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Aerogel Synthesis and Application

A thesis submitted in partial fulfillment of


the requirements for the degree of
Bachelor of Arts in Physics

Pomona College

By
Daniel Sedlacek

Advised by:
Dr. David Tanenbaum

April 24, 2009














Abstract


Aerogel has become a material of interest to scientists in recent decades due to its
unique physical properties that give it the potential to improve technologies in a variety of
fields. In particular, aerogels offer the lowest densities and the lowest thermal conductivities
of any known solid. Silica-based aerogels were first synthesized in 1931 by Steven Kistler.
Since then, many other types of aerogels have been created, including carbon-based and clay-
based aerogels. Silica-based aerogels are the simplest and most widely studied type of
aerogel, with new uses and applications arising every day. As such, silica-based aerogels
offer a unique platform on which to base further research in the small liberal-arts college
setting.
This project examined the process of synthesizing low-density silica-based aerogels.
The goal was to create a reliable, non-toxic method, using inexpensive materials and
equipment already owned by the Pomona College Physics Department. The science involved
was built off of results achieved by the author in Physics 174: Contemporary Experimental
Physics class at Pomona College in the spring of 2008. The recipe used to synthesize the
aerogels was found on the Lawrence Berkely National Laboratory website [9]. Additions to
the recipe were implemented as suggested on William Woods website [24]. The recipe
incorporated the most recent technique in aerogel manufacturing, replacing
tetramethylorthosilicate (TMOS) with tetraethylorthosilicate (TEOS). Both of the chemicals
are precondensed silica precursors, with TEOS being the less toxic of the two. The gel molds
were in the shape of cylinders so that both thin and thick disks could be created depending on
desired speed of production, and desired further experimentation. Specific drying methods
were based on Tousimis Samdri-PVT-3D critical point dryer manual and suggested
techniques from Dr. Tousimis [27]. The scanning electron microscope was then used by Dr.
2
David Tanenbaum to examine the nanoscale structures of a sample achieved from this project
as well as a commercial sample owned by the Pomona College Physics Department. Further
examination was carried out with the departments Fluke thermal imagining camera.









































3
Table of Contents


Chapter 1: Introduction and Background.......................................................................5
1.1 Background
1.2 Motivation
1.3 Methods

Chapter 2: Theory............................................................................................................12
2.1 Chemical Theory
2.2 Methods Theory
2.3 Physical Theory

Chapter 3: Previous Research........................................................................................17

Chapter 4: Experimental Setup and Process.................................................................23
4.1 Materials
4.2 The Gel Stage
4.3 The Mold Stage
4.4 The Bath Stage
4.5 The Drying Stage

Chapter 5: Results and Analysis.....................................................................................28

Chapter 6: Conclusions and Future Work................................................................37
6.1: Conclusions
6.2: Future Work

7: Acknowledgements......................................................................................................41

8: Bibliography.................................................................................................................42

9: Appendix I: Images of Equipment.............................................................................46

10: Appendix II: More Sample Images..........................................................................49

11: Appendix III: Student Manual for Synthesis of Simple SiO
2
Aerogels................52








4
Chapter 1: Introduction


1.1: Background

In 1931, Steven Kistler made a bet with a colleague that he could prove a wet gel
contained a solid matrix the same size and shape of the gel. To do this he began with a
gel and extracted the liquid, leaving a low-density solid behind. Using an autoclave to
drive the liquid past its critical point he was able to conquer the obstacle of surface
tension which would otherwise rip apart the internal solid structure of the gel. His
successful wager produced the first silica-based aerogel. For half a century this curious
material went relatively unnoticed, due to the notorious difficulties and safety issues
involved in its creation.
In the early years, fabricating aerogels meant sending alcohol to volatile pressures
and temperatures in order for it to reach its supercritical point and allow for the
supercritical-extraction of the gel. Then, in the 1980s, interest was renewed when a
French scientist, attempting to improve the fabrication process for the French
government, developed a process which used less-toxic materials. He switched out
methyl alcohol and tetramethylorthosilicate (TMOS) for the safer pairing of ethyl alcohol
and tetraethylorthosilicate (TEOS). The next breakthrough came in the early 1990s when
liquid carbon dioxide replaced the ethyl alcohol involved in the gel before the sample was
taken through the supercritical process. This allowed scientists to bypass the dangerous
pressures and temperatures needed to send the pure ethanol past its supercritical point.
Liquid carbon dioxide has the relatively mundane requirements of 305 K and 1050 psi to
be brought to its supercritical point (Fig.1.1).
5
Fig. 1.1

Above: CO
2
Phase Diagram [29]


Due to these and other breakthroughs, aerogels saw a surge in popularity in the
1990s. Scientists found aerogel to be a new class of material altogether, with untapped
potential due to its varied and unique properties [19]. Making up for its brittleness,
aerogel holds the record as the solid with the lowest density the lowest thermal
conductivity. The lowest density evacuated aerogel ever produced had a density of 1.0
milligrams per cubic centimeter so light that the sample could float in air (1.2
milligrams per cubic centimeter). Though many materials can be used to form the solid
lattice structure of an aerogel, SiO
2
aerogels are the most common. This is due, in part, to
the relative simplicity, safety, and reliability of the manufacturing process. Also, many
materials can be incorporated into the aerogels structure by involving them in the gelling
process, which helps to tailor the properties of the resulting sample. For instance, a new
approach gives aerogels a much higher compressive modulus and improved tensile
strength while still maintaining the incredible low-densities of the aerogels [17].
6
Aerogels are used in such varied fields as: electronics, life-sciences, space
exploration, green technology, and many others. They were used in JPLs recent Pheonix
Lander mission to Mars as thermal insulation on the Lander. Aerogels are predicted to be
the next generation interlayer dielectric for integrated circuits [2, 18], paving the way for
faster computing. They are being used in high-efficiency windows [22], and to clean up
oil spills [21]. New technologies and ideas such as these provide efficient ways to
manage energy and ensure the future heath of the environment. It is clear that aerogels
are creating breakthroughs for clean, renewable energy and energy conservation, as well
as environmental-protection technologies.


1.2: Motivation

The main motivation for this project is that it will expand students access to a
material whose applications are far from exhausted. The reliable synthesis of SiO
2

aerogels in a small liberal arts college setting would give future students at Pomona
College and other colleges the opportunity to produce and experiment on this
extraordinary material. Aerogels created in such a setting could also be donated to other
colleges and high schools for use in introductory materials science classes, such as the
one this author took at Olympia High School. The hands-on nature of such classes allows
students to explore science in both theory and application, and aerogels fit perfectly into
many demonstrations suitable for students of all levels.
Beyond their use in the classroom, aerogels produced at small colleges can give
students the chance to explore a material that is emerging as a cutting-edge material in
green technology. This is a field spawned by the fact that the general warming of our
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planet due to human-produced greenhouse gasses threatens the future stability of our
environment. At the same time, the future of reliable energy is at risk due to dwindling oil
fields and the ever-increasing demand for petroleum products. Incorporation of aerogel
has proven time and time again to increase the energy efficiency of many machines and
systems, thus helping preserve energy supplies by reducing usage. As well, aerogel can
be used to extract pollutants from water, allowing it to capture the harmful particles
before they enter ecosystems [30]. Scientists have realized that they need to do much
more to develop technologies that lead to clean and renewable energy and the
conservation of that energy. Small liberal arts college students can take part in such
research, using this project as a basis to create SiO
2
aerogels.
Another course that research using these aerogels can take is the development of
materials and technologies for space-exploration technology. Aerogels have been
researched for fuel-storage tanks, cryogen-storage tanks, and have been implemented for
such applications as the comet-dust catching structure in NASAs Stardust spacecraft [3].
In the spring of 2008 the author of this paper worked on synthesizing silica-based
aerogels. Two recipes were found online at the Lawrence Berkely National Laboratory
website. Both recipes incorporated the most recent technique in aerogel manufacturing,
replacing TMOS with TEOS as the precondensed silica base. While both recipes
succeeded in creating gels, no gel was successfully evacuated of all liquid and, therefore,
no aerogel sample was produced. However, the necessary equipment and chemicals were
either already owned or were inexpensive to order. In other words, all of the materials
required for the process were in place, assuming corrections to the synthesizing process
could be instituted to allow the production of actual aerogel samples.
8
The most successful run from 2008 resulted in a 2.2 cm long piece with a
density of about 0.2 grams per cubic centimeter, which is too dense to be considered an
aerogel. The sample had a rubbery, moist feel, and the smell of ethanol was apparent.
This suggested that the problem lay within the liquid CO
2
introduction phase of the
critical point drying step. One possible solution was thought to be to allow the sample to
sit at 0 degrees Celsius for longer than the 2 minutes asked for by the Tousimis critical
point dryer manual [27]. The additional time was hypothesized to allow the ethanol
involved in the gel sample to be replaced by the liquid CO
2
present in the rest of the
chamber. After contacting the Tousimis Company, this hypothesis was partially
confirmed. They suggested letting the sample bath two separate times for 15-18 hours,
instead of 2 minutes. The 15-18 hour baths were left at ambient temperature, instead of
being cooled to 0 degrees Celsius as they had been. After each bathing period, two steps
of the process were repeated, as is described in section 4.5.
Fig.1.2

