Journal of Non-Crystalline Solids 350 (2004) 238–243

www.elsevier.com/locate/jnoncrysol

A fast supercritical extraction technique for aerogel fabrication

Ben M. Gauthier a, Smitesh D. Bakrania a, Ann M. Anderson a,*
, Mary K. Carroll b

a
Department of Mechanical Engineering, Steinmetz Hall, Union College, Schenectady, NY 12308, USA
b
Department of Chemistry, Union College, Schenectady, NY 12308, USA

Available online 6 November 2004

Abstract

Aerogels are a class of ceramic materials fabricated from a sol–gel procedure followed by a carefully controlled solvent evacu-
ation. This fabrication results in a porous nanostructure that is approximately 90–99% air by volume. The intricate pore structure of
an aerogel results in remarkable properties. This paper describes a novel rapid supercritical extraction technique for fabricating
aerogel monoliths. The technique uses a temperature controlled hydraulic hot press and a metal mold to contain and heat the pre-
cursors for a tetramethoxysilane-derived (TMOS) aerogel to supercritical state. During heating, the sol gels, strengthens, and ages.
After a short soak at the supercritical state, the hot press restraining force is released and the supercritical gases are evacuated with-
out causing damage to the silica nanostructure. Using a TMOS-based recipe (TMOS:MeOH:H2O:NH4OH with a molar ratio of
1.0:12.0:4.0:3.7 · 10 3), cylindrical silica aerogel monoliths have been fabricated as large as 22 mm in diameter and 17 mm high
in a 5 h process. The thermo-physical properties are comparable to those of aerogels made using conventional techniques with bulk
densities of 0.066 g cm 3, BET surface areas of 320 m2 g 1, thermal conductivities of 30–40 mW K 1 and optical transmittance rates
of 80–90% in the near-infrared.

2004 Published by Elsevier B.V.

PACS: 81.20.F

1. Introduction ique properties. Current application areas include

An aerogel is a porous nanostructure that is approx-
imately 90–99% air by volume. It is formed by a cross-
linking polymerization reaction and a careful drying
phase. The polymerization process forms a solid net-
work surrounded by a liquid (sol–gel). The drying proc-
ess removes the liquid and leaves behind a delicate
structure with nanoscale-sized pores. This structure is
responsible for giving aerogel materials claim to the low-
est known density, index of refraction, thermal, electri-
cal, and acoustical conductivities of any solid material.
First discovered by Kistler [1] in the 1930s, many at-
tempts have been made to take advantage of their un-
*
Corresponding author. Tel.: +1 518 388 6537; fax: +1 518 388
6789.
E-mail address: andersoa@union.edu (A.M. Anderson).
Čerenkov radiation detectors [2,3], electronics [4], ther-
mal insulators [5], insulated windows, [4,6], comet dust
collectors [7], and heat-storage devices for automobiles
[8].
At present, aerogel materials are difficult and expen-
sive to manufacture. It can take days to weeks to make
an unbroken monolith. This manufacturing complexity
has limited their development in commercial applica-
tions. Aerogels are typically formed in a two-step proc-
ess. The first step is to form a wet gel by a sol–gel
polymerization reaction. The second step is to extract
the solvent and dry the wet gel to form the aerogel.
The primary challenge in the fabrication of an aerogel
is to prevent the collapse of the porous structure during
the drying phase. Stress contributors such as thermal
gradients and pressure concentrations are significant in
aerogel fabrication, but relatively easy to minimize.

