Advanced Powder Technol., Vol. 18, No. 1, pp.

81– 91 (2007)
© VSP and Society of Powder Technology, Japan 2007.
Also available online - www.brill.nl/apt

Invited original paper

Surface properties of nanosize hollow silica particles

on the molecular level

MASAYOSHI FUJI 1,∗ , CHIKA TAKAI 1 , YOSHIE TARUTANI 1 ,

TAKASHI TAKEI 2 and MINORU TAKAHASHI 1
1 Ceramics Research Laboratory, Nagoya Institute of Technology,
10-6-29 Asahigaoka, Tajimi 507-0071, Japan
2 Faculty of Urban Environmental Sciences, Tokyo Metropolitan University,
1-1 Minamiohsawa, Hachioji, Tokyo 192-0397, Japan

Received 30 June 2006; accepted 4 September 2006

Abstract—Hollow particles are a newly developing material with the special properties of low
density, thermal insulation and distinct optical activity. A number of preparation methods have been
proposed in the literature. The polymer bead template method is one of the common processes to
synthesize hollow particles, which can easily control particle size. However, byproducts produced
during preparation adversely affect the natural environment. We have proposed an inorganic template
method which overcomes the above disadvantages and also has some strong points. Although
particle surface structure strongly affects wettability and particle dispersability, there are few reports
that have discussed hollow particle structure. In this study, the shell wall structure of hollow
particles was determined in detail by an analysis adsorption mechanism using the nitrogen adsorption
isotherm. The results were compared with those of dense particles. The characteristics of the surface
hydroxyl groups which react with surface modification reagents were then evaluated by water vapor
adsorption. The modified surface was also characterized by Fourier-transform infrared spectroscopy
and thermogravimetry/differential thermal analysis.

Keywords: Hollow particle; silica; surface property; surface structure; pores.

1. INTRODUCTION

Hollow particles form a kind of powder containing an interior hollow structure.

The hollow structure is usually covered by a solid shell. Due to their special
properties, such as low density, thermal insulation and prominent optical activities,
hollow particles have been applied in many areas, including drug delivery [1, 2],
bioencapsulation [3, 4], medical diagnostics [5], catalysis [6], plasmonics [7],

∗ To whom correspondence should be addressed. E-mail: fuji@nitech.ac.jp

82 M. Fuji et al.

and composite electronic and structural materials [8, 9]. Hollow particles with
dimensions from nanometers to micrometers are becoming a focus in nanoscience
and nanotechnology.
Various methods have been developed for the preparation of hollow particles. The
polymer bead template method is one of the common processes to fabricate hollow
particles using polymer as a template [10 –15]. The advantage of this method is to
be able to obtain uniform nanosize hollow particles easily. However, CO2 gas and
waste organic solvent are generated during removal of polymer using calcination
and dissolution. These byproducts adversely affect the natural environment. We
have proposed an inorganic bead template method which uses calcium carbonate
as a template [16]. Coating on the template particles was formed using a sol-
gel method to synthesize core–shell particles. Finally, the calcium carbonate is
removed easily by acid treatment and hollow particles can be obtained. As a
second advantage, it is not necessary to adjust particle surface charge because these
particles have the opposite surface charge. Recently, some new methods based on
in situ templates without using the additional templates have also been developed,
such as the bubble template method [17].
Due to the development of nanotechnology, particle size is now able to be
controlled on a nano-scale. Nanosize hollow particles have properties of both
hollow and nanosize particles. Nanosize particles aggregate easily due to the large
specific surface area. Although particle behavior strongly depends on the surface
structure, there are few reports that have discussed the hollow particle structure.
In this study, surface characterization of hollow particles was attempted using
nitrogen gas adsorption. The shell characteristics were estimated from adsorption
isotherm and Brunauer–Emmett–Teller (BET) specific surface area. The difference
of adsorption mechanism between them is also discussed.
The silica particle surface has lots of silanol groups which react with surface
modification reagents. Here, chemical surface modification was performed and
the modified surfaces were characterized using Fourier-transform infrared (FT-IR)
spectroscopy and thermogravimetry (TG)/differential thermal analysis (DTA).

2. EXPERIMENTAL
2.1. Sample preparation
Hollow particles were synthesized according to our proposed method — the in-
organic template method using calcium carbonate as a template [18, 19]. Cal-
cium carbonate was obtained from Nittetsu Mining, with a particle size of about
50 nm determined from transmission electron microscopy (TEM) observation.
Calcium carbonate, ethanol, tetraethoxysilane (TEOS) and ammonium aqueous
solution were mixed and stirred for 2 h at room temperature in the ratio of
CaCO3 :EtOH:TEOS:NH3 aq = 3.26:15:1:1 to obtain core–shell particles. After re-
moval of the template using acid treatment, hollow silica particles of about 65 nm di-
ameter were obtained. As reference particles, dense silica particles (Aerosil OX50;
 Properties of nanosize hollow silica particles 83

Nihon Aerosil) were used. For surface modification, n-butanol was used as a mod-
ification reagent and hexane as a solvent. The degree of modified surface was con-
trolled by n-butanol content for surface hydroxyl groups. Surface modification was
carried out by use of an autoclave [20, 21]. The reaction was performed at 235◦ C,
30 atm for 1 h. The amount of modification groups was estimated from TG/DTA
analysis.

