AEROGEL

CHAPTER 1

INTRODUCTION

Aerogel is defined as a group of extremely light and porous solid materials. Silica-based
aerogel 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 doesn’t take much force to achieve a pressure concentration equivalent to 2,000
times the material’s 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 Cap’n 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 on–the same way a sculpture can be made out of clay, plastic, papier-
mâché, 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

4.2 Types of Aerogel

1) Silica Aerogel
2) Carbon Aerogel
3) Metal oxide Aerogel
4) Organic Aerogel
5) Alumina Aerogel
6) Semiconducting Metal Chalcogenide Aerogels
7) Metal Aerogels

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4.2.1 Silica Aerogel

Silica aerogel is the most common type of aerogel and the most extensively studied and used.
It is a silica-based substance, derived from silica gel.

The lowest-density silica nanofoam weighs 1,000 g/m3, which is the evacuated version of the
record-aerogel of 1,900 g/m3. The density of air is 1,200 g/m3 (at 20 °C and 1 atm). As of
2013, aero graphene had a lower density at 160 g/m 3, or 13% the density of air at room
temperature. The silica solidifies into three-dimensional, intertwined clusters that comprise
only 3% of the volume. Conduction through the solid is therefore very low. The remaining
97% of the volume is composed of air in extremely small nanopores. The air has little room
to move, inhibiting both convection and gas-phase conduction.
It has remarkable thermal insulative properties, having an extremely low thermal
conductivity: from 0.03 W/mK in atmospheric pressure down to 0.004 W/m·K in modest
vacuum, which correspond to R-values of 14 to 105 (US customary) or 3.0 to 22.2 (metric)
for 3.5 in (89 mm) thickness. For comparison, typical wall insulation is 13 (US customary) or
2.7 (metric) for the same thickness. Its melting point is 1,473 K (1,200 °C; 2,192 °F).
Until 2011, silica aerogel held 15 entries in Guinness World Records for material properties,
including best insulator and lowest-density solid, though it was ousted from the latter title by
the even lighter materials aerographite in 2012 and then aerographene in 2013.

Fig 4.2.1: Silica Aerogel

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4.2.2 Carbon Aerogel

Carbon aerogels are composed of particles with sizes in the nanometer range, covalently
bonded together. They have very high porosity (over 50%, with pore diameter under 100 nm)
and surface areas ranging between 400–1,000 m2/g. They are often manufactured as
composite paper, non-woven made of carbon fiber, impregnated withresorcinol formaldehyde
aerogel, and pyrolyzed. Depending on the density, carbon aerogels may be electrically
conductive, making composite aerogel paper useful for electrodes in capacitors or
deionization electrodes. Due to their extremely high surface area, carbon aerogels are used to
create supercapacitors, with values ranging up to thousands of farads based on a capacitance
density of 104 F/g and 77 F/cm3. Carbon aerogels are also extremely "black" in the infrared
spectrum, reflecting only 0.3% of radiation between 250 nm and 14.3 µm, making
them efficient for solar energy collectors.

The term "aerogel" to describe airy masses of carbon nanotubes produced through
certain chemical vapor deposition techniques is incorrect. Such materials can be spun into
fibers with strength greater than Kevlar, and unique electrical properties. These materials are
not aerogels, however, since they do not have a monolithic internal structure and do not have
the regular pore structure characteristic of aerogels.

Fig 4.2.2: Carbon Aerogel

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4.2.3 Metal Oxide Aerogel

Metal oxide aerogels are used as catalysts in various chemical reactions/transformations or as

precursors for other materials.

Aerogels made with aluminium oxide are known as alumina aerogels. These aerogels are
used as catalysts, especially when "doped" with a metal other than aluminium. Nickel–
alumina aerogel is the most common combination. Alumina aerogels are also being
considered by NASA for capturing hypervelocity particles; a formulation doped
with gadolinium and terbium could fluoresce at the particle impact site, with the amount of
fluorescence dependent on impact energy.