0022-3093/$ - see front matter
2004 Published by Elsevier B.V.

doi:10.1016/j.jnoncrysol.2004.06.044
 B.M. Gauthier et al. / Journal of Non-Crystalline Solids 350 (2004) 238–243
More difficult to control, however, are the capillary
stresses from surface tension that, for the nanoscale pore
structure, are strong enough to cause structural collapse.
As the sol–gel dries, these capillary forces can result
in significant fracture to the structure. The current meth-
ods used to avoid fracture in aerogel fabrication can be
categorized into three general techniques. Each drying
protocol is designed to minimize or eliminate surface-
tension effects. They are (1) ambient pressure tech-
niques; (2) conventional supercritical extraction (CSCE)
techniques; and (3) rapid supercritical extraction
(RSCE) techniques.
The ambient-pressure techniques attempt to dry the
wet gel at ambient pressure. To do so they require chem-
ical processes to reduce the capillary forces. One method
is to treat the surface of the gel with a surfactant, or sur-
face-tension-reducing chemical (see for example Yusuf
[9] or Lev et al. [10]). Another technique used by Hærid
[11] ages the gels in alkoxide/alcohol solutions to stiffen
the microstructure and avoid collapse due to capillary
forces. A technique developed by Prakash, Brinker,
and Hurd [12] manipulates the surface chemistry of
the gel to aid in the solvent evacuation. This method
uses a solvent exchange with hexane, followed by a sur-
face modification with a silylation process to promote a
reversible shrinkage. These techniques have been used
successfully in the fabrication of aerogel films, but have
had limited success for aerogel monoliths.
The conventional supercritical extraction techniques
(CSCE) are multi-step techniques designed to eliminate
surface tension altogether by bringing the sol–gel to
the critical point of the solvent. Above the critical point
there is no surface tension, and the solvent can be evac-
uated without damage to the gel structure. The tech-
nique first developed by Kistler [1] entailed two steps:
the formation of the wet gel, and the subsequent solvent
evacuation in a heated pressure vessel at the supercritical
conditions. The main limitations of this technique are
the difficulties associated with obtaining the high tem-
peratures necessary to reach the critical point of the
alcohol solvent, as well as the safety concerns with oper-
ating the pressure vessel at those conditions. In response
to these concerns, a lengthy solvent exchange with liquid
CO2 can be performed prior to supercritical extraction,
which can then take place at the critical point of CO2
(see for example Tewari et al. [13] or Van Bommel [14]).
The advantages of the CSCE method are a lower crit-
ical temperature and a more stable solvent; however an
additional step is added to the process. Because the crit-
ical pressure requirement is not changed significantly,
this process still requires the use of thick pressure vessels
and places practical limitations on the maximum size of
the aerogel. In addition, the solvent-exchange process
becomes a size deterrent, as the diffusion kinetics of
the solvent exchange depend upon the size of the gel.
Even if a pressure vessel were available to contain a
239
large monolith, the solvent exchange could take weeks
to complete, depending on the size of the monolith.
The third technique, rapid supercritical extraction
(RSCE), was developed by Poco et al. [15] and described
further in Scherer et al. [16]. Similar to the CSCE tech-
niques, RSCE is a supercritical technique designed to
perform the solvent extraction under supercritical condi-
tions. In contrast to the CSCE techniques, however, the
RSCE is a one-step, reactant-to-aerogel process. The
liquid precursor chemicals and catalyst are inserted into
a two-piece mold that is then heated rapidly to speed up
the polymerization. The pressure is initially set by fas-
tening the two mold parts together with properly ten-
sioned bolts, or by applying an external hydrostatic
pressure inside of a larger pressure vessel, or by a com-
bination of these two. Once the supercritical point of the
alcohol is reached, the supercritical fluid is allowed to es-
cape through gaps formed by the roughness in the sur-
face contact between the two portions of the mold, or
through a relief valve set just above the supercritical
pressure. A benefit of this method is that the entire proc-
ess is done in one step, and can be accomplished in
under an hour, as opposed to multiple steps (and time
scales on the order of weeks) for all other available
methods.
The advantage of the ambient-pressure methods is
that they do not require expensive and potentially dan-
gerous pressure equipment. They are currently being
used successfully in the fabrication of aerogel powders
and thin films. For the fabrication of monolithic pieces,
however, this technique has yet to prove reliable. Con-
ventional supercritical extraction has been used exten-
sively in the fabrication of very large aerogel
monoliths, however it can take days to weeks to make
them, and the required multiple steps make the process
complicated. In addition to the reduction in fabrication
time, the rapid supercritical extraction as a one-step
process has the most potential for reliable and repeata-
ble fabrication, as well as increased production volume.
This paper describes a new fast supercritical extraction
technique for fabricating aerogels.
2. Fabrication procedure
The equipment used to fabricate the aerogel mono-
liths by the new fast supercritical extraction technique
includes a 25 ton hydraulic hot press, a stainless-steel
mold, a high-temperature gasket, and Kapton film.
The mold is fabricated from a 10 · 10 · 2 cm3 thick piece
of stainless steel (see Fig. 1). Sixteen 2.2 cm diameter,
1.7 cm-deep holes (with a 7 taper) are spaced uniformly
across the plate. The surface was ground flat to ensure a
good seal between the gasket and the mold.
The fabrication process entails two main steps,
both of which take place inside of the mold during a
240 B.M. Gauthier et al. / Journal of Non-Crystalline Solids 350 (2004) 238–243