2.2. Adsorption measurements

Nitrogen adsorption measurements for the pretreatment samples were carried out
using a surface area analyzer based on the volumetric method (Gemini 2375;
Shimadzu). The measurements were preformed at liquid nitrogen temperature
(−196◦ C) until a relative pressure of 1. The measured data were applied to the
BET equation and a specific surface area was calculated. The cross-sectional area
of nitrogen molecule was taken as 0.162 nm2 . The pore volume in the dry state and
the average pore diameter were determined by the Barrett–Joyner–Halenda (BJH)
method, which can be applied to materials with an average pore size of 0.2 nm and
more.
The properties of the surface silanol groups of the hollow particle were examined
by water vapor adsorption (Belsorp Max; Bel Japan). The samples treated by
degassing at 200◦ C under vacuum for 2 h were exposed to water vapor up to a
relative pressure of P /P0 = 1. The water was used after removal of dissolving
gas using bubbling of nitrogen and freeze–thaw cycles. The cross-sectional area of
water molecules was taken as 0.105 nm2 calculated from density. The v–v plot
is a kind of analysis for adsorption measurement by comparison of the amount
adsorbed between the reference and samples at each relative pressure as well as the
v–t plot and α–s plot. It has been reported that the mechanism of water molecule
adsorption on a smooth surface is as follows [22]. Water molecules tend to adsorb
first on surface hydroxyl groups which have higher hydrophilicity. Next, adsorption
occurs around the above prior adsorption to make island-type adsorption. This is
because the definition of t, which stands for the adsorbed layer thickness in the
v–t plot, becomes unclear. Therefore, the v–v plot was employed to evaluate the
difference of adsorption mechanisms directly from the change of amount adsorbed
in this experiment.

2.3. IR measurement

The unmodified and modified samples were pressed in a die. The samples thus
obtained were placed into a cell. IR spectra were obtained by an FT-IR 6200
spectrometer (JASCO).
84 M. Fuji et al.

2.4. Estimation of the surface density of the modifiers

The surface modification was carried out by the reaction of n-butanol molecules
with hydroxyl groups on the silica surface according to:
\ \
− Si–OH + CH3 CH2 CH2 CH2 OH −→ − Si–O–CH2 CH2 CH2 CH3 + H2 O. (1)
/ /

The surface density modifier was estimated from the number of modifiers and
the specific surface area. The number of n-butoxy groups was determined using
TG/DTA (Thermo Plus TG8120; Rigaku) [23]. The measurement was carried out
under oxygen at a flow rate of 250 ml/min. The surface n-butoxy group density, dA ,
was calculated using:
(wCH − wOH )NA
dA [/nm2 ] = × 10−18 , (2)
MW SN2
where wCH and wOH are the ratios of weight loss for the modified and
unmodified samples measured by TG, MW is the molar weight of the n-butanol
group, SN2 is the BET specific surface area measured from the nitrogen adsorption
isotherm, and NA is Avogadro’s number.
The ratio of surface modification is represented by that of conversion from surface
hydroxyl groups to n-butoxy groups. The density of surface hydroxyl groups for
an unmodified sample was determined to be 2.8 OH/nm2 by the Grignard reagent
method [24].

3. RESULTS AND DISCUSSION

3.1. Characterization of hollow particle surface

Figure 1 shows adsorption–desorption isotherms of nitrogen on hollow particles
(triangles) and smooth dense particles as reference (diamonds). Black and white
symbols indicate adsorption and desorption, respectively. The appearance of the
isotherm for hollow particles was almost the same as that of dense particles which
indicates type II of the BDDT classification [25]. Detecting no hysteresis loop
indicates that no meso-pores (20–50 nm) exist in the shell wall of hollow particles.
The hollow structure has no influence on the adsorption mechanism. In addition,
using the BET equation, specific surface area was calculated as 130.9 m2 /g. The
dense particles have a specific surface area of 48.3 m2 /g.
A hollow particle has a shell which has inside and outside surfaces. To examine
the meaning of specific surface area for a hollow particle, the proposed model is
shown in Fig. 2. In this model, the core particle diameter is fixed as 50 nm.
The relationship between the specific surface area and thickness of the shell wall
calculated using this model is also shown in Fig. 2. Here, total stands for the sum
of the outside and inside wall surfaces. In our hollow particles, the thickness of the
 Properties of nanosize hollow silica particles 85

Figure 1. Adsorption isotherms of nitrogen on hollow particles (triangles) and dense particles
(diamonds) at 77 K. Black and white symbols indicate adsorption and desorption, respectively.

