Materials Science and Engineering B 135 (2006) 38–43

Preparation of low-density superparamagnetic microspheres by

coating glass microballoons with magnetite nanoparticles
Xiang Li a , Haibin Yang a,b,∗ , Wuyou Fu b , Cunxi Wu a , Shikai Liu b ,
Hongyang Zhu b , Xiaofen Pang b
a Institute of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, PR China
b National Laboratory of Superhard Materials, Jilin University, Changchun 130012, PR China

Received 26 June 2006; accepted 14 August 2006

Abstract
A novel low-density (0.4–0.5 g/cm3 ) hollow composite material with the superparamagnetic character has been synthesized by coating glass
microballoons (GMBs) with magnetite (Fe3 O4 ) nanoparticles via chemical deposition process. The products were characterized by X-ray diffraction
(XRD), field emission scanning electron microscopy (FESEM), energy dispersion X-ray spectroscopy (EDS) and vibrating sample magnetometer
(VSM). A uniform and continuous Fe3 O4 -coating with thickness ca. 400–500 nm was obtained under the given conditions. The size of Fe3 O4
particles of the coating was below 25 nm. The magnetization of the Fe3 O4 -coated GMBs can be controlled by changing the GMB content and
the reaction temperature. These low-density magnetic microspheres are expected to have many advantages in applications such as microwave
absorbing materials and catalysts.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Fe3 O4 nanoparticles; Bulk density; Superparamagnetism; Reduction–precipitation; Surfaces

1. Introduction [18,19]. Coating Fe3 O4 nanoparticles on hollow microspheres

of low density might be a feasible way to overcome the
Magnetite (Fe3 O4 ) is an important member of ferrite that problem.
has a cubic inverse spinel structure with Fe cations occupying By virtue of the very low bulk density and excellent chem-
interstitial tetrahedral sites and octahedral sites of the fcc stack ical stability, glass microballoons (GMBs), which are hollow
of oxygen [1]. The electrons can hop between Fe2+ and Fe3+ microspheres with dimension of ca. 40–60 ␮m, are highlighted
ions in the octahedral sites at room temperature renders Fe3 O4 in recent years as a light-weight filling material in various kinds
an important class of half-metallic materials [2–4]. Fe3 O4 of metallic materials, ceramics, concretes, plastics, etc. It is a
nanoparticles are mainly found useful in various applications good idea that GMBs could be imparted with magnetic property
for its unique magnetic and electronic properties [5–7], such as by coating the microspheres with Fe3 O4 nanoparticles, in order
magnetic storage media, printing inks, magnetic refrigeration, to obtain the low-density magnetic microspheres. However, as
photoelectric devices, ferrofluids, magnetic resonance imaging far as we know, little work has been done to combine Fe3 O4
(MRI), magnetically guided drug delivery, magnetic biosepara- nanoparticles with GMBs.
tion, biosensors and bioprocessing [8–17]. However, the density In this study, we coated Fe3 O4 nanoparticles on the
of the Fe3 O4 (ca. 4.9–5.2 g/cm3 ) restricts its applications in surfaces of the pretreated GMBs by reduction–precipitation
fields requiring light-weight mass, for instance, microwave method to provide the magnetic hollow microspheres with
absorbing materials of stealthy defense system for aircraft low density (0.4–0.5 g/cm3 ). The Fe3 O4 -coated GMBs exhibit
the superparamagnetic character and their magnetization
can be adjusted by altering the GMB content and the reac-
∗ Corresponding author at: Institute of Materials Science and Engineering,
tion temperature. It can be expected that these composite
Henan Polytechnic University, Jiaozuo 454003, PR China.
microspheres could have potential applications in some
Tel.: +86 431 5168763; fax: +86 431 5168258. fields, such as microwave absorbing materials and catalysts
E-mail address: yanghb@jlu.edu.cn (H. Yang). [20–22].