One of the most notable difference between silica aerogels and metal oxide aerogel is that
metal oxide aerogels are often variedly colored.

Aerogel Color

Silica, Alumina, Titania, Zirconia Clear with Rayleigh scattering blue or

white

Iron Oxide Rust red or yellow, opaque

Chromia Deep green or deep blue, opaque

Vanadia Olive green, opaque

Neodymium Oxide Purple, transparent

Samarium Oxide Yellow, transparent

Holmium Oxide, Erbium Oxide Pink, transparent

Table 4.2.3: Different color of different metal oxide aerogels.

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4.2.4 Organic Aerogel

Organic aerogels have been around as long as any aerogel-in fact, the first aerogel Samuel
Kistler is believed to have prepared was aerogel made from jelly. Kistler also prepared
aerogels of gelatin and rubbers, both of which are composed of organic polymers.

Basically, an organic aerogel is any aerogel with a framework primarily comprised of organic
polymers. Generally, organic aerogels have very different properties from inorganic aerogels
such as silica aerogel and metal oxide aerogels. They are generally less friable and less fragile
than inorganic aerogels, instead squishing when compressed. The term “organic aerogel” can
refer to one of many different kinds of aerogels, each with properties arising from the
polymer. Organic aerogels can be made from resorcinol formaldehyde, phenol formaldehyde,
melamine formaldehyde, cresol formaldehyde, phenol furfuryl alcohol, polyacrylamides,
polyacrylonitriles, polyacrylates, polycyanurates, polyfurfural alcohol, polyimides,
polystyrenes, polyurethanes, polyvinyl alcohol dialdehyde, epoxies, agar agar, agarose, and
many others.

Although organic aerogels have been around since the first aerogels were prepared, they
were, for the most part, overlooked until the 1980’s when Lawrence Livermore National
Laboratory scientists began producing organic aerogels made of phenolic resins. The bulk of
this work was done by scientists Dr. Rick Pekala and Dr. Joe Satcher, who synthesized the
first resorcinol- formaldehyde polymer aerogels (or RF aerogels for short).-essentially,
aerogels composed of the same material as the plastic “Bakelite”. Depending on their density,
RF aerogels range from light orange to deep red to black in color and range from translucent
to opaque. Low density organic aerogels (<0.020 g cm -3) are generally irreversibly squishy,
similar in feel to green floral potting foam. High density organic aerogels (>0.5 g cm -3) can be
extremely robust and very hard to squeeze, almost like a car seat cushion

4.2.5 Alumina Aerogel

These aerogels are made with aluminium oxide and are used as catalysts, especially when
"metal-doped" with another metal. Alumina aerogels have many fascinating properties, such
as high temperature stability and high surface area, which result in them having great
potential applications. However, their mechanical properties are very poor, which greatly
limits their practical application and commercialization. In this communication we
successfully synthesized monolithic alumina aerogels via ambient pressure drying by using
attapulgite (ATP) as a reinforcing agent. The resulting attapulgite/alumina composite
aerogels exhibit strong mechanical properties. TEM/SEM analysis showed that alumina
particles firmly adhered to the surface of the rod shaped crystal of attapulgite and attapulgite
played a supporting role as the skeleton in the structure of the composite aerogels.

4.2.6 Semiconducting metal chalcogenide Aerogel

Semiconducting metal chalcogenide aerogels possess a unique combination of porosity,

optical translucency, and photoluminescence, and show great promise for use as chemical
sensors and energy, applications such as photovoltaics and extraction of hydrogen from
water using

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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

4.2.7 Metal Aerogel

Metal aerogels combine the unique properties of metals with the unique properties of
aerogels. They exhibit high specific surface areas and electrically conductive. Until very
recently, metal aerogels did not exist. This is partly because there were (and still are) no
known synthetic routes for producing wet gels of metals, although numerous synthetic routes
for preparing solutions of metal nanoparticles (sols) do exist. In principle, if a gel composed
of a network of metal nanoparticles could be prepared, it could also be supercritical dried to
produce a metal aerogel. This said, like enlightenment and entropy, aerogel is a state
function-it doesn’t matter how you get there but just that you do. The most consistent
definition of aerogel implies that for a material to qualify as an aerogel, it must possess no
less than 50% liquid-free porosity by volume and must be primarily mesoporous.