Above: A shrunken, low-density silica sample from Physics 174


Another problem encountered in 2008 was that the molds were not waterproof
and the gels would not form in them, so instead the gels were allowed to form in beakers.
The resulting gels were too large for the critical point drying chamber and breaking them
9
apart before synthesizing damaged their surfaces and possibly their internal structure.
Because of this, the development of better molds was successfully taken on for this
project. Hollow Teflon cylinders with screw-on caps were developed (see Appendix I).
Due to their inert and non-stick nature, the molds allowed for continuous, smooth-
surfaced gels to be formed for this project. This ensured that the surface was unmarred
and that the interchange of liquids at the surface was equal across the entire sample.

1.3: Methods

There are three main methods for aerogel fabrication, representing three unique
solutions to the surface tension problems involved in the process. The two methods that
will not be used are rapid supercritical extraction and ambient pressure drying. Though
rapid supercritical extraction is a much faster method than the one proposed here, it also
involves specialized pressure molds and equipment that the Pomona College Physics
Department does not own. The ambient pressure drying method is an elegant solution,
which involves chemically altering the surface of the gels to relieve tension and allow for
drying at ambient pressures, but involves chemicals not currently on hand as well as
difficult-to-reproduce purification processes. The third method, which shall be used here,
is the slower supercritical drying process. This method requires either an autoclave or a
critical point dryer. Professor Tanenbaums research lab owns a Tousimis Company
Samdri-PVT-3D critical point dryer.
The three goals for this project were as follows: First, synthesize reproducible,
stable aerogels. This required several important steps: The critical-point dryers CO
2
inlet
valve was broken and had to be fixed before experiments could take place. The
department ordered a valve replacement from the Tousimis Company and Glenn Flohr
10
executed the repairs. Another step was to research whether or not the planned recipe
would produce hydrophilic or hydrophobic aerogels, and what steps would need to be
taken to make hydrophilic samples stable. It was found that the aerogels made from the
recipe should be innately hydrophobic upon drying and would hold up to air moisture
indefinitely [19]. The second goal for this project was to characterize the resulting aerogel
samples. This was carried out for several physical and optical properties of the samples using
methods described in Chapter 5. The third goal was to consolidate the research performed
herein into a laboratory manual for future Pomona College and other small liberal arts college
students to follow. To view the student manual for synthesizing simple SiO
2
aerogels, please
see Appendix III.



























11
Chapter 2: Theory


2.1: Chemical Theory

Aerogels begin life as a silica (SiO
2
) gel. Though aerogels have also been created
with alumina, chromia, tin oxide, carbon and other materials, silica versions are the
easiest and most reliable to produce. The silica gels are about 99% liquid by weight, but
contain matrices that give the liquid surface tension. In a silica gel these molecular
networks are made up of silica dendrites.
The first step in making aerogels is to create what is called a wet gel. Currently,
the best way to create the wet gels is to begin with a silicon-alkolyde precursor, such as
TEOS, which was used for this project. The chemical makeup of TEOS is
Si(OCH
2
CH
3
)
4
, which, when added to water, achieves the chemical reaction.
Si(OCH
2
CH
3
)
4 (liq.)
+ 2(H
2
O)
(liq.)
SiO
2 (solid)
+ 4(HOCH
2
CH
3
)
(liq.)
eq.2.1 [9]

The amount of water indicated in eq.2.1 is only enough to exactly balance the
reaction. In practice, anywhere from 4 to 30 times more water should be used to increase
the strength of the gels [9]. This chemical reaction is generally accomplished in ethanol.
Acid or base catalysts are added to this reaction in order to decrease gelation time
from several days to around an hour. Base catalysts were used in this project due to their
tendency to create clearer aerogels. Base-catalyzed aerogels also retain more of their
volume throughout processing than do their acid-catalyzed counterparts.
The current precursors are largely alkoxides M(OR)
n
which are compounds
consisting of a metal M and an alkoxide group OR [19]. With silicon precursors the R
designating the alkyl group is often a methyl CH
3
group or an ethyl C
2
H
5
group. The
reason silica-based aerogels have been studied much more than any other type is because
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silicon atoms carry a reduced partial positive charge
+
. In Si(OEt)
4

+
is about 0.32 [19].
This reduced partial positive charge makes the gelation kinetics of the silicon precursor
extremely slow. Because of this, the speed of the hydrolysis rate, compared to the
condensation rate, can be controlled through catalysts. Controlling these kinetics allows
silica aerogels to be adapted at this stage for their future application [19].
This project made use of Silbond H-5, a pre-polymerized TEOS silica source. It is
created by adding heat and an acid catalyst to a solution containing TEOS, ethanol and a
sub-stoichiametric amount of water [9]. The resulting fluid is has higher molecular
weight silicon alkoxy-oxides. Because of this, Silbond H-5 only requires processing with
a basic catalyst in order to achieve gelation. The resulting gel is clearly a combination of
a silicon dioxide solid and the liquid HOCH
2
CH
3,
as well as left-over ethanol, water, and
Silbond H-5 that did not undergo the reaction. It is the removal of all leftover liquids that
turns the wet gel into an aerogel and gives the material its unique physical properties.

2.2: Supercritical Fluid Theory

If a wet gel were to dry at normal room temperature and pressure, the liquid
within the gel would evaporate into a gas and the lattice-structure that gives the gel its
shape would shrink and crumble due to surface tension. The deforming comes from the
capillary pressures, which arise from the diminishing meniscus of the liquid. When these
pressures build up in the lattices pores they destroy the lattice. This problem is solved by
introducing the sample into a temperature and pressure controlled environment, such as
an autoclave or a critical point dryer. The pressure in the samples environment is raised,
followed by the temperature, until the liquid turns into a supercritical fluid. The point at
which this happens is called the critical point - the point at which a gas cannot be turned
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into a liquid simply by increasing pressure. At the critical point the fluid will lose all
surface tension properties associated with a liquid and become completely miscible. With
small changes in pressure, the supercritical fluid experiences large changes in density.
Because the liquid-gas interface is eliminated, and therefore no surface tension is present,
the sample can be dried without deformation.
In this project, carbon dioxide was introduced to the sample in liquid form,
replacing the pure ethanol which had been in the gel. The liquid CO
2
was then brought
past its critical point of 304.1 K and 72.8 atm. The pressure of the supercritical fluid was
then lowered, while maintaining higher than critical temperatures in order to take
advantage of its properties of low viscosity and high diffusivity. In this manner the
supercritical fluid becomes more gas-like and is vented off, leaving the silicon-dioxide
lattice structure intact.