0921-5107/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2006.08.036
 X. Li et al. / Materials Science and Engineering B 135 (2006) 38–43 39

2. Experimental

The GMBs (diameter: 40–60 ␮m) were supplied by Beijing

Lucid Ltd. of China. Chemicals used in our experiment, hexahy-
drate ferric chloride (FeCl3 ·6H2 O), anhydrous sodium sulfite
(Na2 SO3 ), sodium hydroxide (NaOH), ammonia (NH3 ·H2 O,
25 wt.%) and ethanol (CH3 CH2 OH), were analytical reagent
grade and used without further purification. Deionized water
with conductivity larger than 10 M cm was used during the
sample preparation.
All the GMBs were pretreated to improve the surface activ-
ity by two steps: (1) washing a proper quantity of GMBs with
deionized water and ethanol for several times, then filtering and
drying at 80 ◦ C; (2) immersing the GMBs in NaOH solution
(0.5 mol/l) and supersonic cleaning for 30 min, then selecting
the floating GMBs and drying at 80 ◦ C.
The coating procedure was as follows: 1.620 g (6 mmol)
FeCl3 ·6H2 O and 0.252 g (2 mmol) Na2 SO3 were dissolved in Fig. 1. XRD patterns of (a) bare GMBs and products synthesized at: (b) 20 ◦ C,
(c) 40 ◦ C, (d) 60 ◦ C and (e) 80 ◦ C.
10 ml deionized water, respectively. Then the two solutions were
mixed under stirring. It was observed that the color of the mixed
solution changed from light yellow to red, indicating forma- They tally with the PDF card (No. 88-0315) of PCPDFWIN soft-
tion of complex ions [23]. When the color altered from red to ware. The corresponding diffraction indices are (2 2 0), (3 1 1),
light yellow again, a proper quantity (2, 3, 4 g) of the pretreated (4 0 0), (5 1 1) and (4 4 0). Although there is little difference
GMBs were placed into above mixed solution, subsequently, between the XRD patterns of Fe3 O4 and ␥-Fe2 O3 (maghemite)
a predetermined amount of NH3 ·H2 O was added into it under for the same inverse spinel structure and nearly the same lattice
intensive stirring (pH > 12). The reactions were processed at dif- parameter [24], the characteristic reflection of (2 2 1) plane cor-
ferent temperatures (20, 40, 60, 80 ◦ C) and all continuing for responding to ␥-Fe2 O3 [25] is found to be absent in Fig. 1. It
60 min. When the reaction temperature reached 40 ◦ C or higher, indicates that the coating of GMBs is Fe3 O4 instead of ␥-Fe2 O3 .
some black resultants were formed. After coating, the products Furthermore, the black color of these samples suggests the for-
were filtered off, washed with deionized water to remove excess mation of Fe3 O4 -coating on account of the red–brown color of
ions, and dried at room temperature for 12 h. ␥-Fe2 O3 . These Fe3 O4 peaks become sharper with the reaction
The phase structure analysis of products was identified temperature elevating, which indicates that the Fe3 O4 -coating
(within 2θ range of 25–70◦ ) using a X-ray diffractometer is better crystallized and the particle size of Fe3 O4 increases.
(XRD; Rigaku D/max-rA) utilizing Cu K␣ X-radiation of wave- The FESEM analysis of GMBs before pretreatment shows
length 1.5418 Å. A field emission scanning electron microscopy that these microspheres have spherical smooth surface morphol-
(FESEM; JSM-6700F) equipped with an energy dispersion X- ogy (Fig. 2(a)). But the spheres which were pretreated can be
ray spectroscopy (EDS; INCA X-sight 7421) was used to ana- seen many eroded speckles on their surfaces (Fig. 2(b)). The
lyze the surface morphology and the size distribution of the chemical constituents of these spheres are revealed by EDS anal-
microspheres, while EDS analysis was performed to understand ysis. It shows that they are mainly composed of a mixture of SiO2
their chemical constituents. To avoid any charging, the sam- and Al2 O3 , while other oxides of trace elements such as K, Fe
ples were coated with a thin layer of gold using an auto fine and Ca are also present (Fig. 2(c)).
coater (JFC-1600) for FESEM analysis. Their magnetic proper- Typical FESEM micrographs of the Fe3 O4 -coated GMBs,
ties were evaluated on a vibrating sample magnetometer (VSM; synthesized under different reaction temperatures, are presented
JDM-13), and the field reached up to 104 Oe. Bulk densities of in Fig. 3(a–e), while EDS analysis is presented in Fig. 3(f).
different samples were obtained by pouring the material in a In Fig. 3(a–c), GMBs appear to be successfully coated using
10 ml measuring cylinder and tapping it to a constant volume of the precipitation coating process. It can be observed that the
the material. The bulk density is calculated by the mass of the products synthesized at 80 ◦ C are coated most uniformly and
microspheres to the volume. continuously of the three samples. Further, the coating appears
to be made up of the nanoparticles having average size below
3. Results and discussion 25 nm (Fig. 3(d)). The hollow structure can be clearly observed
from the image of the broken microsphere (Fig. 3(e)). The thick-
The XRD patterns of bare GMBs and the products synthe- ness of the coating is within a range from 400 to 500 nm. The
sized at different reaction temperatures are shown in Fig. 1. XRD EDS analysis of one of the Fe3 O4 -coated GMBs (Fig. 3(f))
analysis of GMBs shows that these spheres are mainly com- shows that there are more Fe element and O element appear-
posed of mixture of mullite and quartz. After coating, and the ance. Thus, FESEM and EDS analyses suggest the uniform and
reaction temperature reaches 40 ◦ C or higher, some more peaks continuous Fe3 O4 -coating coated on the surfaces of GMBs by
at 2θ = 30.1◦ , 35.5◦ , 43.2◦ , 57.1◦ and 62.7◦ appear in the spectra. the reduction–precipitation coating process.
40 X. Li et al. / Materials Science and Engineering B 135 (2006) 38–43

