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CHAPTER 1
INTRODUCTION
Aerogel is defined as a group of extremely light and porous solid materials. Silica-based
aerogels are among the lightest ones, can be less than four times as dense as dry air, and some
are nearly transparent, its nickname is solid smoke or frozen smoke.
By Technical Definition,
An aerogel is an open-celled, mesoporous, solid foam that is composed of a network of
interconnected nanostructures and that exhibits a porosity (non-solid volume) of no less than
50%.
The term mesoporous refers to a material that contains pores ranging from 2 to 50 nm in
diameter.Since this definition is good for most porous materials, the term aerogels became
reserved for the porous gels obtained by removing solvent from highly swollen gels at the
conditions that no or minimal collapse occurs, which causes the liquid in the gel to become
supercritical (in a state between a liquid and a gas) and lose its surface tension. The result is an
open porous material with a backbone morphology that can be modeled in terms of three
dimensionally interconnected strings of nanoscopic pearls. The length scale of both the pearls
as well as the interconnected voids can be independently tailored over a wide range, i.e. from
a few nanometers to several microns.One of the striking advantages of aerogels compared to
other porous materials is that both porosity and inner surface area can be tuned independently.
Porosities of up to 99.9 % are achievable; when microporosity is present, the specific surface
area can exceed 1500 m2/g. Because of their unique properties, i.e., large surface area, very
small pores and very low bulk density, aerogels are potentially important candidates for a wide
range of applications.
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CHAPTER 2
HISTORY
Steven. S. Kistler
Steven. S. Kistler of the College of the Pacific in Stockton, California set out to prove that a
"gel" contained a continuous solid network of the same size and shape as the wet gel. It is
believed that Kistler's interest was stimulated by a friendly wager with fellow worker Charles
Learned. They competed to see if one of them could replace the liquid inside a jelly jar with
gas without causing any shrinkage. Kistler won the bet, and published his findings in a 1931
edition of the journal Nature.
As is often the case, the obvious route included many obstacles. If a wet gel were simply
allowed to dry on its own, the gel would shrink, often to a fraction of its original size. This
shrinkage was frequently accompanied by severe cracking of the gel. Kistler surmised,
correctly, that the solid component of the gel was microporous, and that the liquid-vapor
interface of the evaporating liquid exerted strong surface tension forces that collapsed the pore
structure. Kistler then discovered the key aspect of aerogel production:
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CHAPTER 3
What Does an Aerogel Feel Like? How Strong Are They?
To the touch, an inorganic aerogel (such as a silica or metal oxide aerogel) feels something like
a cross between a Styrofoam peanut, that green floral potting foam used for potting fake
flowers, and a Rice Krispie. Unlike wet gels such as Jell-O, inorganic aerogels are dry, rigid
materials and are very lightweight.
In general aerogels are pretty fragile. Inorganic aerogels are friable and and will snap when
bent or, in the case of very low density aerogels, when poked, cleaving with an irregular
fracture. This said, depending on their density, aerogels can usually hold a gently applied load
of up to 2,000 times their weight and sometimes more. But since aerogels are so low in density,
it doesnt take much force to achieve a pressure concentration equivalent to 2,000 times the
materials weight at a given point. The amount of pressure required to crush most aerogels with
your fingers is about what it would take to crush a piece of Capn Crunch cereal.
Organic polymer aerogels are less fragile than inorganic aerogels and are more like green
potting foam in consistency in that they are squish irreversibly. Carbon aerogels, which are
derived from organic aerogels, have the consistency of activated charcoal and are very much
not squishy.
There are several examples, however, of remarkably strong aerogels that can withstand tens of
thousands of times their weight in applied force. A class of polymer-crosslinked inorganic
aerogels called x-aerogels are such materials and can even be made flexible like rubber in
addition to being mechanically robust. One type of x-aerogel made from vanadia (vanadium
oxide) is extraordinarily strong in compression with the highest compressive strength to weight
ratio of any known type of aerogel and rivals that of materials such as aerospace-grade carbon
fiber composites! Regardless of composition, most types of aerogel can be made stronger
simply by making them denser (between 0.1 and 0.5 g cm-3), however only at the expense of
their light weight and ultralow thermal conductivity.