Figure 2. Relationship between specific surface area and shell wall thickness calculated from the
inserted figure described as a core–shell particle. Total stands for the sum of the outside and inside
surface areas of the shell. The inside diameter is fixed at 50 nm.

shell wall is about 7.5 nm. From this graph, the total specific surface area is 130
m2 /g, which agrees with experimental data (130.9 m2 /g).
The particle shape has no influence on the adsorption mechanism based on BET
theory. As a reference sample to investigate the adsorption mechanism, a sample
with similar chemical surface properties should be used [25]. It is also necessary
for it to be nonporous. The hollow particle material used in this study is amorphous
silica. Therefore, amorphous dense particles having a spherical shape have been
selected.
86 M. Fuji et al.

Figure 3. Nitrogen adsorption mechanism of hollow particles compared with that of dense particles.
This figure is published in color on http://www.ingenta.com

The difference of adsorption mechanism between hollow and dense particles is

described in Fig. 3. It can be assumed that the surface area of hollow particles is the
same as the outside surface area of the dense particles. If the adsorbed multilayer
grows on both sides of the shell wall by obeying the same mechanism as for dense
particles, the adsorbed amount and surface area of hollow particles would be double
of that of dense particles.
In order to evaluate the difference of adsorption mechanism between hollow and
dense particles, a comparison of adsorption isotherms between them at the same
relative pressure is shown in Fig. 4. The results showed a linear trend at a slope of
about 2.7. On the other hand, the ratio of specific surface area is also 2.7 and agrees
well with the slope constant. Therefore, a hollow particle shell would have pores
by which nitrogen molecules can penetrate from the outside to the inside. However,
the pore size is too small to observe experimental results using nitrogen.
Figure 5 shows the water adsorption isotherms of hollow and dense particles at
the same relative pressure. The isotherm of hollow particles has a strong knee
under a low relative pressure. It is obvious that ultramicropores exist on the
hollow particle surface which can be observed by water vapor adsorption, but not
by nitrogen. This is because molecule size of water vapor is much smaller than
nitrogen. A rapid increasing in the isotherm under high pressure would be caused
by capillary condensation on meso-pores among particles.
Figure 6 shows the comparison of the amount of adsorbed water at the same
relative pressure between hollow and dense particles. The resulting plots showed
two different slopes of linear trend to form a boundary at a relative pressure of
about 0.35. It indicates that both particles have same the adsorption mechanism;
however, it now changes at this point. A rapidly increasing slope was observed
 Properties of nanosize hollow silica particles 87

Figure 4. Comparison of amount of adsorbed nitrogen between hollow and dense particles using v–v
plots.

Figure 5. Water vapor adsorption isotherms of hollow and dense particles. The isotherm for hollow
particles has a strong knee at a low relative pressure.

due to the existence of ultramicropores on hollow particles [26]. Then it showed a

gradual increase in relative pressure above 0.35.
88 M. Fuji et al.

Figure 6. Comparison of the amount of adsorbed water between hollow and dense particles.

3.2. Modified surface analysis

Surface modification for hollow and dense particles with different amounts of n-
butanol was completed well. Figure 7a and b shows FT-IR spectra for unmodified
and modified hollow and dense particles. Both particles had similar trends with
increasing alcohol amount. For unmodified particles, the 3747 cm−1 band caused
by the OH stretching vibration of the surface free silanol groups was observed.
With increasing alcohol content, the silanol band decreased significantly and the
appearance of three new bands between 2915 and 2985 cm−1 due to C–H stretching
vibration indicates the attachment of alcohol to the silica surface.
Figure 8 shows the estimation of surface butoxy group density for particles. For
hollow particles, the density increased with increasing alcohol content. Surface
butoxy group density reached 0.70/nm2 for hollow particles and 0.89/nm2 for dense
particle. The estimation of surface butoxy group density on hollow particles showed
it to be almost the same as that on dense particle. A small difference between the
results would be caused by the reaction on macro-pores which slightly exists on the
shell wall of hollow particle.

4. CONCLUSION
In this study, the surface structure of hollow particles was characterized to compare
it with that of dense particles using the adsorption isotherm. The results can be
summarized as follows.
(1) From the adsorption isotherm of nitrogen gas on hollow particles, there are no
meso-pores on the shell wall.
 Properties of nanosize hollow silica particles 89

Figure 7. FT-IR spectra of unmodified and modified particles with different amounts of n-butanol:
(a) hollow and (b) dense particles.

Figure 8. Estimation of the surface n-butoxy group density using TG/DTA for (a) hollow and
(b) dense particles.

(2) There is a small amount of micro pores on the shell wall by which nitrogen gas
can penetrate from the outside to the inside. Therefore, the specific surface area
for the hollow particles would be the sum of both surfaces of the shell wall.
90 M. Fuji et al.

(3) It can be estimated from water vapor adsorption that surface free silanol groups
on hollow particles have the same characteristics as on dense particles.

Acknowledgements
Part of this study has been financed under a contract from the METI (Ministry
of Economy Trade and Industry) from 2004 to 2006 as a part of the Industrial
Science and Technology Research and Development ‘Research and Development
of the Ultra Low Dielectric Insulation Film and Anticorrosive Film using Hollow
Nanoparticles’.

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