corresponding response of the transmittance of the magnetic uids with dierent concentrations (0.8 vol% and 3 vol%). When the eld (H 0:08 T) is applied to the magnetic uid with a lower concentration of 0.8 vol% (Fig. 7(a)), the transmittance increases to a large value within 0.06 s, while it takes a much longer time (about 0.5 s) for the transmittance to decrease to zero when the applied eld is turned o. When the concentration is increased to 3 vol% while other parameters are kept unchanged (Fig. 7(b)), the transmittance acquires a maximum after applying the magnetic eld and then decreases to a constant value in about 0.07 s. After removal of the magnetic eld, the transmittance increases to a maximum and then decreases to zero in about 0.8 s. In the third case where the magnetic eld is reduced to 0.01 T and the concentration of the magnetic uid is kept at 3 vol% (Fig. 7(c)), the switch behavior is similar to 0.8 vol% (0.08 T) with a shorter time (0.25 s) for the transmittance to reduce to zero after the eld is turned o. As discussed above, magnetic chains formed in the ferrouid under a magnetic eld result in

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force between nanoparticles is far smaller than the magnetic force acted by the magnetic eld. The large dierence of these forces may explain the result shown in Fig. 7(a). As we mentioned above, the transmittance decreases if there are too many magnetic chains in the uid. Therefore, for the concentration of 3 vol% and the magnetic eld of 0.08 T, the number of magnetic chains increases from zero to a big one after applying a magnetic eld. After removing the magnetic eld, the magnetic chains diminish slowly in the uid, which leads to the abnormal situation we have seen in Figs. 3(b) and 7(b). The individual nanoparticles which are dispersed in the uid will have a magnetic attractive force on the chains under a eld, so it needs much less time for the uid of 3 vol% at 0.01 T than for the uid of 0.8 vol% at 0.08 T to have its transmittance drop to zero (compare Figs. 7(a) and 7(b)).

4. Conclusions
In summary, we have investigated magneto-optical properties in kerosene colloids of oleic acid coated Fe3 O4 nanoparticles. The magnetic uids show birefringence under a magnetic eld. Our systematical studies of the ono switch times upon application of the ono magnetic eld under varied experimental conditions indicate that the switch response time depends on the experimental parameters such as the strength of the magnetic eld, the concentration of the magnetic nanoparticles in the uid, and the polarization direction of the incident light. We tentatively explain the data in terms of the formation of magnetic nanoparticle chains under a magnetic eld. The important magneto-optical properties of the magnetic uid allow us to design a tunable optical switch.

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Acknowledgments
This work was supported by the National Natural Science Foundation of China (10874095), the Natural Science Foundation of China, Zhejiang (Y407267), the Department of Science and Technology Foundation of China, Zhejiang (2009C31149), the Natural Science Foundation of Ningbo (2008B10051), and K. C. Wong Magna Foundation in Ningbo University.

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Fig. 7. Time-dependent external magnetic eld (solid blue line) and the corresponding variation of the transmittance (red dots) for the magnetic uids with the concentrations of 0.8 vol% (a) and of 3 vol% ((b) and (c)).

birefringence and the change of the transmittance. These chains are formed quickly under a magnetic eld because of the magnetic force, while the chains need a longer time to diminish because the repulsive

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