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CHAPTER 4
Aerogel
4.1 What Are Aerogels Made Of?
The term aerogel does not refer to a particular substance, but rather to a geometry which a
substance can take onthe same way a sculpture can be made out of clay, plastic, papier-mch,
etc., aerogels can be made of a wide variety of substances, including:
Silica
Most of the transition metal oxides (for example, iron oxide)
Most of the lanthanide and actinide metal oxides (for example, praseodymium
oxide)
Several main group metal oxides (for example, tin oxide)
Organic polymers (such as resorcinol-formaldehyde, phenol-formaldehyde,
polyacrylates, polystyrenes, polyurethanes, and epoxies)
Biological polymers (such as gelatin, pectin, and agar agar)
Semiconductor nanostructures (such as cadmium selenide quantum dots)
Carbon
Carbon nanotubes
Silica Aerogel
Carbon Aerogel
Metal oxide Aerogel
Organic Aerogel
Alumina Aerogel
Semiconducting Metal Chalcogenide Aerogels
Metal Aerogels
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Aerogel
Color
Iron Oxide
Chromia
Vanadia
Neodymium Oxide
Purple, transparent
Samarium Oxide
Yellow, transparent
Pink, transparent
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sunlight as the energy source. They consist of a network of interconnected nanoparticles which
form a sponge-like, open-celled, nonporous framework.
Semiconducting metal chalcogenide (say kal-kah-jih-nide) aerogels are a new, exciting class
of aerogels materials. First prepared in 2002, these aerogels possess a unique combination of
porosity, optical translucency, and photoluminescence, and show great promise for use as
chemical sensors (artificial nose?) and energy applications such as photovoltaics (solar cells)
and extraction of hydrogen from water using sunlight as the energy source.
Like other aerogels, metal chalcogenide aerogels consist of a network of interconnected
nanoparticles which form a sponge-like, open-celled, nonporous framework. But it is the
carefully-engineered nanoparticles used to make these aerogels that makes them so special
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1.1.1 Values
1.1.2 Unit
s
Class
Silica
Composition
SiO2
Density Range
g cm-3
C
0.02-0.5
600-800
500-950
Pore Volume
cm g-1
nm
2.0-3.0
nm
20
Transparency
Clear to foggy
Appearance
Monolithicity
Monolithic
Flexibility
Rigid, friable
Hydrolysis of silicon
alkoxide or acid-driven
condensation of waterglass
Supercritical CO2 or hightemperature drying from
organic solvent
Gel Synthesis
Drying Method
Index of Refraction
Carbon
0.0011-0.650
Surface Area
Thermal
Conductivity at
Room Temperature
Electrical
Conductivity
W m-1 K-1
0.016-0.03
S cm-1
110-18
Dimensionl
ess
1.002-1.046
3.0-20
7.0-20.0
Opaque
Opaque black, shiny or
matte
Monolithic, charcoal like
Rigid, breaks like charcoal
Polymerization of 1,3dihydroxybenzene with
methanal
Supercritical CO2 followed
by pyrolysis at 400C1050C under inert gas
120-320
1-14.7
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CHAPTER 5
HOW IS AEROGEL MADE
As described in the What is Aerogel? , an aerogel is the intact, dry, ultralow density, porous
solid framework of a gel (that is, the part that gives a gel its solid-like cohesiveness) isolated
from the gels liquid component (which takes up most of the volume in the gel). But how do
you isolate such a material from a gel?
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that the kinetic energy of the molecules in the liquid overwhelms the attractive forces that hold
them together as a liquid. In short, as the pressure and temperature in the container get closer
to the critical point, the liquid phase becomes more gas-like and the vapor phase more liquidlike. Finally, the critical point is reached and the meniscus dividing the two phases blurs away,
resulting in a single supercritical phase. As this occurs, the surface tension in the fluid gradually
drops to zero, and thus the ability of the fluid to exert capillary stress does too.
