Journal of Sol-Gel Science and Technology 26, 645–649, 2003

c 2003 Kluwer Academic Publishers. Manufactured in The Netherlands.

Sol-Gel Route to Direct Formation of Silica Aerogel Microparticles

Using Supercritical Solvents

M. MONER-GIRONA∗, A. ROIG AND E. MOLINS

Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus UAB, 08193 Bellaterra, Catalunya, Spain
magda@icmab.es

J. LLIBRE
Carburos Metálicos SA, R&D, Passeig de la Zona Franca 14-20, 08038 Barcelona, Catalunya, Spain

Abstract. A simple and versatile method to obtain silica aerogel particles based on the hydrolysis and subsequent
condensation of silicon alkoxides in supercritical fluids is proposed. This microparticle production route reduces
the number of steps of traditional microparticle sol-gel processing.
A case example is explained in more detail. Spherical and fiber silica morphologies were obtained by a one
step method using a sol-gel process with supercritical acetone as a solvent. Particle size was controlled by varying
the relative amounts of alkoxysilane, water and acetone. The resulting materials are influenced by a large number
of experimental parameters; it has been observed that a quite relevant one is the supercritical fluid venting rate.
The morphology of the particles was characterized by electron microscopy (SEM and TEM) and Atomic Force
Microscopy (AFM). Alternatively, a low temperature synthesis can be performed by using supercritical carbon
dioxide as solvent and formic acid as condensation agent.

Keywords: supercritical fluid, aerogel, microparticle, silica, acid formic

Introduction Supercritical fluids have received considerable at-

Silica microspheres is a material of interest in sev-
eral fields such as medicine, materials science or phar-
maceutics. Silica aerogel microparticles have several
applications, including: as additives for conventional
foaming operations, chromatography packing materi-
als, controlled release agents, encapsulation of prod-
ucts, catalysis and high surface-area adsorbents [1].
Several methods have been developed for the for-
mation of silica microparticles. The sol-gel process us-
ing metal alkoxides, such as tetraalkoxysilanes, have
been widely used for the synthesis of silica based
materials [2–4]. In this paper monodisperse, micro-
spherical aerogel powders were produced inside an
autoclave by sol-gel process and using supercritical
fluids.
∗ To whom all correspondence should be addressed.
tention as solvent or reaction media for the processing
of powders, particles, fibers and coatings [5–8], since
they offer a combination of gas like properties (vis-
cosity, diffusion coefficient) and liquid like properties
(density). Other powder processing methods are based
on the solvent power of supercritical fluids, for instance
the so-called RESS process [8, 9]. Moreover, super-
critical carbon dioxide is an attractive medium for the
synthesis of ceramics powders because is a non-toxic,
non-flammable and inexpensive fluid with a low critical
temperature.
Sol-gel reactions have been directly performed in
supercritical carbon dioxide as a reactive medium by
using formic acid as condensation agent [10]. Our ap-
proach for preparing aerogel powders mainly deals
with the dissolution of precursor in supercritical flu-
ids, followed by the sol-gel process and drying under
supercritical conditions. In the present work we have
646 Moner-Girona et al.
investigated the influence of different synthesis param-
eters and the conditions of the synthesis media on the
structure and morphology of the obtained aerogel silica
particles.
Experimental
Reagent grade alkoxides and solvents were used with-
out further purification. Reactions were carried out in
either a specially designed high-pressure 300 ml cell or
in a 2000 ml reactor. The basic components of the sys-
tem include a syringe pump capable of pumping fluids
inside the autoclave through a nozzle. Different ap-
proaches were undertaken and two routes will be used
depending on the supercritical fluid chosen. High tem-
perature method when acetone or ethanol were used as
solvents, and low temperature method if using carbon
dioxide.
In the first process, a sol in a colloidal initial stage,
(containing acetone as a solvent, tetrametoxysilane
(TMOS) as a precursor and water) was placed inside the
reactor. The reactor was then driven above supercritical
values of the acetone, Pc = 47 Bar, Tc = 408 K. The sol
was solubilized in the supercritical acetone distributing
it over the entire reactor leading to the formation of gel
particles. Finally the solvent was extracted. In all the
experiments the TMOS:acetone volume ratio was of
0.05, the hydrolysis parameter, h, is defined as the mo-
lar ratio H2 O:TMOS. The h value was varied from 2
Figure 1. (a) Referring to sample A. Scanning electron micrograph of aerogel spherical shape silica particles narrowly distributed in size,
particle diameter between 0.50 and 2 µm. (b) Fiber-like structure with a diameter of 75 nm and a length of some microns.
Table 1. Mean particle size obtained by varying
the hydrolysis parameter, h.
Sample h Particle size
A 2 1.2 µm
B 4 1.7 µm
C 8 2.2 µm
to 8 obtaining samples A (h = 2), B (h = 4) and C
(h = 8) (see Table 1).
Particles were collected and characterized by a
Leica 360 Scanning Electronic Microscope (SEM),
a JEM 100CX Transmission Electron Microscope
(TEM), a Nanoscope III Digital Instruments Atomic
Force Microscope (AFM), N2 adsorption-desorption
(Micromeritics ASAP 2000 instrument), and He-
pycnometry.
In the second method the sol reaction was directly
performed in supercritical carbon dioxide as a reac-
tive medium. This approach consisted in injecting the
precursor (TEOS) and condensation solutions (formic
acid) in supercritical CO2 , under several critical condi-
tions. The reactor conditions were in the temperature
range of 313–368 K and pressure range of 100–150
Bar. After a residence time of several hours the auto-
clave was vented and the aerogel silica particles were
deposited all over the autoclave. The contact time be-
tween precursor and hydrolysis solution at supercriti-
cal CO2 conditions was varied from 1 to 48 hours and
 Direct Formation of Silica Aerogel Microparticles 647