There are now a number of ways to make nonporous metal foams that almost fit both criteria,
however, and one way that unambiguously fits both. Here we will discuss the three major
approaches:

 Combustion Synthesis of Metal Nanofoams

 Dealloying of Templated Au Alloys
 Nanosmelting of Iron Aerogel

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4.3 PHYSICAL PROPERTIES OF AEROGEL

1.1.2 Unit 1.1.4 Carbon Aerogel

1.1.1 Values 1.1.3 Silica Aerogel
s
Carbon
Class Silica
C
Composition SiO2
0.02-0.5
Density Range g cm-3 0.0011-0.650
600-800
Surface Area 500-950

Pore Volume cm g-1

3.0-20
Primary Particle Size nm 2.0-3.0
7.0-20.0
Average Pore Size nm 20
Opaque
Transparency Clear to foggy
Transparent or white with Opaque black, shiny or
Appearance blue cast from Rayleigh matte
scattering
Monolithic, charcoal like
Monolithicity Monolithic
Rigid, breaks like charcoal
Flexibility Rigid, friable
Hydrolysis of silicon Polymerization of 1,3-
Gel Synthesis alkoxide or acid-driven dihydroxybenzene with
condensation of waterglass methanal
Supercritical CO2 or high- Supercritical CO2 followed
Drying Method temperature drying from by pyrolysis at 400°C-
organic solvent 1050°C under inert gas
Thermal 120-320
Conductivity at W m-1 K-1 0.016-0.03
Room Temperature
Electrical 1-14.7
S cm-1 1×10-18
Conductivity
Dimensionl
Index of Refraction 1.002-1.046
ess

Table 4.3: Physical property of Carbon and Slilica Aerogels

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4.4 World records hold by Aerogels.

Many aerogels boast a combination of impressive materials properties that no other materials
possess simultaneously. Specific formulations of aerogels hold records for the lowest bulk
density of any known material (as low as 0.0011 g cm-3), the lowest mean free path of
diffusion of any solid material, the highest specific surface area of any monolithic (non-
powder) material (up to 3200 m2 g-1), the lowest dielectric constant of any solid material,
and the slowest speed of sound through any solid material. It is important to note that not all
aerogels have record properties.

By tailoring the production process, many of the properties of an aerogel can be adjusted.
Bulk density is a good example of this, adjusted simply by making a more or less
concentrated precursor gel. The thermal conductivity of an aerogel can be also be adjusted
this way, since thermal conductivity is related to density. Typically, aerogels exhibit bulk
densities ranging from 0.5 to 0.01 g cm-3 and surface areas ranging from 100 to 1000 m2 g-1,
depending of course on the composition of the aerogel and the density of the precursor gel
used to make the aerogel. Other properties such as transparency, color, mechanical strength,
and susceptibility to water depend primarily on the composition of the aerogel.

Records held by some specially-formulated silica aerogels:

 Lowest density solid (0.0011 g cm-3)

 Lowest optical index of refraction (1.002)

 Lowest thermal conductivity (0.016 W m-1 K-1)

 Lowest speed of sound through a material (70 m s-1)

 Lowest dielectric constant from 3-40 GHz (1.008)

 Highest specific surface area for a monolithic material (3200 m g-1)

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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 gel’s liquid component (which takes up most of the volume in the gel). But how do
you isolate such a material from a gel?