25000 350
Temperature
Soak Pressure
Release 300
20000
250
Temperature
Temperature
15000 Ramp
Cool Down 200

P, kPa

T, oC
150
10000
T 100
5000
P 50

0 0
0 1 2 3 4 5 6
Fig. 1. Schematic of the mold and press configuration for aerogel Time, hr
processing. The stainless-steel aerogel mold is sandwiched between
Kapton and a high-temperature gasket material. The hydraulic hot Fig. 2. The in-mold temperature (thick line) and pressure (thin line)
press provides a restraining force during processing. data for aerogel processing shows the temperature ramp, soak and cool
down processes that occur during the 5 h cycle. For this test, the
temperature ramp rate was set at 1.1 C min 1 and cool down rate at
5 C min 1.
continuous process. The first step is to polymerize the sil-
ica to form the sol–gel, and the second is to safely evac-
uate the water and alcohol solution. Initially, the
chemical precursors for the aerogel are mixed and 25000
poured into the mold (for a tetramethoxysilane-derived Temperature
(TMOS) aerogel these are TMOS, deionized water, Soak
methanol, and ammonium hydroxide with molar ratios 20000
TMOS:MeOH:H2O:NH4OH with a molar ratio of
1.0:12.0:4.0:3.7 · 10 3). The top of the mold is covered
15000
with a 1 mil thick Kapton film and a piece of high- Pressure
P, kPa

temperature gasket material. The setup is illustrated in Release

Temperature
Fig. 1. Ramp
10000
The mold is placed in the hydraulic hot press and the
processing begins by applying and holding a 75 kN
restraining force. Typically, a temperature ramp of
5000
1.25 C min 1 is applied to heat the mold from ambient Temperature
temperature to a supercritical temperature (265– Cool Down
300 C). The internal pressure of the mold increases as
0
a result of the temperature rise as dictated by the ther- 0 100 200 300 400
modynamics of the system. Following a 15–30 min soak T C
o