5.4 Aerogelification
In the case of making aerogels, a gel is placed in a pressure vessel under a volume of the same
liquid held within its pores (lets say ethanol for example). The pressure vessel is then slowly
heated to the liquids critical temperature. As this happens, the vapor pressure of the liquid
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increases, causing the pressure in the vessel to increase and approach the critical pressure of
the liquid. The critical point is then surpassed, gently transforming the liquid in the gel (as well
as the liquid and vapor surrounding the gel) into a supercritical fluid. Once this happens, the
ability of the fluid in the gel to exert capillary stress on the gels solid framework structure of
the gel has decreased to zero.
With supercritical fluid now present throughout the entire vessel and permeating the pores of
the gel, the fluid in the gel can be removed. This is done by partially depressurizing the vessel,
but not so much as to cause the pressure in the vessel to drop below the critical pressure. The
temperature of the vessel must also remain above the critical temperature during this step. The
goal is to remove enough fluid from the vessel while the fluid is still supercritical so that when
the vessel is fully depressurized/cooled down and drops below the fluids critical point, there
will simply not be enough substance left in the vessel left for liquid to recondense. This might
require several cycles of heating (and thus pressurizing) followed by depressurization (again
all done above the critical point). Once enough fluid has been removed from the vessel, the
vessel is slowly depressurized and cooled back to ambient conditions. As this happens, the
fluid in the vessel passes back through the critical point, but since much of the fluid has been
removed and the temperature is still elevated as the vessel depressurizes, the fluid reverts to a
gas phase instead of a liquid phase. What was liquid in the gel has been converted into a gas
without capillary stress every arising, and an aerogel is left behind.
It is important to note, however, that most of the liquids used in the preparation of gels are
organic solvents such as methanol, ethanol, acetone, and acetonitrile, and such liquids are
potentially dangerous at the temperatures and pressures required to make them supercritical.
To make the aerogelification process less dangerous, the liquid component of a gel can be
exchanged with a non-flammable solvent that mixes well with organic solventsliquid carbon
dioxide
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Solvent.
As molecules assemble together (polymerize) into nanoparticles, the solvent needs to be able
to keep the nanoparticles dissolved so that they dont precipitate out of the liquid. Also, the
solvent can play a role in helping nanoparticles connect together. As a result, the solvent makes
a big difference in ensuring a gel network can form.
Temperature.
The chemical kinetics of the different reactions involved in the formation of nanoparticles and
the assembly of nanoparticles into a gel network are accelerated by temperature, meaning the
gel time is affected by temperature. If the temperature is too low, gelation may take weeks or
months. If the temperature is too high, the reactions that join nanoparticles together into the gel
network occurs so quickly that clumps form instead and solid precipitates out of the liquid.
Reaction-generated heat
Heat released from chemical reactions involved in the formation of nanoparticles and gel
networks can feed back into the solution and cause things to react faster, releasing even more
heat, causing things to react even faster, etc.
Time.
Depending on the type of gel being made, different steps in the gel formation process work
differently over different time scales. In general, slower is better for sol-gel. If a gel is allowed
to form slowly, it usually has a much more uniform structure. This often means a stronger gel
and, in the case of potentially transparent gels like silica, results in a clearer gel that Rayleigh
scatters less (appears less blue). Speeding reactions up too much causes precipitates to form
instead of gel network, and can make a gel cloudy and weak or simply not form.
Catalysts.
A catalyst is a chemical that accelerates a chemical reaction but does not get used up in doing
so. In a lot of sol-gel chemistry, both acids (H+) and bases (OH) are catalysts, but accelerate
chemical reactions by different mechanisms. This is another reason why sol-gel chemistry is
usually pH sensitive. In silica gel chemistry, fluoride ion (F) can catalyze gel formation, as it
exploits a special ability of silicon to temporarily form five bonds. Small amounts of catalysts
(catalytic amounts), on the order of milligrams per tens of milliliters of solution can cause
drastic changes in gel timein many cases reducing gel time from hours, days, or weeks to
minutes.
Agitation.