2.3: Physical Theory

The solid nanoscale silica dendrite networks of silica-based aerogels give them
their unique properties. The ionic fraction of the polar covalent bonds for several
different metal oxides yields the following results.
f
ionic
= 1 exp(-0.25(X
M
X
O
)
2
)

eq.2.2 [19]
X
O
and X
M
represent the Allred-Rochow electronegativities of O and M. For
Al
2
O
3
, TiO
2
, ZrO
2
, and Na
2
O, f
ionic
gives 0.64, 0.70, 0.71, and 0.78. SiO
2
on the other
hand has an f
ionic
of 0.54, allowing the Si-O-Si angle value to range widely, which gives
the resulting structure a random network [19]. The other four oxides given have higher
ionic fractions, leading to a lower range of bond angle values. This means that the
random bonding only occurs on a more macro scale with bigger, denser, colloidal
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particles. When this happens the resulting gel is particulated instead of forming a random
network of dendrites. This means that achieving gelation with higher f
ionic
valued oxides
is difficult and even impossible with a value as high as the 0.78 of Na
2
O [19].
The silica dendrite network which makes up the aerogels creates an extremely
strong material for its relative weight. The same network also makes aerogels brittle,
causing the material to shatter under sharp pressures. Aerogels are amazing thermal
insulators. The reason for this property is threefold. The air inside of the silica lattice
cannot pass through the nanoscale pores, so convection cannot occur. Silica has a very
low heat transfer coefficient and because of this the heat conductivity through the
physical solid matrix of the aerogel follows the formula for solid conductivity
s
(eq.2.3).

s
~

eq.2.3 [19]
Where is the density of the aerogel, and has a value between 1.2 and 1.8.
Lastly, small amounts of carbon can be added to the aerogel, absorbing infrared radiation
and all but halting radiative heat transfer. Because of this, aerogels have thermal
conductivities of 0.03-0.004 W/(mK), up to 6.25 times lower than air. At best, aerogels
have thermal conductivities of up to 10 times lower than wood or polyurethane foam
insulation [19]. Due to this fact, windows no longer need to be the weak point in energy
efficiency for buildings if the windows incorporate aerogels. Out of any currently known
materials, aerogels hold the record for the lowest thermal conductivity, refractive index,
sound velocity, dielectic constant, and bulk density.
The gels produced in this project used Silbond H-5 as the precondensed silica
precursor. Silbond H-5 is derived from TEOS whose chemical formula is Si(OCH
2
CH
3
)
4
.

Due to the non-polar chemical group CH
3
-Si bond, that accompanies the normal CH
2

15
ethyl group, the resulting aerogel is hydrophobic [19]. This allows the aerogel to be
exposed to water and not have its structure collapse due to the pressures involved.
Because of this trait, intrinsically hydrophobic aerogels are more appropriate for a small
liberal arts college setting where obtaining exotic chemicals to treat the surface, or
providing moisture-free environments in which to conduct experiments can be
prohibitively expensive and difficult to create.

































16
Chapter 3: Previous Research


The area of aerogel research expands enormously each year and profiling a
complete history of previous research done in the area is impossible. Instead, we
document here breakthrough research that opened the door to entirely new applications
based on different properties of the aerogels. Highlighted is research done on a small
scale, as well as research done with silica-based aerogels. This will have the most uses
for this project as the research can be mimicked or examined further in a small liberal arts
college setting.
For further inspection of application and synthesis techniques, one can turn to
Pierre and Pajonk, who have developed new catalysts by using aerogels, as well as
extensively cataloguing previous methods and applications of aerogels. In their 2002
paper, Chemistry of Aerogels and Their Application, they put emphasis on the fact that
aerogels should be considered a different class of material than have ever been seen
before. They provide an in-depth analysis on the chemical processes behind the creation
of different types of aerogels. The paper provides both the history and chemical process
behind each step in aerogel fabrication, as well as the uses of the end-product. Because of
this, Pierre and Pajonk to date have provided the most exhaustive background for any
small liberal arts college aerogel researcher. Most importantly, it maps out the creation of
carbon aerogels, an important material due to its electrical properties. This paper also
details how aerogels are being used in catalysts and the life-sciences, which will provide
a new angle for further research in a small liberal arts college setting [19].
The first method for removing water from a jelly without an accompanying large
shrinkage [13] was devised by Steven S. Kistler in 1931 on a very small scale with
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relatively inexpensive materials. He followed up with studies on Thermal Conductivity of
silica Aerogels in 1938, and Sorption and Surface Area in Silica Aerogel in 1943 [13,
14]. Though modern-day aerogels are produced through different methods and materials,
and are manufactured to exhibit much more specialized properties, it was obvious to
scientists like Kistler from the very beginning that aerogels exhibited extraordinary traits
including low density and low thermal conductivity.
After half a century of relatively little study, aerogels came back into the research
spotlight in the early 1980s as a material suitable for employment as a Cerenkov
radiator. Carlson et al utilized the refractive index (n = 1.01 to 1.02) and the transparent
nature of silica aerogels to incorporate them in a Cerenkov detector design. Aerogels
represented a breakthrough for Cerenkov detector designs because the detectors no longer
had to involve liquefied hydrogen or helium to provide the correct indices of refraction
[1].
Many researchers look to utilize one or two of aerogels record-breaking
properties. In 1992, Tillotson and Hrubesh examined the possibility of maximizing the
low density and transparency of aerogels by using a two-step process. This two step
process is performed with tetramethylorthosilicate as the precondensed silica precursor in
their paper Transparent Ultralow-Density Silica Aerogels Prepared by a Two-Step Sol-
Gel Process. However, this method can be done just as well with tetraethylorthosilicate
(TEOS) and is one of the most widely-used processes to develop low-density highly-
transparent aerogels 17 years later. The authors also attempted to characterize aerogel
samples with a scanning electron microscope. They found that while electron-charging on
the surface of the aerogels makes high-magnification, high-resolution images impossible,
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lower magnification images yield high enough resolution to be useful in showing the
various microstructures of aerogels synthesized through different processes [26].
In 2001, Reynolds et al utilized the absorption properties of aerogels in order to
create a cheap, quick, and environmentally safe method of cleaning up crude oil spills in
salt water. Hydrophobic aerogels functionalized with CF
3
groups were used to absorb oil
from an oil-seawater solution. After absorption, both the water and the oil were purified
and could be reused. This experiment took place on a scale that is easily reproducible,
though the exotic nature of the aerogels makes them hard to fabricate. This research also
has the benefit of using aerogel powders over solid monoliths, a fact that lowers the cost
of materials significantly. The authors publication of Hydrophobic Aerogels for Oil-Spill
Cleanup - Intrinsic Absorbing Properties led to a patent for their environment-saving
aerogel technology [21].
The theory for further green technology based on aerogels was developed in 2001
by Krainov and Smirnov. The scientists hypothesized that absorbing deuterium in SiO
2

aerogels would yield an improved target for inertial confinement laser fusion. Laser
Induced Fusion in Aerogel details the theoretical arguments behind their suggestion and
shows that the fractal nature of the aerogel skeleton should lead to a Coulomb explosion
of the fibers [15], increasing the power generated through fusion by a factor of ten. The
theory developed in this paper will soon be put to test at the just-finished National
Ignition Facility at the Lawrence Livermore National Laboratory in Livermore,
California. The aerogels used for this theory were simple SiO
2
aerogels, unveiling yet
another way in which aerogels might help advance green technology, this time by
providing a theoretical solution for clean, renewable energy [15].
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The dielectric properties of aerogels led to them being used in commercial
capacitors. By 2002, the PowerStor
R
aerogel capacitors, which use carbon aerogels as the
electrodes, were up to 5000 times smaller for a given capacitance when compared to
normal electrolytic capacitors. Juzkow diagramed the design process of the aerogel
capacitors. Following the methods presented, it should be relatively easy to create and
test aerogel capacitors on a case-by-case basis. The only requirement would be to make
or obtain carbon-based aerogel samples, as they are best suited for use as electrodes [12].
The dielectric properties of aerogels also give them a potential future in integrated
circuits, as long as several key hurdles can be overcome. In 2005, Cho et al examined a
process to seal the pores at the surface of the aerogels in order to make them useful as
interlayer dielectrics without compromising the other important properties of the
aerogels. The authors found that if the pores were not sealed before CVD processes
involved in making integrated circuits were carried out, then the entire aerogel interlayer
dielectric became contaminated and useless. The solution presented was to seal the pores
by exposing them to CHF
3
plasma. The model created predicted that a one-minute
treatment in a 90 mTorr CHF
3
plasma would suffice to seal the pores. If hydrophilic gels
were to be created in a small liberal arts college setting, then this method of pore sealing
could allow further experimentation on the gels, without having to provide a moisture-
free environment. The only requirement would be the ability to create a 90 mTorr CHF
3