5.1 The Start of an Aerogel: A Gel

Aerogels start their life out as a gel, physically similar to Jell-O ®. A gel is a colloidal system
in which a nanostructured network of interconnected particles spans the volume of a liquid
medium. Gels have some properties like liquids, such as density, and some properties like
solids, such as a fixed shape. In the case of Jell-O, this network of particles is composed of
proteins and spans the volume of some sort of fruit juice. A gel is structurally similar to a wet
kitchen sponge, only with pores a thousand to a million times smaller. Because a gel’s pores
are so small, the capillary forces exerted by the liquid are strong enough to hold it inside the
gel and prevent the liquid from simply flowing out. It’s important to remember that gelatin
isn’t the only type of gel–in fact, chemists can prepare gels with backbones composed of
many organic and inorganic substances and many liquid interiors.
Once a gel is prepared, it must be purified prior to further processing. This is because the
chemical reactions that result in the formation of a gel leave behind impurities throughout the
gel’s liquid interior that interfere with the drying processes used to prepare aerogel (as
described below). Purification is done by simply soaking the gel under a pure solvent
(depending on the gel this could be acetone, ethanol, acetonitrile, etc.), allowing impurities to
diffuse out and pure solvent to diffuse in. The solvent in which the gel is soaked is typically
exchanged with fresh solvent multiple times over the course several days. Depending on the
volume and geometry of the gel, diffusive processes can take any where from hours to weeks.
A ice-cube size sample can usually be purified in 1 or 2 days.

5.2 The Dire Consequences of Evaporativelly Drying a Gel

Now, if you’ve ever left Jell-O uneaten and uncovered in the refrigerator for a long while (on
the order of a week or so), you may have observed the gel shrinks gradually. This occurs
when the liquid trapped in the gel evaporates from the gel’s surface. As molecules of liquid
escape into the air, the surrounding liquid molecules are pulled together by capillary action
and tug on the framework of the gel. Continued evaporation results in collapse of the
framework of the gel, forming a dense, hard substance with less than 10% of the volume of
the original gel. This is called xerogel (pronounced zeroGEL). In fact, 1980’s-style hard
contact lenses used to be manufactured by drying silica gels into lens-shaped silica xerogels.

Aerogel is the solid framework of a gel isolated from its liquid component, prepared in such a
way as to preserve the framework’s pore structure (or at least most of it). In other words,

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Fig 5.1: Formation of Xeroxel

Aerogel is what would be left over if you could remove the liquid from a gel without causing
it to shrink. This is most effectively done through a special technique called supercritical
drying (although as you will see below, there are other ways to make aerogel as well).

5.3 Supercritical Drying

In general, supercritical drying is used when liquid needs to be removed from a sample that
would be damaged by evaporative or other drying techniques. Biological specimens, for
example, are often preserved through supercritical drying.

Supercritical drying is a clever technique by which we can pull the rug out from under
capillary action (so to speak). As mentioned earlier, capillary action induced by liquid
evaporating from a gel’s pores causes the gel to shrink. So what if there were some way to
avoid capillary forces to begin with? This is where supercritical drying comes in.

All pure substances (that won’t decompose) have what’s called as acritical point–a specific
and characteristic pressure and temperature at which the distinction between liquid and gas
disappears. For most substances, the critical point lies at a fairly high pressure (>70
atmospheres) and temperature (>400°F). At the critical point, the liquid and vapor phases of a
substance merge into a single phase that exhibits the behavior of a gas (in that it expands to
fill the volume of its container and can be compressed) but simultaneously possesses the
density and thermal conductivity of a liquid. This phase is called supercritical fluid.

Say we have a sealed container containing a liquid below its critical point inside and
equipped with a pressure gauge on top. In fact, a certain amount of liquid will evaporate in
the container until the vapor pressure of the liquid is reached in the container, after which no
more liquid will evaporate and the gauge will read a corresponding stable pressure. Now if
we heat this container, we will notice the pressure in the container increases, since the vapor
pressure of a liquid increases with increasing temperature. As the critical point draws near,
the pressure in the container squeezes molecules in the vapor close enough together that the
vapor becomes almost as dense as a liquid. At the same time, the temperature in the container
gets high enough

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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
liquid- like. 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.