at supercritical conditions (for methanol, Tcrit = 240 C

and Pcrit = 8.1 MPa), the load is dropped to 4 kN, allow-
ing supercritical fluid to escape, and the temperature is
decreased at a rate of up to 2.5 C min 1. Upon reaching
ambient temperature, the platens of the hydraulic press
retract, and the resulting aerogels are collected. The
overall time to complete the process as described is 5 h.
Process temperature and pressure data were acquired
by instrumenting the mold with a melt pressure trans-
ducer. Fig. 2 plots the temperature and pressure data
as a function of time and Fig. 3 plots pressure versus
temperature superimposed on a methanol liquidus line
(indicated by the dashed line). The temperature ramp
phase lasted 3 h. As the mold temperature increased
Fig. 3. The pressure versus temperature data for the 5 h process
depicted in Fig. 2 shows that the solution stays above the methanol
liquidus line (indicated by dashed line) until critical temperature and
pressure are reached.
the pressure rose to approximately 21 MPa. At this point
some of the gases were released and the pressure
dropped to about 13 MPa, which is still above the criti-
cal point. (This step demonstrates that the press is capa-
ble of acting as a pressure-relief valve when the internal
pressure gets too high.) At about 3.25 h, the press
restraining force was dropped to 4 kN, the supercritical
gases were evacuated and the internal mold pressure
 B.M. Gauthier et al. / Journal of Non-Crystalline Solids 350 (2004) 238–243
Fig. 4. Sample aerogel monoliths produced by the fast supercritical extraction technique. These monoliths are (a) 25.4 mm diameter · 12.5 mm high
and (b) 24 mm diameter · 17 mm high.
dropped rapidly to ambient pressure while maintaining
a high temperature. In the final stage, the press was
cooled down to ambient temperature in 1.5 h. From
Fig. 3 we see that the process successfully avoids cross-
ing the methanol liquidus line.
3. Results
Using this simple technique we have succeeded in
making monolithic cylindrical aerogel samples that are
22 mm in diameter by 17 mm high. Bulk density meas-
urements were made using a caliper and mass balance.
Values as low as 0.066 g cm 3 were measured. Sample
aerogel monoliths are shown in Fig. 4.
The aerogel pore-size data were characterized using a
Micromeritics ASAP 2010 Nitrogen Adsorption system
(Micromeritics Instrument Corporation). Samples were
outgassed for 5 h at 200 C prior to analysis. A 5-point
Brunauer–Emmett–Teller (BET) analysis was used to
determine surface area. Mesopore distributions were
determined from the desorption branch of the nitrogen
isotherm using the Barrett–Joyner–Halenda (BJH)
method. The BET surface areas were found to be
320 m2 g 1 and the BJH desorption average pore size
was found to be 15 nm. Incremental pore volume was
found to peak at 68 nm. Fig. 5 presents the desorption
pore-size distribution. The 320 m2 g 1 surface area is rel-
atively low for an aerogel. Poco et al. [15] also report
low BET surface areas (compared to CSCE aerogels)
for their RSCE aerogels. They attribute this to the accel-
erated gelation phase, which occurs at high temperatures
in the RSCE process and may cause larger necks be-
tween particles. Further investigation into this matter
is ongoing.
We used a Hot Disk Thermal Constants Analyzer
(HD-01) to perform the aerogel thermal conductivity
measurements. This system sensor is sandwiched be-
tween two pieces of aerogel material and heated by an
electric current for a short period of time. The tempera-
ture response of the sensor is recorded and the transient
record is analyzed to determine thermal properties. Our
241
1.6
1.4 Sample 1
Sample 2
1.2
Pore Volume, cm^3/g 1.0
0.8
0.6
0.4
0.2
0.0
1 10 100 1000
Pore Diameter, nm
Fig. 5. The BJH Desorption oV =o log D pore-volume data for
fabricated two sample aerogels. The solid lines are used to visually
connect the data and do not represent an analytical relation between
pore diameter and pore volume.
aerogel samples had conductivity values between 30 and
40 mWmK 1.
A Perkin-Elmer Lambda 900 Series spectrophotome-
ter was used to perform the transmission measurements
in the 300 to 2500 nm range. The transmission results are
presented in Fig. 6 for two aerogel samples. Although
both samples were prepared using the same process,
one of the samples was cloudy and had low transmissiv-
ity in the visible range. Both samples transmitted 60–
90% of the light at near-infrared wavelengths (1200 to
2200 nm). Peaks observed in the near-infrared region
are characteristic of silica sol–gels and agree well with
the literature [17]. Transmission in the visible region is
limited (particularly for the cloudy sample) due to Ray-
leigh scattering, which is particularly significant at lower
wavelengths. We note that the aerogels transmit suffi-
ciently in the visible region to be used as platforms for
optical sensors based on entrapped fluorescent probes
[18].
242 B.M. Gauthier et al. / Journal of Non-Crystalline Solids 350 (2004) 238–243