Fig. 2. FESEM micrographs of GMBs: (a) before and (b) after pretreatment. (c) EDS analysis of GMBs.

The bulk density (ρB ) of these composite microspheres air. Fe2+ ions are not added, but instead are formed from the Fe3+
measured [26] by the mass of the spheres to the volume is ions by partial reduction with SO3 2− ions before NH3 ·H2 O is
0.4–0.5 g/cm3 as listed in Table 1. added. The reason that reoxidation of Fe2+ as formed through
In the reduction–precipitation reaction of synthesizing the reduction can be avoided is Fe3+ can form complex ions with
Fe3 O4 -coating, we started from Fe3+ ions, which are stable in SO3 2− [23]. The Fe3 O4 particles of the coating were synthesized
as following processes:
Table 1
2Fe3+ + SO3 2− → [Fe2 (SO3 )]4+ (1)
Bulk densities and saturation magnetizations of different samples
Sample Addition mass Reaction ρB a (g/cm3 ) Ms (emu/g) [Fe2 (SO3 )]4+ + H2 O → 2Fe2+ + SO4 2− + 2H+ (2)
of GMBs (g) temperature (◦ C) −
2Fe 3+
+ Fe 2+
+ 8OH → Fe3 O4 + 4H2 O (3)
S1 2 40 0.49 18.5
S2 2 60 0.49 22.6 According to above processes, the theoretical initial
S3 2 80 0.50 30.0 molar ratio R = [Fe3+ ]/[SO3 2− ] should be six in order that
S4 3 80 0.45 20.5 [Fe3+ ]/[Fe2+ ] = 2 after reduction to obtain a pure Fe3 O4 -coating.
S5 4 80 0.42 14.2
However, varied factors can affect the equilibrium of the reduc-
a The bulk density of bare GMBs measured by the same method is 0.39 g/cm3 . tion reaction, such as the concentration of FeCl3 and Na2 SO3 .
 X. Li et al. / Materials Science and Engineering B 135 (2006) 38–43 41

Fig. 3. FESEM micrographs of Fe3 O4 -coated GMBs synthesized at: (a) 40 ◦ C, (b) 60 ◦ C and (c) 80 ◦ C. (d) The Fe3 O4 nanoparticles of Fe3 O4 -coating and (e) the
cross-section of the Fe3 O4 -coated GMBs synthesized at 80 ◦ C. (f) EDS analysis of Fe3 O4 -coated GMBs.
42 X. Li et al. / Materials Science and Engineering B 135 (2006) 38–43

Fig. 4. The process of how Fe3 O4 -coating is formed.