Figure 2. (a) Sample C, SEM micrograph of the spherical particles and its particle size distribution. (b) Sample B, SEM micrograph and
particle size distribution.

the duration of the pressure release in all the exper-
iments was of 30 min. The injection of liquids was
achieved through a very fine nozzle using a syringe
pump.
An alternative route to this one was to inject the
reactives in liquid CO2 and dissolving the remaining
water and alcohols from the sol reaction in a continuous
flow of liquid CO2 , then reach the CO2 supercritical
parameters and venting the autoclave.
Results and Discussion
In all the experiments a white dry powder was uni-
formly distributed all over the walls and base of the
reactor. No liquid was found, indicating a complete
reaction.
The apparent powder density was between
0.06 g/cm3 and 0.08 g/cm3 depending on the initial
parameters.
648 Moner-Girona et al.
Figure 3. Sample C, TEM microphotograph shows the contact area
between particles.
The porosity of the particles was characterized
by nitrogen absorption (Brunauer, Emmet and Teller
method). The technique allows us to obtain the surface
area of a material using the adsorption and desorption
of an inert gas, usually nitrogen. Gas adsorption mea-
surements reveal the microspheres to have surface ar-
eas from 400 to 600 m2 /g, similar values to those found
Figure 4. Sample C, Surface of a microsphere by AFM. Lateral dimensions: (500 nm×500 nm). The gray scale corresponds to vertical
amplitude of 15 nm.
on their monolithic counterparts. By pycnometry tech-
nique it was checked that the skeleton density has the
same value to that of the silica (2.2 g/cm3 ) [11].
The particle surface microstructure was character-
ized by several microscopy techniques (SEM, TEM
and AFM). AFM was used in a high amplitude reso-
nant mode (‘tapping’ mode). The scale rate was around
1 Hz. Squared images were acquired by using a digi-
talization rate of 256 points per line.
An example of a SEM micrograph is shown in Fig. 1,
the formation of two kinds of morphologies: interlinked
fibers and isometric spherical particles with a narrow
size distribution is evidenced.
The mean particle diameter and the particle size dis-
tribution could be modified by changing the values of
the h parameter. See Figs. 2(a) and (b).
Table 1 shows the variation in the high tempera-
ture experiments of the mean pore diameter when the
TMOS dilution in acetone was fixed at 0.05 and the
hydrolysis parameter, h, was changed.
TEM analysis was useful as to visualize with more
detail the contact region between the microparticles as
can be seen in Fig. 3, although the resolution was not
good enough as to visualize the fine nanostructure of
the microspheres.
To visualize the microstructure of the C particle’s
surface an AFM was used. The images were taken at
 Direct Formation of Silica Aerogel Microparticles
Figure 5. Scanning electron micrograph of aerogel silica particles
obtained in supercritical carbon dioxide at 323 K, 9.9 MPa.
the upper part of the sphere. From the micrograph it
was possible to make surface analysis by image treat-
ment as shown in Fig. 4. The existence of interlinked
nanoparticles of 5–30 nm of diameter and the presence
of pores of 5–50 nm of diameter was observed. This
structure is very similar to that of an aerogel [12, 13].
