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

Magnetite (Fe3 O4 ) is an important member of ferrite that
has a cubic inverse spinel structure with Fe cations occupying
interstitial tetrahedral sites and octahedral sites of the fcc stack
of oxygen [1]. The electrons can hop between Fe2+ and Fe3+
ions in the octahedral sites at room temperature renders Fe3 O4
an important class of half-metallic materials [2–4]. Fe3 O4
nanoparticles are mainly found useful in various applications
for its unique magnetic and electronic properties [5–7], such as
magnetic storage media, printing inks, magnetic refrigeration,
photoelectric devices, ferrofluids, magnetic resonance imaging
(MRI), magnetically guided drug delivery, magnetic biosepara-
tion, biosensors and bioprocessing [8–17]. However, the density
of the Fe3 O4 (ca. 4.9–5.2 g/cm3 ) restricts its applications in
fields requiring light-weight mass, for instance, microwave
absorbing materials of stealthy defense system for aircraft
∗ Corresponding author at: Institute of Materials Science and Engineering,
Henan Polytechnic University, Jiaozuo 454003, PR China.
Tel.: +86 431 5168763; fax: +86 431 5168258.
E-mail address: yanghb@jlu.edu.cn (H. Yang).
of low density might be a feasible way to overcome the
problem.
By virtue of the very low bulk density and excellent chem-
ical stability, glass microballoons (GMBs), which are hollow
microspheres with dimension of ca. 40–60 ␮m, are highlighted
in recent years as a light-weight filling material in various kinds
of metallic materials, ceramics, concretes, plastics, etc. It is a
good idea that GMBs could be imparted with magnetic property
by coating the microspheres with Fe3 O4 nanoparticles, in order
to obtain the low-density magnetic microspheres. However, as
far as we know, little work has been done to combine Fe3 O4
nanoparticles with GMBs.
In this study, we coated Fe3 O4 nanoparticles on the
surfaces of the pretreated GMBs by reduction–precipitation
method to provide the magnetic hollow microspheres with
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-
tion temperature. It can be expected that these composite
microspheres could have potential applications in some
fields, such as microwave absorbing materials and catalysts
[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
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
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-
tion of complex ions [23]. When the color altered from red to
light yellow again, a proper quantity (2, 3, 4 g) of the pretreated
GMBs were placed into above mixed solution, subsequently,
a predetermined amount of NH3 ·H2 O was added into it under
intensive stirring (pH > 12). The reactions were processed at dif-
ferent temperatures (20, 40, 60, 80 ◦ C) and all continuing for
60 min. When the reaction temperature reached 40 ◦ C or higher,
some black resultants were formed. After coating, the products
were filtered off, washed with deionized water to remove excess
ions, and dried at room temperature for 12 h.
The phase structure analysis of products was identified
(within 2θ range of 25–70◦ ) using a X-ray diffractometer
(XRD; Rigaku D/max-rA) utilizing Cu K␣ X-radiation of wave-
length 1.5418 Å. A field emission scanning electron microscopy
(FESEM; JSM-6700F) equipped with an energy dispersion X-
ray spectroscopy (EDS; INCA X-sight 7421) was used to ana-
lyze the surface morphology and the size distribution of the
microspheres, while EDS analysis was performed to understand
their chemical constituents. To avoid any charging, the sam-
ples were coated with a thin layer of gold using an auto fine
coater (JFC-1600) for FESEM analysis. Their magnetic proper-
ties were evaluated on a vibrating sample magnetometer (VSM;
JDM-13), and the field reached up to 104 Oe. Bulk densities of
different samples were obtained by pouring the material in a
10 ml measuring cylinder and tapping it to a constant volume of
the material. The bulk density is calculated by the mass of the
microspheres to the volume.
3. Results and discussion
The XRD patterns of bare GMBs and the products synthe-
sized at different reaction temperatures are shown in Fig. 1. XRD
analysis of GMBs shows that these spheres are mainly com-
posed of mixture of mullite and quartz. After coating, and the
reaction temperature reaches 40 ◦ C or higher, some more peaks
at 2θ = 30.1◦ , 35.5◦ , 43.2◦ , 57.1◦ and 62.7◦ appear in the spectra.
39
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.
They tally with the PDF card (No. 88-0315) of PCPDFWIN soft-
ware. The corresponding diffraction indices are (2 2 0), (3 1 1),
(4 0 0), (5 1 1) and (4 4 0). Although there is little difference
between the XRD patterns of Fe3 O4 and ␥-Fe2 O3 (maghemite)
for the same inverse spinel structure and nearly the same lattice
parameter [24], the characteristic reflection of (2 2 1) plane cor-
responding to ␥-Fe2 O3 [25] is found to be absent in Fig. 1. It
indicates that the coating of GMBs is Fe3 O4 instead of ␥-Fe2 O3 .