Table 2 and zero remanence. The superparamagnetism of these sam-

Experimental results of coatings obtained at different initial ratios: ples should be attributed to the size of the Fe3 O4 nanoparticles
R = [Fe3+ ]/[SO3 2− ]
coated on GMBs below the superparamagnetic critical size. It
MFeCl3 ·6H2 O (mmol)a MNa2 SO3 (mmol)a R Coating is because that fine particles are easier to be thermally activated
6 1 6 Fe(OH)3 to overcome the magnetic anisotropy [27]. If the size of Fe3 O4
6 1.2 5 Fe3 O4 + Fe(OH)3 particle is smaller than the superparamagnetic critical size (DP )
6 1.5 4 Fe3 O4 + Fe(OH)3 [28], above the blocking temperature (TB ) [29], the magneti-
6 2 3 Fe3 O4 zation intensity becomes zero with the applied magnetic field
a FeCl3 and Na2 SO3 were dissolved in 10 ml deionized water, respectively. decreasing to zero and aggrandizes fleetly with the aggrandize-
ment of the applied magnetic field. The saturation magnetization
Experiments at different R-values were carried out and the (Ms ) is listed in Table 1. With the same GMB content (S1–S3),
results are summarized in Table 2. It shows that the ideal initial the saturation magnetization values increase with the reaction
ratio is R = 3. temperatures elevating. It is due to the Fe3 O4 -coating better crys-
The formation of Fe3 O4 -coating is illustrated in Fig. 4. When tallizing and larger crystal size as indicated by XRD (Fig. 1). At
GMBs were added into the NaOH solution for pretreatment, the same reaction temperature (S3–S5), the saturation magne-
many –OH function groups got adsorbed on their surfaces. There tization values decrease with increased GMB content. Because
were also lots of –OH function groups on the surfaces of the the weights of all samples used for measurement of magnetic
Fe3 O4 nanoparticles which were formed in the alkaline solution. properties are constant, the decrease of saturation magnetiza-
Then these Fe3 O4 nanoparticles combined with the GMBs by tion is due to the increased quantity of GMBs incorporated in
the condensation reaction. In the late period, further Fe3 O4 was the Fe3 O4 -coated GMBs. These results suggest that it is possible
continuously formed on the prior Fe3 O4 nucleation layer to form to control the magnetization value of the magnetic microspheres
a uniform and continuous Fe3 O4 -coating on the surface of GMB. by controlling the reaction temperature and the GMB content.
The magnetic properties of different samples, which were
measured at room temperature, are shown in Fig. 5. It can 4. Conclusion
be observed that the hysteresis loops of all samples demon-
strate a typical superparamagnetic behavior with zero coercivity In summary, low-density (0.4–0.5 g/cm3 ) composite micro-
spheres with the superparamagnetic character have been suc-
cessfully synthesized by coating GMBs with Fe3 O4 nanopar-
ticles. These GMBs appear to be coated most uniformly and
continuously and their saturation magnetization intensity is
the strongest of all the samples when the reaction tempera-
ture reaches 80 ◦ C. The thickness of the Fe3 O4 -coating is ca.
400–500 nm and the size of Fe3 O4 particles of the coating is
below 25 nm. The magnetization value of the Fe3 O4 -coated
GMBs can be adjusted by controlling the GMB content and the
reaction temperature. Furthermore, the low-density and the mag-
netic properties of these composite microspheres make them a
good candidate in microwave absorbing materials and catalysts.