Mixing a sol as it gels is important to ensure that the chemical reactions in the solution occur
uniformly and that all molecules receive an adequate supply of chemicals they need for the
reactions to proceed properly. However, as a sol gels, there are microscopic and macroscopic
domains of partially-formed gel network throughout the liquid, and agitation can sometimes
disrupt the formation of these domains, meaning they get broken up, however usually the
broken network fragments regrow and a solution-wide network results.
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Fig 5.4
High-porosity aerogel
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CHAPTER 6
AEROGEL APPLICATIONS
A nearly transparent, very lightweight material that is a dry gel principally made from silica
(silicon dioxide) and 96% air. Dubbed a "Super Material", aerogel is the world's lightest solid,
weighing as little as three times that of air and exhibiting superb insulating properties.
Although aerogel looks like it could float away, it has very high compression strength.
Theoretically, a block weighing less than a pound could support a weight of half a ton.
Aerogels real strength is its incredible insulating effects on any kind of energy transfer; thermal,
electrical or acoustic. Aerogel can damp out almost any kind of energy. A one-inch thick
Aerogel window has the same insulation value as 15 panes of glass and trapped air - which
means a conventional window would have to be ten-inches thick to equal a one-inch thick
aerogel window.The following applications for aerogels are associated with certain properties
of aerogel materials. In many cases, the application is associated with a single property even if
the aerogels have a combination of properties appropriate to the given application.
Fig 6.1: The crayons on top of the aerogel are protected from the flame underneath.
Similar silica aerogels were used to insulate the Mars rover
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MARS ROVER
Aerogels were used to insulate the Mars Rover, where its lightness and strength were
established as ideal. That's the primary reason aerogel was used as insulation on the Sojourner
Mars rover in 1997. As night fell on Mars, the temperature dropped down to -67 C (-88 F).
Although the temperature outside was colder than Antarctica in winter, it remained a balmy 21
C (70 F) inside the Rover, where sensitive electronics were protected from the hard freeze.
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CHAPTER 7
MARKET AND TREND OF AEROGEL
7.1 The Market for Aerogels
With its unique properties of being extremely lightweight, a great thermal insulator and given
the vast applications already discovered for this material type, the potential markets for
aerogels look promising. According to Electronics.ca research network, the market for aerogels
by 2013 is estimated to be $646.3 million with a compound annual growth rate of 50.8%. A
number of industries have shown active interest in the material and applications have been
extend to the automotive, oil and gas, constructions, cryogenics, shipping and other industries.
With new applications being discovered and innovation activity around the development of
aerogels still at a high, the production and demand for various types of aerogels will continue
to be strong. The current high production costs associated with manufacturing aerogels makes
it expensive often costing up to $1000 per ounce. However, this hasnt appeared to have
deterred demand and as with most new materials, we can perhaps expect costs to come down
later in the life cycle.
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CHAPTER 8
FUTURE
Today significant efforts are underway to further mechanically strong aerogels, aerogels of
new compositions for sensors and energy production, and to apply aerogels for use as hydrogen
storage media. Metal aerogels are just around the corner. More advanced supercapacitors that
rival todays batteries are becoming likely. Hydrogen production using cleverly-engineered
semiconductor aerogels will change the way we think about energy and fuel. Smart materials
made possible by the unique combinations of materials properties exhibited by aerogels will
enhance and impact our daily lives.
Dr. Debra Rolison at the Naval Research Laboratory calls aerogel the original nanotech. But
aerogels have come a long way since the days of Kistler, and there are endless possible
applications of aerogel materials.
CONCLUSION
Aerogel will probably be a common household name. Although it is not yet ready for
commercial use, Americas Fortune magazine's "Technology to Watch" column mentioned 800
potential products that could be manufactured out of aerogel, citing everything from surfboards
to satellites. With the use of aerogel in the Sojourner Mars rover, in the Star Dust spacecraft,
and in the hundreds of other possible products and applications, the "unobtainium" once only
dreamed about may finally be just around the corner.
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GLOSSARY
Hydrolysis:
The reaction of a metal alkoxide (M-OR) with water, forming a metal hydroxide (M-OH).