Regarding the second method, that uses liquid CO2
as a reactive medium, depending on the experimental
concentration ratios of TEOS/HCOOH/SCCO2 , differ-
ent particle agglomerations were obtained. Figure 5
shows SEM micrographs of the aerogel microparticles
collected when (a) supercritical carbon dioxide as a re-
active media was used and (b) injecting the reactives
in liquid carbon dioxide.
Conclusions
Reactions inside an autoclave open a whole range of
possibilities for one step synthesis of microparticles.
The sol was solubilized in supercritical acetone to ob-
tain powders of small particle and a narrow size dis-
tribution. Indeed, these microspheres syntheses were
based on hydrolysis and condensation in the super-
critical fluid. The size of the collected particles was
649
very sensitive to the water/alkoxide concentration ra-
tio: the higher the ratio, the smaller the particles. More-
over, small changes on the depressurization rates results
on very differentiated morphologies, a slow and con-
trolled venting of the autoclave leads to the formation
of monodispersed particles, spherical in shape, and nar-
rowly distributed in the range of 0.5 to 2 µm, otherwise
fiber-like structures are present.
In the case of using supercritical carbon dioxide as a
solvent the resulting particles are less spherical in shape
due to necking formation between two or more parti-
cles. The particle size distribution is also narrow and, in
general, the mean particle size is smaller (<1 micron)
than in the previously described method.
Classical ways for obtaining particles involve high-
temperature and high-pressure reactions. However
there are other ways to obtain aerogel particles based
on the use of supercritical CO2 medium and a condensa-
tion agent sufficiently soluble in CO2 (formic acid has
been proved to be a suitable one). In this case, the work-
ing temperature is lower. Aerogel particle formation in
the supercritical phase under the conditions employed
is dependent on the solubility of the reactives.
References
1. D.L. Wilcox, M. Berg, T. Bernat, D. Kellerman, and J.K.
Cochran, in Hollow and Solids Spheres and Microspheres: Sci-
ence and Technology Associated with Their Fabrication and Ap-
plications (Material Research Society Proceedings, Pittsburg,
1995), p. 372.
2. W. Stöber, A. Fink, and E. Bohn, J. Colloid Interface Science
26, 62 (1968).
3. C.J. Brinker and G. Scherer, in Sol-Gel Science (Academic Press,
New York, 1990).
4. A. Van Blaader and A.P.M. Kentgens, J. Non-Cryst. Solids 149,
161 (1992).
5. M. Barj, J.F. Bocquet, K. Chhor, and C. Pommier, J. Mater. Sci.
27, 2187 (1992).
6. K. Chhor, J.F. Bocquet, and C. Pommier, Mater. Chem. Phys.
32, 249 (1992).
7. X.Y. Zeng, Y. Arai, and T. Furuya, Trends Chem. Eng. 3, 205
(1996).
8. D.W. Matson and R.D. Smith, J. Am. Ceram. Soc. 72, 871
(1989).
9. P.G. Debenedetti, in 3rd International Symposium on Supercrit-
ical Fluids, Strasburg (1994), p. 213
10. D.A. Loy, E.M. Russick, S.A. Yamanaka, and B.M. Baugher,
Chem. Mater 4, 749 (1997).
11. N. Tohge, G.S. Moore, and J.D. Mackenzie, J. Non-Cryst. Solids
63, 95 (1984).
12. R.W. Stark, T. Drobek, M. Weth, J. Fricke, and W.M. Heckel,
Ultramicroscopy 75, 161 (1998).
13. C. Marlière, F. Despetis, P. Etienne, T. Woignier, P. Dieudonné,
and J. Phalippou, J. Non-Cryst. Solids 285, 148 (2001).