plasma that a sample can be exposed to for one minute [2].
In their 2007 paper Effective Preparation of Crack-Free Silica Aerogels via
Ambient Drying, Hwang et al detail experimental techniques and designs used to make
solid silica aerogel preparation safer and less costly - the two main hurdles that must be
20
overcome before the potential of aerogels becomes fully recognized. The research skirts
the normal technique of using expensive chemicals, such as alkoxides, and the expensive
and somewhat dangerous method of supercritical drying. With the idea to create
inexpensive aerogels for the scientific community, the authors used waterglass as the
base material, a low-cost replacement for tetraethylorthosilicate (TEOS) and other
chemicals. They also developed a technique to dry the aerogels at ambient pressures, and
overcome surface tension problems through surface modification. As long as the
inexpensive, but intricate ion-exchange system built by the authors to purify the silica
solution can be reproduced, this process should be easy to mimic [10].
In 2008, Meador et al explored a new approach to synthesizing aerogels that
resulted in samples with a much higher compressive modulus and tensile strength than
previously achieved. In order to maintain the desirable low-densities of aerogels, carbon
nanofibers were included in the gel-process, allowing them to become involved with the
resulting silica aerogel dendrite network. Though the chemical reaction involved in this
paper is not identical to this authors process, the process of incorporating carbon
nanofibers can be appropriated to provide a platform for further research with the Silbond
H-5 process. The carbon nanofibers are processed through sonication into the liquid silica
solution. The authors also detailed how to test the tensile strength of fabricated aerogels
[17].
One aerogel technology that has been developed and awaits only a cheaper mode
of production is the integration of aerogels into modern high-efficiency windows.
Aerogel windows make use of the thermal-conductivity and transparent properties of the
material. This technology was implemented in a standard Danish house in 2008 and was
21
found to reduce annual energy needs by 19% [22]. When implemented in low-energy
Danish houses, the aerogel windows reduced annual energy needs by 34% [22].
Other ongoing research includes producing aerogels in a weightless environment,
because they are much more transparent than their blue smoke brethren and would
allow for insulating windows with more favorable optical properties. Aerogels are also a
common material in spacecraft insulation and were famously used as the sample-
collection material on NASAs Stardust spacecraft, which collected specimens from the
tail of the comet Wild 2. The comet dust created a trail as it broke through the silica
lattice, before stopping at some point in the aerogel structure. Due to the strength, the
varying density, and the transparent quality of the aerogel structure, scientists were able
to pinpoint the position of the comet dust and study it when Stardust returned [11].
























22
Chapter 4: Experimental Setup and Process


4.1: Materials

The Silbond H-5 Company donated 500 mL of the Silbond H-5 precondensed
silica solution to the author. Though it is not sold in such small quantities, Silbond H-5 is
similar to TEOS, which goes for about $50 per liter. The physics department had enough
pure ethanol on hand for both the recipe and the following baths. The water was
obtained from the Millipore Direct Q 3 UV water filter in the Physics department. The
30% aqueous ammonia solution was acquired from the Chemistry Department. One 100-
1000 uL pipette was borrowed from Professor Kwok. The second 100-1000 uL pipette
and all other glassware was bought or borrowed from the Chemistry Department. The
Teflon was purchased by Glenn Flohr. The screws in the molds were fitted by Glenn
Flohr. The Tousimis PVT-3D critical point dryer is owned by Professor Tanenbaums
research lab.

4.2: The Gel Stage

The first step in synthesizing aerogels was to create a gel. This thesis made use of
the two-step acid-base catalyzed silica aerogel recipe from the Lawerence-Berkely
National Laboratory website [9]. The recipe was prepared underneath a fume hood for
safety. The steps were as follows.
1) In a 500 mL beaker 25 mL of Silbond H-5 was mixed with 25 mL of ethanol.

2) The catalyst solution was mixed in a 100 mL graduated cylinder; its
components were 17.5 mL of ethanol, 37.5 mL of water, and 0.175 mL of 30%
23
aqueous ammonia. The 0.175 mL of 30% aqueous ammonia required the digital
pipette due to the small amount of liquid.
3) The catalyst solution was poured slowly into the Silbond H-5 solution stirring
the entire time. The pouring took a minimum of 45 seconds. Any quicker and a
foam developed on top of the mixture, compromising future gels.
4) The resulting mixture was then poured into the Teflon molds.


4.3: The Mold Stage

The LBNL website claimed that this recipe would take 30-90 minutes to gel,
assuming no temperature extremes. The gels created in this paper were gelled by the 90
minute mark. After the gels were set, the following solution was prepared as suggested by
the website on William Woods aerogels [24].
17.5 mL ethanol. 37.5 mL water.
The molds holding the samples were then set in 50 mL beakers and completely
covered with the new solution. This kept the samples from being exposed to air which
would dry them out and destroy the silicon lattice structure [24]. The 50 mL beakers were
then covered with tin foil in order to keep the evaporation rate of the covered solution
low. The gels were allowed to set in the molds for over 48 hours in order to have the
lattice structure fully develop.

4.4 The Bath Stage

After the gels were fully set, the next step was to remove them from the molds
and set them in ethanol baths. A 50 mL beaker containing 25 mL of pure ethanol was
prepared for each gel. The molds were then extracted from their previous beakers, the
24
bottoms unscrewed and the gels pushed gently into their individual baths. The baths were
drained and replenished with an equal amount of ethanol every 8 to 24 hours. Each
sample was introduced to a total of at least 5 pure ethanol baths in order to ensure that the
liquid held within the gel matrix was pure ethanol with no water. Because the volume of
pure ethanol in each bath was 1.5 times the volume of the gel (the gel recipe is 35.7%
water by volume), the final sample should not have contained more than .4% water by
volume. At this point the gels were ready for the critical point dryer step. The gels
appeared absolutely clear in the beakers and had only several small bubbles in them
acquired in the mixing stage. While able to be moved by hand, the more contact with
pressure and air, the higher probability that the gel would weaken, develop cracks, or
even break. The best method was to leave the gels in one beaker, and if they had to be
moved, to slide them gently from beaker to beaker. Even when care was taken in every
step to minimize pressures and stresses endured by the gel, about half the samples still
broke, fell apart, or did not form a coherent gel matrix.