Condensation:
A condensation reaction occurs when two metal hydroxides (M-OH + HO-M) combine to give
a metal oxide species (M-O-M). The reaction forms one water molecule.
Sol: A solution of various reactants that are undergoing hydrolysis and condensation reactions.
The molecular weight of the oxide species produced continuously increases. As these species
grow, they may begin to link together in a three-dimensional network.
Gel Point:
The point in time at which the network of linked oxide particles spans the container holding
the Sol. At the gel point the Sol becomes an Alcogel.
Precursors:
In the sol-gel process, the precursors (starting compounds) for preparation of a colloid consist
of a metal or metalloid element surrounded by various ligands (appendages not including
another metal or metalloid atom). The latter is an example of an alkoxide, the class of
precursors most widely used in sol-gel research.
Shrinkage:
Shrinkage of a gel, either during syneresis or as liquid evaporates during drying, involves
deformation of the network and transport of liquid through the pores.
Aerosol:
A colloidal suspension of particles in a gas (the suspension may be called a fog if the particles
are liquid and a smoke if the are solid).
Aging:
The term aging is applied to the process of change in structure and properties after gelation.
Bond formation does not stop at the gel point. In the first place, the network is initially
compliant, so segments of the gel network can still move close enough together to allow further
condensation (or other bond-forming processes). Moreover, there is still a sol within the gel
network, and then those smaller polymers or particles continue to attach themselves to the
network.
Colloid:
A mixture in which one substance is divided into minute particles (called colloidal particles)
and dispersed throughout a second substance. The dispersed phase is so small (11000 nm)
that gravitational forces are negligible and interactions are dominated by short-range forces,
such as van der Waals attraction and surface charges. The mixture is also called a colloidal
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system, colloidal solution, or colloidal dispersion. Familiar colloids include fog, smoke, and
homogenized milk.
Emulsion:
Is a suspension of liquid droplets in another liquid, these types of colloids can be used to
generate polymers or particles from which ceramic materials can be made
Gel:
A gel consists of two parts, a solid part and a liquid part. The solid part is formed by the threedimensional network of linked oxide particles. The liquid part (the original solvent of the sol)
fills the free space surrounding the solid part. The liquid and solid parts of a gel occupy the
same apparent volume. Thus, a gel is a substance that contains a continuous solid skeleton
enclosing a continuous liquid phase. The gel can be removed from its original container and
can stand on its own. The continuity solid structure gives elasticity to the gel (as in the familiar
gelatin dessert).
Alcogel (wet gel):
At the gel point, the mixture forms a rigid substance called an alcogel. The alcogel can be
removed from its original container and can stand on its own. An alcogel consists of two parts,
a solid part and a liquid part. The solid part is formed by the three-dimensional network of
linked oxide particles. The liquid part (the original solvent of the Sol) fills the free space
surrounding the solid part. The liquid and solid parts of an alcogel occupy the same apparent
volume.
Supercritical fluid:
A substance that is above its critical pressure and critical temperature. A supercritical fluid
possesses some properties in common with liquids (density, thermal conductivity) and some in
common with gases (fills its container, does not have surface tension).
Aerogel:
What remains when the liquid part of an alcogel is removed without damaging the solid part
(most often achieved by supercritical extraction). If made correctly, the aerogel retains the
original shape of the alcogel and at least 50% (typically >85%) of the alcogel's volume.
Xerogel:
What remains when the liquid part of an alcogel is removed by evaporation, or similar methods.
Xerogels may retain their original shape, but often crack. The shrinkage during drying is often
extreme (~90%) for xerogels.
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REFERENCES
Magda Moner i Gerona in: Phd thesis on SILICA AEROGELS: SYNTHESIS AND
CHARACTERIZATION (university of Barcelona)
C.J. Brinker, G.W. Sherer, Sol-Gel Science. Physics and Chemistry of Sol Gel Processing,
Academic Press, New York, 1990
www.scribd.com
www.wikipedia.org
http://www.springerlink.com/content/0928-0707
http://www.aerogel.org
http://www.tonyboon.co.uk/aerogel/aerogel.htm
http://www.springerlink.com/content/0928-0707
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