Acknowledgements

The authors are grateful to Professors Z.X. Guo and G. Peng

of Jilin University, who made the FESEM and XRD analyses
Fig. 5. Magnetization curves of different samples. possible.
 X. Li et al. / Materials Science and Engineering B 135 (2006) 38–43 43

References [14] N. Kohler, C. Sun, J. Wang, M. Zhang, Langmuir 21 (2005) 8858–

8864.
[1] R.M. Cornell, U. Schwertmann, The Iron Oxides: Structure, Properties, [15] T. Sen, A. Sebastianelli, I.J. Bruce, J. Am. Chem. Soc. 128 (2006)
Reactions, Occurrences and Uses, Wiley-VCH, New York, 1996, pp. 7130–7131.
28–29. [16] J.M. Perez, F.J. Simeone, Y. Saeki, L. Josephson, R. Weissleder, J. Am.
[2] E.J.W. Verwey, Nature 144 (1939) 327–328. Chem. Soc. 125 (2003) 10192–10193.
[3] J.M.D. Coey, A.E. Berkowitz, L. Balcells, F.F. Putris, F.T. Parker, Appl. [17] L. Nixon, C.A. Koval, R.D. Noble, G.S. Slaff, Chem. Mater. 4 (1992)
Phys. Lett. 72 (1998) 734–736. 117–121.
[4] S. Soeya, J. Hayakawa, H. Takahashi, K. Ito, C. Yamamoto, A. Kida, H. [18] K. Hatakeyama, T. Inui, IEEE Trans. Magn. 20 (1984) 1261–1263.
Asano, M. Matsui, Appl. Phys. Lett. 80 (2002) 823–825. [19] M. Matsumoto, Y. Miyata, IEEE Trans. Magn. 33 (1997) 4459–4464.
[5] D.G. Rethwisch, J.A. Dumesic, Appl. Catal. 21 (1986) 97–109. [20] Y.D. Deng, X. Liu, B. Shen, L. Liu, W.B. Hu, J. Magn. Magn. Mater. 303
[6] J.P. Jolivet, E. Tronc, J. Colloid Interface Sci. 125 (1988) 688–701. (2006) 181–184.
[7] U. Häfeli, W. Schütt, J. Teller, M. Zborowski, Scientific and Clinical Appli- [21] F. Pinna, T. Fantinel, G. Strukul, A. Benedetti, N. Pernicone, Appl. Catal.
cations of Magnetic Carriers, Plenum, New York, 1997. A 149 (1997) 341–351.
[8] K. Yamaguchi, K. Matsumoto, T. Fujii, J. Appl. Phys. 67 (1990) 4493–4495. [22] D.L. Wilcox, T. Bernat, D. Kellerman, J.K. Cochran, Materials Research
[9] V.T. Peikove, K.S. Jeon, A.M. Lane, J. Magn. Magn. Mater. 193 (1999) Society Proceedings, vol. 375, MRS, Pittsburgh, 1995.
307–310. [23] E. Danilczuk, A. Swinarski, Roczn. Chem. 35 (1961) 1563–1572.
[10] R.D. McMichael, R.D. Shull, L.J. Swartzendruber, L.H. Bennett, R.E. Wal- [24] D.O. Smith, Phys. Rev. 102 (1956) 959–963.
son, J. Magn. Magn. Mater. 111 (1992) 29–33. [25] S.Z. Wang, H.W. Xin, Y.T. Qian, Mater. Lett. 33 (1997) 113–116.
[11] D.K. Kim, Y. Zhang, W. Voit, K.V. Rao, M. Muhammed, J. Magn. Magn. [26] I.N. Bhattacharya, P.K. Gochhayat, P.S. Mukherjee, S. Paul, P.K. Mitra,
Mater. 225 (2001) 30–36. Mater. Chem. Phys. 88 (2004) 32–40.
[12] Y. Shahoo, A. Goodarzi, M.T. Swihart, T.Y. Ohulchanskyy, N. Kaur, E.P. [27] X.B. Gao, L. Gu, Nanotechnology 16 (2005) 180–185.
Furlani, P.N. Prasad, J. Phys. Chem. B 109 (2005) 3879–3885. [28] J. Lee, T. Isobe, M. Senna, J. Colloid Interface Sci. 177 (1996) 490–
[13] H. Lee, E. Lee, D.K. Kim, N.K. Jang, Y.Y. Jeong, S. Jon, J. Am. Chem. 494.
Soc. 128 (2006) 7383–7389. [29] Y.L. Hou, J.F. Yu, S. Gao, J. Mater. Chem. 13 (2003) 1983–1987.