4.5: The Drying Stage

The Tousimis Samdri PVT-3D critical point dryer was used in the drying stage of
this process. The critical point dryer chamber contained two openings, the liquid CO
2

entry line and the exhaust line. Because the gels could potentially run into these openings
and block up the lines, filter paper was cut and folded into a cylindrical pipe with one
bottom. Because it did not interact with the CO
2
or ethanol, the filter paper was able to
effectively block the two openings from gel particulate, while remaining invisible to the
other chemicals in the experiment.
25
After the filter paper was in place, lining the drying chamber, ethanol was poured
into the chamber until it was half full. Then the gel sample was extracted gently from its
bath and placed into the drying chamber. The gel was then processed according to the
Tousimis Advanced Manual Critical Point Dryer Samdri-PVT-3D user manual [27].
However, there was one important difference between the instructions and the procedures
used in this project. As per Dr. A.J. Tousimis suggestion, after step 7 was accomplished,
the sample was allowed to sit for 15-18 hours without moving on to step 8. After that
time period, steps 6 and 7 were repeated and the gel was allowed to sit in the same
manner as before for 15-18 hours. During these wait times, the chamber did not need to
be kept below ambient temperature. After the second waiting period, steps 6 and 7 were
repeated for a third time and then the procedure continued as normal with step 8 until the
end.
When repeating steps 6 for the second and third time, it is imperative that viewing
chamber be watched to guarantee that the liquid CO
2
level does not drop below the
sample. This misstep is easy to do because the liquid CO
2
is cooling quickly from above
ambient temperature to around 0 degrees Celsius. While cooling, the pressure drops
significantly, and if it drops below 850 psi, a gas pocket develops in the chamber. If the
liquid drops below the sample, allowing the gas pocket to come in contact with the
sample, then the sample quickly develops cracks and begins to turn opaque. This change
in appearance represents the deforming of the solid matrix within the gel, and will result
in shrunken, denser, and highly-weakened samples. The critical point dryer, including the
viewing chamber, can be seen in Appendix I.
26
Each time, when performing step 6 from the Tousimis critical point dryer manual,
the beaker connected to the exhaust line should be monitored. When opaque white solids
enter the beaker, looking like snow, then the critical point dryer chamber has been
evacuated of ethanol and only liquid CO
2
is left, except for any ethanol involved in the
gel matrix. This should only take about 10 minutes of purging and replacing the liquid in
the chamber. An image of the exhaust beaker can be found in Appendix I.
At the point when the CO
2
was extracted for the final time, the gel sample became
an aerogel, with only the solid silicon matrix of the gel left over. Each sample was
removed from the chamber, measured, weighed, and placed into a container, ready for
further testing.













27
Chapter 5: Results and Analysis

5.1: Qualitative Results

In 2008 the author attempted to create aerogels, but only succeeded in creating
shrunken low-density silicon dioxide solids that still had ethanol inside them. The best
result was a 2.2 cm long piece with a density of about 0.2 g/cm
3
, or about a factor of 3
larger than expected from the recipe. When crushed between two fingers, the sample felt
rubbery and moist and the smell of ethanol was evident. Since the sample had been
bathed 8 times in ethanol equal to its volume, the problem was not with water being
involved in the matrix. Instead, the presence of the ethanol pointed to the fact that that the
sample had not bathed long enough during the liquid carbon dioxide replacement stage of
the critical point drying phase. The sample shrank continuously from the time of
extraction and initial measurement until about 24 hours later when it was about half the
size and much more dense.
Fig.5.1
Above: Failed aerogel sample from Physics 174
28
The shrinking of the failed sample led the author to the initial, incorrect
conclusion that the recipe produced hydrophilic aerogels, whose solid matrix would
deform due to moisture in the air. However, successful samples proved this hypothesis
incorrect, showing no shrinking after weeks of contact with the air. The first successful
sample was roughly in the shape of a cylinder 2.40 cm in height and 1.34 cm in radius.
With a weight of .3115 grams, the sample had an overall density of .079 g/cm
3
, exactly
on par with the .08 g/cm
3
that the recipe predicted.
Fig.5.2

Above: First successful aerogel from the improved method


The optical properties of the aerogels produced herein included the following:
The sample was generally clear, with some white opaqueness when laid against a white
background. When laid on a dark background, especially a black background, the sample
took on a smoky, blue tinge. Cracks ran along the height of the cylinder derived from one
of the last two liquid CO
2
replacement stages.
29
The sample produced in the next run resulted in a failed aerogel. Because the
result turned out qualitatively identical to the failed samples from the Physics 174 project,
it pointed to the fact that the sample failed to exchange all of its pure ethanol for liquid
CO
2
, even after the two 18-hour baths in the critical point drying phase. The baths did not
suffice because the sample was from the larger of the molds, which was designed to
produce a gel with a volume just smaller than that of the critical point dryer chamber.
This meant that not enough liquid CO
2
could ever be present to replace all of the pure
ethanol present in the sample. Because of this result, later gels produced using the
maximum-capacity mold were cut in half.
The second successful batch of aerogels consisted of sections from two gels that
were broken when being extracted from their molds. The point of this run was to see if
broken gels could still produce useful samples. The results were interesting: The viewing
chamber was monitored at the point when the liquid CO
2
levels fell below the level of the
top-most samples. The exposed portions of these samples immediately developed an
opaque white appearance and developed deep cracks. When the CO
2
level was brought
back up, the samples stopped degenerating. It is clear from Fig.5.3 which of the smaller
samples was exposed to the gas pocket in the critical point dryer. One small sample to the
left of the screw has a single opaque white face where the liquid momentarily dipped
below the sample. The sample at the bottom left-hand corner of the cylindrical aerogel
sample was the topmost sample in the chamber and was fully exposed to the gas pocket
for several seconds, giving it its deeply cracked, opaque, and eroded look.


30
Fig.5.3

Above: Aerogel samples and a screw on the hot plate


Due to the amazing capacity of aerogels to be thermal insulators, this property
was the target of several tests carried out in this project. The first was to program a hot
plate to 150 degrees Celsius and place the aerogels samples on top. After allowing the
samples 10 minutes to equilibrate, the aerogels were imaged alongside a metal screw with
a Fluke thermal imaging camera. Even though the screws emissivity was not the same as
the aerogels, and thus appeared cooler than it actually was, it still showed higher heat
conduction than the large aerogel sample. While it was difficult to focus well enough on
the small samples to see their heat conduction properties, the large sample demonstrated
this trait extraordinarily well, remaining at a much cooler temperature than the hot plate
and showing almost no thermal gradient within its height.




31
Fig.5.4

Above: the larger aerogel sample alone on the 150 degrees Celsius hot plate


Below: the larger sample accompanied by the smaller samples and a screw on

the 150 degrees Celsius hot plate


Fig.5.5



The screw pictured in fig.5.5 seems to be at only a slightly higher equilibrium
temperature than the aerogel. However, the screw and the hot plate were both made of
reflective material, so that their emissivity was not the same as the aerogel. Because of
this, and the fact that the hot place was programmed to be at 150 degrees Celsius, it is
32
clear that both the screw and the hot plate were actually 10 - 20 degrees Celsius warmer
than they appear in the image.
Fig.5.6
Above: aerogel sample on the makeshift hot plate

In the second test the aerogel was heated up with an oxy-acetylene torch. Direct
exposure to the torch caused the surface of the aerogel to begin deforming. Because of
this, a makeshift hot plate was constructed (Fig.5.6) that would allow the aerogel to be
about 100 degrees Celsius hotter than the commercial hot plate, but would not deform the
aerogel. It is clear from Fig.5.7 and Fig.5.8 that even under temperatures hot enough to
begin bending the steel plate it sat on, the aerogel did allow heat to transfer along its
height.
33
Fig.5.7
Above: Thermal side view of the aerogel on the heated makeshift hot plate


Fig.5.8
Above: Thermal top view of the aerogel on the heated makeshift hot plate

Due to their low densities of 0.08 g/cm
3
, the silica solids produced in this thesis
classify as aerogels. Below are scanning electron micrographs of an aerogel produced in
this project, and a commercial aerogel owned by the Pomona College physics
department. While charging of the aerogels made anything beyond 50,000 times
magnification impossible, it is easy to see that both solids exhibit nanoscale structures.
34
The lattice and porous nature of this structure is evident, agreeing with the theoretical
ideal that aerogels are almost completely air by volume.


Above Left: Fig.5.9. Thesis sample at 30,000x mag. [23]

Above Right: Fig.5.10. Commercial sample at 20,000x mag. [23]


Further magnification does help to show the 3-dimensional nature of the lattice
structure. Below, the crater at the surface of an aerogel produced in this project shows the
lattice structure as a continuous 3-dimensional network as was expected. The individual
dendrites are on the order of several nanometers wide. The right-hand image shows the
same magnification of a commercial sample, which exhibits a homogenous surface of
pores and dendrites.