100 held there to ensure that the entire specimen exceeds the
critical temperature. At that point the restraining force
on the hydraulic press is relaxed nearly instantaneously
to a nominal load (4 kN). This nominal load is main-
75 tained to prevent air from entering the mold and oxidiz-
ing any remaining precursor chemicals while at high
% Transmission

temperature. As the restraining force is released, the

supercritical fluid escapes through newly formed gaps
50
between the gasket and the mold. It is important to
the design of the mold gasket assembly that the fluid re-
mains completely trapped under the restraining force,
25
yet escapes relatively easily during the relaxation.
After the extraction, the aerogel is formed, but re-
Clear Aerogel
mains inside the mold at an elevated temperature. At
Cloudy Aerogel this point the solvent has been evacuated and the cool-
0 ing path is no longer constrained by the liquidus curve.
0 500 1000 1500 2000 2500 Thermal stresses are less problematic during the cooling
Wavelength (nm) stage because the network has already formed and the
solvent has been evacuated. At present, the cooling rate
Fig. 6. The transmission results as a function of wavelength of light
for two aerogel samples show transmission of 60–90% in the near- is limited by the capabilities of the hot-press.
infrared region.

5. Conclusion
4. Discussion
The new fabrication technique has proven to be a
successful method for fabricating silica aerogel
The Union College Fast Supercritical Extraction
monoliths. We are able to make aerogels in 5 h with
Technique is a one-step precursor to aerogel method.
thermo-physical properties that are comparable to those
During processing, the specimen experiences the stages
of aerogels made using conventional techniques. The
of gelation, aging/strengthening, solvent extraction,
process offers a number of distinct advantages over
and cooling to ambient temperature. Gelation refers to
existing techniques. The process is fast, simple, and eas-
the polymerization reaction that results in a solid net-
ily automated, which may make it more amenable to
work suspended in the liquid solvent. The specimen is
large-scale assembly-line fabrication applications. The
said to have gelled when the polymer network has
process is also inherently safe. The hydraulic press pro-
spanned all sides of the container, although the polym-
vides a restraining force capable of (1) containing the
erization reactions continue as the products approach
internal pressure and (2) controllably releasing excess
equilibrium compositions. The post-gelation polymeri-
pressure. The only pressurized volume is the gel itself,
zation is referred to as the aging and strengthening
not an entire hydrostatic volume as is the case when
stage. In a separate gelation study, we have shown that
using an autoclave or an external hydrostatic pressure
gelation occurs in the first 120 min of the temperature
as in the RSCE process. Additional safety concerns
ramp phase [19]. During the remaining 120 min of the
associated with the release of supercritical alcohol can
ramp and during the upper-temperature soak, the gel
be alleviated by encasing the inter-platen working area
has a chance to strengthen and age. Although thermal
and flushing the working area with a nitrogen purge to
stresses are a primary concern in setting the temperature
eliminate the possibility of auto-ignition of hot solvent
ramp rate, the process must allow sufficient time for the
(e.g., methanol) should it escape from the mold and
gelation and aging/strengthening stages.
mix with air. Future work will concentrate on optimiz-
The processing cycle eliminates the capillary forces
ing the fabrication process by studying the effects of
that cause fracture by avoiding liquid-gaseous inter-
processing parameters and chemical reagents on the
faces. This control is achieved by staying on the liquid
aerogel properties.
side of the methanol liquidus curve until the critical tem-
perature and pressure are reached (as shown in Fig. 3).
As a supercritical fluid, the processing curve can go Acknowledgments
around the liquidus curve (without crossing it) to ensure
that the removal of the liquid phase does not take place Funding for the instrumentation in the Union College
in the presence of a gas phase. Aerogel Fabrication Characterization and Applications
During the high-temperature soak step of the process, Laboratory (AFCAL) was provided by an NSF-MRI
the system is brought to a supercritical temperature and grant (CTS-0216153). B.M.G. and S.D.B. acknowledge
 B.M. Gauthier et al. / Journal of Non-Crystalline Solids 350 (2004) 238–243
support from the Union College undergraduate research
fund. The authors are grateful for the helpful suggestions
of Professors Michael Hagerman and Richard Wilk, and
the other members of the Union College Aerogel Re-
search Team.
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