Furthermore, the black color of these samples suggests the for-
mation of Fe3 O4 -coating on account of the red–brown color of
␥-Fe2 O3 . These Fe3 O4 peaks become sharper with the reaction
temperature elevating, which indicates that the Fe3 O4 -coating
is better crystallized and the particle size of Fe3 O4 increases.
The FESEM analysis of GMBs before pretreatment shows
that these microspheres have spherical smooth surface morphol-
ogy (Fig. 2(a)). But the spheres which were pretreated can be
seen many eroded speckles on their surfaces (Fig. 2(b)). The
chemical constituents of these spheres are revealed by EDS anal-
ysis. It shows that they are mainly composed of a mixture of SiO2
and Al2 O3 , while other oxides of trace elements such as K, Fe
and Ca are also present (Fig. 2(c)).
Typical FESEM micrographs of the Fe3 O4 -coated GMBs,
synthesized under different reaction temperatures, are presented
in Fig. 3(a–e), while EDS analysis is presented in Fig. 3(f).
In Fig. 3(a–c), GMBs appear to be successfully coated using
the precipitation coating process. It can be observed that the
products synthesized at 80 ◦ C are coated most uniformly and
continuously of the three samples. Further, the coating appears
to be made up of the nanoparticles having average size below
25 nm (Fig. 3(d)). The hollow structure can be clearly observed
from the image of the broken microsphere (Fig. 3(e)). The thick-
ness of the coating is within a range from 400 to 500 nm. The
EDS analysis of one of the Fe3 O4 -coated GMBs (Fig. 3(f))
shows that there are more Fe element and O element appear-
ance. Thus, FESEM and EDS analyses suggest the uniform and
continuous Fe3 O4 -coating coated on the surfaces of GMBs by
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
Experimental results of coatings obtained at different initial ratios:
R = [Fe3+ ]/[SO3 2− ]
MFeCl3 ·6H2 O (mmol)a MNa2 SO3 (mmol)a R Coating
6 1 6 Fe(OH)3
6 1.2 5 Fe3 O4 + Fe(OH)3
6 1.5 4 Fe3 O4 + Fe(OH)3
6 2 3 Fe3 O4
a FeCl3 and Na2 SO3 were dissolved in 10 ml deionized water, respectively.
Experiments at different R-values were carried out and the
results are summarized in Table 2. It shows that the ideal initial
ratio is R = 3.
The formation of Fe3 O4 -coating is illustrated in Fig. 4. When
GMBs were added into the NaOH solution for pretreatment,
many –OH function groups got adsorbed on their surfaces. There
were also lots of –OH function groups on the surfaces of the
Fe3 O4 nanoparticles which were formed in the alkaline solution.
Then these Fe3 O4 nanoparticles combined with the GMBs by
the condensation reaction. In the late period, further Fe3 O4 was
continuously formed on the prior Fe3 O4 nucleation layer to form
a uniform and continuous Fe3 O4 -coating on the surface of GMB.
The magnetic properties of different samples, which were
measured at room temperature, are shown in Fig. 5. It can
be observed that the hysteresis loops of all samples demon-
strate a typical superparamagnetic behavior with zero coercivity
Fig. 5. Magnetization curves of different samples.
and zero remanence. The superparamagnetism of these sam-
ples should be attributed to the size of the Fe3 O4 nanoparticles
coated on GMBs below the superparamagnetic critical size. It
is because that fine particles are easier to be thermally activated
to overcome the magnetic anisotropy [27]. If the size of Fe3 O4
particle is smaller than the superparamagnetic critical size (DP )
[28], above the blocking temperature (TB ) [29], the magneti-
zation intensity becomes zero with the applied magnetic field
decreasing to zero and aggrandizes fleetly with the aggrandize-
ment of the applied magnetic field. The saturation magnetization
(Ms ) is listed in Table 1. With the same GMB content (S1–S3),
the saturation magnetization values increase with the reaction
temperatures elevating. It is due to the Fe3 O4 -coating better crys-
tallizing and larger crystal size as indicated by XRD (Fig. 1). At
the same reaction temperature (S3–S5), the saturation magne-
tization values decrease with increased GMB content. Because
the weights of all samples used for measurement of magnetic
properties are constant, the decrease of saturation magnetiza-
tion is due to the increased quantity of GMBs incorporated in
the Fe3 O4 -coated GMBs. These results suggest that it is possible
to control the magnetization value of the magnetic microspheres
by controlling the reaction temperature and the GMB content.
4. Conclusion
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
possible.
 X. Li et al. / Materials Science and Engineering B 135 (2006) 38–43
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