35


Above Left: Fig.5.11. Thesis sample at 50,000x mag. [23]

Above Right: Fig.5.12. Commercial sample at 50,000x mag. [23]































36
Chapter 6: Conclusions and Future Work


6.1: Conclusions

The questions and hurdles involved in devising a method to create simple SiO
2

aerogels in a small liberal arts college were met and resolved by this project. Future
students at Pomona College will have access to the attached manual (see Appendix III),
which outlines the steps to produce silica aerogels. With this, they can bypass the
problems encountered by this author. Though the method takes about a week from start to
finish, the time that the student must be in the laboratory is only about 6 hours in total.
While the larger samples produced herein exhibit cracks, many of the smaller ones do
not, and all samples held up during experimentation.
New technologies and ideas such as these provide solutions that will help improve
the future of energy and the environment. Cheap, reliable access to aerogels for
undergraduate students, in particular, can help increase interest and research into clean,
renewable energy and energy conservation, as well as environmental-protection
technologies.

6.2: Future Work

The sustained application of this project lies in the utilization of this method by
small liberal arts college students to create SiO
2
aerogels as a springboard for future
research and application.
One application that would be useful to lower-level physics courses, including
high school classes, would be to develop demonstrations or lab experiments with the
aerogel samples. Demonstrations that could potentially fill this niche are varied: A
demonstration of the thermal insulation properties of aerogels could include setting a
37
piece of paper, or a match on top of a piece of aerogel, and then holding a blow-torch or
Bunsen burner below. The idea would be to examine how heat travels through different
materials, with aerogels being the least-conductive of any material presented. Because the
strength-to-weight ratio of aerogels is very high, a demonstration or laboratory could be
developed to show why, and how, aerogels were used to capture comet dust in NASAs
Stardust mission. This might include weighing the aerogel and then gently placing many
times its own weight on top of it in the form of obviously heavy materials, such as metal,
or a section of wood. One problem with developing laboratories will be the propensity for
the aerogel samples to shatter if handled incorrectly. Because of this limitation, CF
3
-
functionalized aerogels could provide a great lab that does not involve moving or
touching the aerogel samples. The CF
3
-functionalized aerogels would allow the creation
of a lab that would show the water purification capabilities of the samples [21]. Another
lab could show why aerogels are replacing conventional windows in some instances,
even though the aerogels are chemically identical to, but more expensive than, everyday
glass. The lab could provide images of the differences between lattice networks of the
low-density aerogel versus an image of the compact, non-porous glass surface. The
difference in electromagnetic radiation transfer through glass and aerogel would bring the
point home [22].
Another goal of future research should be to execute original experiments.
Because of this, the molds for the samples were made to yield cylindrical samples of
scalable height. If little of the solution is introduced into the mold, then a thin disk will result,
which will aid in the fast production of the aerogels and increase their usefulness as a
platform for further experimentation.
38
One experiment that should be possible would be based off of the research of
Meador et al that incorporated carbon nanofibers into the aerogel structure. Because of
this research, it seems clear that basic SiO2 aerogels should serve as a good platform on
which to grow carbon nanotubes [17]. Meador et al also showed that involving carbon
nanofibers in aerogel production yields aerogels with similar densities, but much higher
tensile strengths and compressive modulii than unaltered samples. This mans that it might
be possible to involve carbon nanotubes in the chemical process of creating silica
aerogels, just as Meador et al included carbon nanofibers, because the two materials are
identical in chemistry. If, for instance, aerogels could be grown around a field of carbon
nanotubes, it might provide a use in electronics as a super-strong, super-small circuit
material. The method of incorporating the carbon nanofibers sonication into the liquid
silica solution could be used in the case of carbon nanotubes as well, or the aerogels
could be grown around a smaller aerogel sample with nanotube growth already present
on its surface. A scanning electron microscope can be used to examine the surface of the
aerogels and the nanotubes grown on top of it [26]. An atomic force microscope will
likely not be useful in examining the aerogel surface because the porous structure will
preclude high-quality imaging.
Further methods and recipes to create aerogels may be examined. This might
include using different techniques, but the same chemicals, or, using the same critical
point-drying technique, but using different chemicals, such as hydrogen silsesquioxane
(HSQ) [23]. If other recipes are attempted which produce hydrophilic aerogels, then the
methods of Liu et al address the issue of altering the surface chemistry of the aerogels by
treating them with isopropyl alcohol (IPA) and trimethylchlorosilane (TMCS) [16]. This
39
processing should allow the samples to be exposed to air and moisture indefinitely, if this
fails to alter the surface chemistry, then it might be possible to carry out experiments in
an N
2
-purged glovebox, or some other moister-free environment [23].




















40
7: Acknowledgements

I would like to thank Professor Tanenbaum for his guidance and interest in this
project over the past year and a half. A big thank you to Glenn Flohr who has been an
incredible help, both by fixing the critical point drying machine, and spending his own
time to help purchase and thread the Teflon molds. I wish to thank David Haley for his
help in gathering various minor materials for the project, and Professor Kwok for
supplying a digital pipette. I would like to thank Christina Frausto of the Chemistry
Department for her help in acquiring the necessary glassware and various measuring
equipment for this project. I would like to thank Professor Taylor of the Chemistry
Department for providing suggestions and solutions to several of the hurdles initially
faced in this project. I also wish to thank Dr. A.J. Tousimis of the Tousimis Company for
his willingness to share aerogel-synthesis procedures developed by him and his staff in
his lab.
















41
8: Bibliography

[1] Carlson, P.J.; Johansson, K. E.; Norrby, J.. 1980. Development of Silica Aerogel
Cerenkov Detectors. IEEE Transactions on Nuclear Science Vol. NS-27, (1):
96-100.
[2] Cho, Woojin; Saxena, Ravi; Rodriguez, Oscar; Ojha, Manas; Achanta, Ravi;
Plawsky, Joel L.; Gill, William N. 2005. Polymer Penetration and Pore Sealing in
Nanoporous Silica by CHF
3
Plasma Exposure. Journal of The Electrochemical
Society 152 (6): F61-F65.
[3] Fesmire, J.E.; and Sass, J.P.. 2008. Aerogel Insulation Application for Liquid
Hydrogen Launch Vehicle Tanks. Cryogenics 48: 223-231.
[4] Fricke, J; and Tillotson, T.. 1997. Aerogels: Production, Characterization, and
Applications. Thin Solid Films (297): 212-223.
[5] Gao, Siliang; Wang, Yujun; Wang, Tao; Luo, Guangsheng; Dai, Youyuan. 2009.
Immobilization of Lipase on Methyl-Modified Silica Aerogels by Physical
Adsorption. Bioresource Technology 100: 996-999.
[6] Gauthier, Ben M.; Bakrania, Smitesh D.; Anderson, Ann M.; Carrol, Mary K. 2004.
A fast supercritical extraction technique for aerogel fabrication. Journal of Non-
Crystalline Solids 350: 238-243.
[7] Hostler, S. R.; Abramson, A. R.; Gawryla, M. D.; Bandi, S. A.; Schiraldi, D. A..
2008. Thermal Conductivity of a Clay-Based Aerogel. International Journal of
Heat and Mass Transfer. doi:10.1016/j.ijheatmasstransfer.2008.07.002.
[8] Hrubesh, Lawrence W. 1998. Aerogel Applications. Journal of Non-Crystalline
Solids 225 (1): 335-342.
42

[9] Hunt, Arlon; Ayers, Michael. Silica Aerogels. Microstructured Materials Group
Lawrence Berkely National Laboratory. http://eetd.lbl.gov/ecs/aerogels/sa-
home.html. 2009.
[10] Hwang, Sung-Woo; Jung, Hae-Hyun; Hyun, Sang-Hoon; Ahn, Young-Soo. 2007.
Effective Preparation of Crack-Free Silica Aerogels via Ambient Drying. J Sol-
Gel Sci Techn 41: 139-146.
[11] Jones, Steven M. 2006. Aerogel Space Exploration Applications. J Sol-Gel Sci
Technology 40: 351-357.
[12] Juzkow, Marc. 2002. Aerogel Capacitors Support Pulse, Hold-Up, and Main Power
Applications. Power Electronics Technology 28 (2): 58-60.
[13] Kistler, S. S. 1933. Coherent Expanded Aerogels. Journal of the American
Chemical Society 65 (10): 1909-1919.
[14] Kistler, S.S. 1938. Thermal Conductivity of Silica Aerogels. Ind. Eng. Chem. 30 (9):
1082-1086.
[15] Krainov, V.P. and Smirnov, M.B. 2001. Laser Induced Fusion in Aerogel. Laser
Physics 12 (4): 781-785.
[16] Liu, Ming-Long; Yang, De-An; Qu, Yuan-Fang. 2008. Preparation of Super
Hydrophobic Silica Aerogel and Study on its Fractal Structure. Journal of Non-
Crystalline Solids 354: 4927-4931.
[17] Meador, Mary Ann B.; Vivod, Stephanie L.; McCorkle, Linda; Quade, Derek;
Sullivan, Roy M.; Ghosn, Louis J.; Clark, Nicholas; Capadona, Lynn A. 2008.
Reinforcing Polymer Cross-Linked Aerogels with Carbon Nanofibers. Journal of
43
Materials Chemistry 18: 1843-1852.
[18] Park, Sung-Woo; Jung, Sang-Bae; Yang, Jun-Kyu; Park, Hyung-Ho; Kim, Hae-
Cheon. 2002. Ambient pressure dried SiO
2
aerogel film on GaAs for application
to interlayer dielectrics. Thin Solid Films 420-421: 461-464.
[19] Pierre, Alain C. and Pajonk, Gerard M. 2002. Chemistry of Aerogels and Their
Applications. Chem. Rev. 102: 4243-4265.
[20] Pietron, Jeremy J.; Stux, Arnold M.; Compton, Ratonya, S.; Rolison, Debra R..
2007. Dye-Sensitized Titania Aerogels as Photovoltaic Electrodes for
Electrochemical Solar Cells. Solar Energy Materials & Solar Cells 91: 1066-
1074.
[21] Reynolds, John G.; Coronado, Paul R.; Hrubesh, Lawrence W. 2001. Hydrophobic
Aerogels for Oil-Spill Cleanup - Intrinsic Absorbing Properties. Energy Sources
23: 831-843.
[22] Schultz, J.M. and Jensen, K.I. 2008. Evacuated aerogel glazings. Vacuum 82: 723-
729.
[23] Tanenbaum, David. Discussions with author. 2008-2009.
[24] Ten-Year-Old Child Produces Homemade Aerogels. Adzoe
http://adzoe.8m.com/Aerogelsa.htm. 2008.
[25] Timothy, B. Roth; Anderson, Ann M.; Carrol, Mary K. 2008. Analysis of a rapid
supercritical extraction aerogel fabrication process. Prediction of thermodynamic
conditions during processing. Journal of Non-Crystalline Solids 354 (31): 3685-
3693.
[26] Tillotson, T.M. and Hrubesh, L.W. 1992. Transparent ultralow-density silica
44
aerogels prepared by a two-step sol-gel process. Journal of Non-Crystalline Solids
145 (1-3): 44-50.
[27] Tousimis, A. J; Staff. 2005. Tousimis Advanced Manual Critical Point Dryer
Samdri-PVT-3D. 15-17. Tousimis Inc.
[28] Wikipedia. Thermal Conductivity.
http://en.wikipedia.org/wiki/Thermal_conductivity. 2009
[29] Wood, Alan. CO
2
Phase Diagram.
http://www.teamonslaught.fsnet.co.uk/co2_info.htm. 12/11/2008.
[30] Xu, Pei; Drewes, Jorg; Heil, Dean; Wang, Gary. 2008. Treatment of Brackish
Produced Water Using Carbon Aerogel-Based Capacitive Deionization
Technology. Water Research 42: 2605-2617.
[31] Yao, Yunjin; Zhang, Suping; Yan, Yongjie. 2008. CVD Synthesis and Purification
of Multi-walled Carbon Nanotubes. 2008 2
nd
IEEE International Nanoelectronics
Conference (INEC 2008): 562-565.









45
9: Appendix I: Images of Equipment


Above: Maximum-capacity mold and best-sample-producing mold and screwdriver.


Above: Filter paper cut to fold up into a cylindrical cup to hold the gel sample inside the
critical point dryer chamber.




46


Above: Samdri-PVT-3D critical point dryer and liquid CO2 supply canister setup. The
viewing chamber is the central silver disk on the lower half of the dryer.


Above: The exhaust beaker which catches liquid ethanol and CO2 while allowing gasses
to pass through the left tube to the fume hood.
47

Above: The fluke thermal imaging camera.











48
10: Appendix II: More Sample Images


Above: Two areas of thesis sample at 50,000x mag. [23].


Left: Birds-eye view of thesis sample. Right: Side view of thesis sample and screw on
hot plate under white light.

49

Left: an image of the bare hot plate. Right: the larger sample alone on the hot plate.


Above: A birds eye view of the aerogel on the hot plate


Above: a side view of the larger sample with smaller samples and the screw.
50

Above: A torch in direct contact with the aerogel sample, which caused deformation.


Above: Top-down view of the aerogel on the makeshift hot plate.






51
11: Appendix III
Student Manual for Synthesizing SiO
2
Aerogels
In 1931, Steven Kistler made a bet with a colleague that he could prove a wet gel
contained a solid matrix the same size and shape of the gel. To do this he began with a
gel and extracted the liquid, leaving a low-density solid behind. Using an autoclave to
drive the liquid past its critical point he was able to conquer the obstacle of surface
tension which would otherwise rip apart the internal solid structure of the gel. His
successful wager produced the first silica-based aerogel. Silica aerogels begin life as a
silica (SiO
2
) gel and are about 99% liquid by weight, but contain a network of silica
dendrites that give the liquid surface tension.
The first step in making aerogels is to create what is called a wet gel. Currently,
the best way to create the wet gels is to begin with a silicon-alkolyde precursor, such as
TEOS, which was used for this project. The chemical makeup of TEOS is Si(OCH
2
CH
3
)
4

and when added to water, achieves the chemical reaction.
Si(OCH
2
CH
3
)
4 (liq.)
+ 2(H
2
O)
(liq.)
SiO
2 (solid)
+ 4(HOCH
2
CH
3
)
(liq.)
eq.1 [9]
The amount of water indicated in eq.1 is only enough to exactly balance the
reaction and in practice anywhere from 4 to 30 times more water should be used to
increase the strength of the gels. This chemical reaction is generally accomplished in
ethanol.
The reason silicon-based aerogels have been studied much more than any other
type is because silicon atoms carry a reduced partial positive charge
+
. In Si(OEt)
4

+
is
about 0.32 [19]. This reduced partial positive charge makes the gelation kinetics of the
silicon precursor extremely slow. Because of this, the speed of the hydrolysis rate
compared to the condensation rate can be controlled through catalysts. Controlling these
kinetics allows silica aerogels to be adapted at this stage for their future application [19].
This project makes use of Silbond H-5, a pre-polymerized TEOS silica source
which only requires processing with a basic catalyst in order to achieve a gel. It is the
removal of all left-over liquids that turn the wet gel into an aerogel and give the material
its unique physical properties.

Supercritical Fluid Theory

If a wet gel were to dry at normal room temperature and pressure, then the liquid
within the gel would evaporate into a gas and the lattice-structure that gives the gel its
shape would shrink and crumble. The deforming comes from the capillary pressures
arising from the diminishing meniscus of liquid. When these pressures build up in the
lattices pores, they destroy the lattice. This problem is solved by introducing the sample
into a temperature and pressure controlled environment, such as an autoclave or a critical
point dryer. The pressure in the samples environment is raised, followed by the
temperature, until the liquid turns into a supercritical fluid. The point at which this
happens is called the critical point. This is the point at which a gas cannot be turned into a
liquid simply by increasing pressure. At the critical point the fluid will lose all surface
tension properties associated with a liquid and become completely miscible. With small
changes in pressure, the supercritical fluid experiences large changes in density.
52


Above: CO
2
Phase Diagram [29]

In this project, carbon dioxide will be introduced to the sample in liquid form,
replacing the pure ethanol in the gel. The liquid CO
2
will then brought past its critical
point of 304.1 K and 72.8 atm. The pressure of the supercritical fluid is then lowered,
while maintaining higher than critical temperatures in order to take advantage of its
properties of low viscosity and high diffusivity. In this manner the supercritical fluid
becomes more gas-like and is vented off, leaving the silicon-dioxide lattice structure
intact.

Physical Theory

The solid nanoscale silica dendrite network of silica-based aerogels give them
their unique properties. The ionic fraction of the polar covalent bonds for several
different metal oxides yields the following results.
f
ionic
= 1 exp(-0.25(X
M
X
O
)
2
)

eq.2 [19]
X
O
and X
M
represent the Allred-Rochow electronegativities of O and M. For
Al
2
O
3
, TiO
2
, ZrO
2
, and Na
2
O, f
ionic
gives 0.64, 0.70, 0.71, and 0.78. SiO
2
on the other
hand has an f
ionic
of 0.54, allowing the Si-O-Si angle value to range widely which give the
resulting structure a random network [19]. The other four oxides given have higher
ionic fractions, leading to a lower range of bond-angle values. This means that the
random bonding only occurs on a more macro scale with bigger, more dense colloidal
particles. When this happens the resulting gel is particulated instead of forming a random
network of dendrites of particles. This means that achieving gelation with higher f
ionic

valued oxides is difficult and even impossible with a value as high as the 0.78 of Na
2
O
[19].
The silica dendrite network, which makes up the aerogels create an extremely
strong material for its relative weight, though they can shatter under sharp pressure.
Aerogel is also an amazing thermal insulator. The reason for this is threefold: The air
inside of the silica lattice cannot pass through the nanoscale pores, so convection cannot
occur. Silica has a very low heat transfer coefficient and because of this, the heat
53
conductivity through the physical solid matrix of the aerogel follows the formula for solid
conductivity
s
.

s
~

eq.3 [19]
Where is the density of the aerogel, and has a value between 1.2 and 1.8.
Small amounts of carbon can be added to the aerogel, absorbing infrared radiation and all
but halting radiative heat transfer. Because of this, aerogels have thermal conductivities
of 0.03-0.004 W/(mK), up to 6.25 times lower than air. At best, aerogels have thermal
conductivities of up to 10 times lower than wood or polyurethane foam insulation [21].
Due to this fact, windows no longer need to be the week point in energy efficiency for
buildings if the windows incorporate aerogels. Out of any currently known materials,
aerogels hold the record for the lowest thermal conductivity, refractive index, sound
velocity, dielectic constant, and bulk density.

The Gel Stage

To first step in creating aerogels is to produce a gel from the following recipe [9].

1) In a 500 mL beaker mix 25 mL of Silbond H-5 with 25 mL of ethanol
2) Then mix the catalyst solution in a 100 mL graduated cylinder; its components
are 17.5 mL of ethanol, 37.5 mL of water, and 0.175 mL of 30% aqueous
ammonia. The 0.175 mL of 30% aqueous ammonia requires a digital pipette due
to the small amount of liquid.
3) Then pour the catalyst solution slowly into the Silbond H-5 solution stirring the
entire time. This should take 45 seconds at minimum.
4) Then pour the resulting mixture carefully into the Teflon molds.

The Mold Stage

The gels should set in 30-90 minutes, assuming no temperature extremes [9].
After the gels are set, the following solution needs to be prepared [24].
17.5 mL ethanol. 37.5 mL water.
Set the molds holding the samples in 50 mL beakers and completely cover them
with the new solution. This keeps the samples from being exposed to air which would dry
out the samples and destroy the silicon lattice structure [24]. Cover the beakers with tin
foil, or other material. Allow the gels to set in the molds for over 48 hours in order to
give the lattice structure time to fully develop. The Teflon molds should not be tightened
beyond snug due to their softness and the possibility of breakage.

The Bath Stage

After the gels are fully set, the next step is to remove them from the molds and set
them in ethanol baths. Set aside a 50 mL beaker containing 25 mL of pure ethanol for
each sample. Then, extract the samples from the molds by unscrewing the bottoms and
gently pushing the gels into the prepared ethanol baths. The baths need to drained and
replenished with an equal amount of ethanol every 8 to 24 hours. Each sample should be
introduced to a total of at least 5 pure ethanol baths in order to ensure that the liquid held
54
within the gel matrix is pure ethanol. While able to be moved by hand, the more contact
with pressure and air, the higher probability that the gel will weaken, develop cracks, or
even break. The best method is to leave the gels in one beaker, and if they have to be
moved, slide them gently from beaker to beaker. Even when care is taken in every step to
minimize pressures and stresses endured by the gel, do not be surprised if about half the
samples break, fall apart, or do not form a coherent gel matrix.

The Drying Stage

The Tousimis Samdri PVT-3D critical point dryer is used in the drying stage of
this process. The critical point dryer chamber contains two openings, the liquid CO
2
entry
line and the exhaust line. Because the gels could potentially run into these openings and
block up the lines, filter paper needs to be cut and folded into a cylinder with one end.
Because it does not interact with the CO
2
or ethanol, the filter paper will be able to
effectively block the two openings from gel particulate while remaining invisible to the
rest of the chemicals in the experiment.
After the filter paper is in place, lining the drying chamber, pour ethanol into the
chamber until it is half full. Then, extract the gel sample from its bath and place it into the
drying chamber. Process the sample according to the Tousimis Advanced Manual Critical
Point Dryer Samdri-PVT-3D user manual. The instructions for operation of the critical
point dryer begin on page 15 and end on page 17 [27]. However, there is one important
difference between the instructions and the procedures used in this project. As per Dr. A.J
Tousimis suggestion, after step 7 is accomplished, the sample should be allowed to sit
for 15-18 hours without moving on to step 8. After that time period, steps 6 and 7 are to
be repeated and the gel needs to be allowed to sit in the same manner as before for 15-18
hours. During these wait times, the chamber does not need to be kept below ambient
temperature. After the second waiting period, steps 6 and 7 are repeated for the third time
and then the procedure continues as normal, with step 8 until the end.
When repeating steps 6 for the second and third time, it is imperative that viewing
chamber be watched to guarantee that the liquid CO
2
level does not drop below the
sample. This misstep is easy to do because the liquid CO
2
is cooling quickly from above
ambient temperature to around 0 degrees Celsius. While cooling the pressure drops
significantly and if it drops below 850 psi, a gas pocket develops in the chamber. If the
liquid drops below the sample, allowing the gas pocket to come in contact with the
sample then the sample quickly develops cracks and begins to turn opaque. This change
in appearance represents the undermining of the solid matrix within the gel, and will
result in shrunken, denser and highly-weakened samples. The critical point dryer,
including the viewing chamber, can be seen in Appendix I.
Each time when performing step 6 from the Tousimis critical point dryer manual
the beaker connected to the exhaust line should be monitored. When opaque white solids
enter the beaker, looking like snow, then the critical point dryer chamber has been
evacuated of ethanol and only liquid CO
2
is left except for any ethanol involved in the gel
matrix. This should only take about 10 minutes of purging and replacing the liquid in the
chamber. An image of the exhaust beaker can be found in Appendix I.
At the point when the CO
2
is extracted for the final time, the gel sample becomes
an aerogel.
55

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