Fig 5.2: Supercritical Drying

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 (let’s say ethanol for example). The pressure vessel is then
slowly heated to the liquid’s 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 gel’s 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
fluid’s 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 solvents–liquid carbon
dioxide

Fig 5.3 : State of Aerogel during processs

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5.5 The Sol-Gel Process

The term sol-gel (say “sahl-jell”) refers to a process in which solid nanoparticles dispersed in
a liquid (a sol) agglomerate together to form a continuous three-dimensional network
extending throughout the liquid (a gel). The term sol-gel is sometimes used as a noun to refer
to gels made through the sol-gel process, but this is somewhat of an abuse of the term, since
pretty much all gels are made through the sol-gel process.

5.5.1 Sols, Gels, and Aerogels are Colloids:

A colloid is a mixture in which at least two different phases are intimately mixed at the
nanolevel. The term “phase” generally refers to a solid, liquid, or gas form of some
substance. A colloid typically has a continuous phase in which something else with a
different phase is dispersed (the “dispersed phase”). Different phases can still be the same
phase of matter, for example, two different phases could both be liquids, just not miscible
liquids.
Colloids are different from homogeneous solutions, in which a substance is dissolved or
mixed with another substance and does not separate out, in that the components of colloids
are nanoparticles or macromolecules (giant molecules), typically with a length or diameter
ranging from a few nm to several hundred nm in diameter.

Sols:
A sol is a liquid. The continuous phase in a sol is a liquid and the dispersed phase is a solid.
The difference between a sol and a non-colloidal liquid is that solid nanoparticles are
dispersed throughout the liquid in a sol. If you put a sol in a centrifuge, you can force the
nanoparticles dispersed in the liquid to precipitate out. This will not happen for a non-
colloidal liquid solution, for example, salt dissolved in water.
An example of a sol is black inkjet ink (carbon black dispersed in water).

Gels:
A gel is a wet solid-like material in which a solid network of interconnected nanostructures
spans the volume of a liquid medium. The continuous phase is a solid network and the
dispersed phase is a liquid. Gels tend to be mostly liquid in composition and typically exhibit
the density of a liquid as result but have cohesiveness like a solid.
An example of a gel is Jell-O gelatin.

Aerogels:
An aerogel is solid with air pockets dispersed throughout. Aerogels are essentially the solid
framework of a gel isolated from the gel’s liquid medium. Some aerogels, such as carbon
aerogels and iron aerogels, are derived from other types of aerogels, but the aerogels they’re
derived from came from a gel directly.
Production of Sols
Sols of all sorts of compositions can be made several different ways. Nanoparticles of any
solid dispersed in any liquid in such a way that the solid phase does not spontaneously
precipitate or settle out is considered a sol.

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5.5.2 Generally there are two ways sols are made:

(a) Nanoparticles are grown directly in a liquid.

This happens when you make Jell-O, or a silica gel. Basically you mix ingredients that
contain molecules that can interconnect together to form bigger molecules and eventually
nanoparticles. These nanoparticles then hook up together to form a gel network. See the
Silica Aerogel article under Flavors of Aerogel for a detailed example.

(b) Nanoparticles are synthesized and then dispersed in a liquid.

This is how more advanced gels are made. Nanoparticles such as quantum dots or carbon
nanotubes are made through some process and then dissolved in a liquid directly or dispersed
using the help of a surfactant (a detergent, like shampoo or dish soap). This is how metal
chalcogenide aerogels and carbon nanotube aerogels start out. In the case of quantum dots,
these nanoparticles are usually synthesized in a liquid, centrifuged out, and then redissolved
in the desired liquid medium for whatever you’re using them for. Carbon nanotubes, on the
other hand, are grown at high temperatures outside of a liquid medium.

5.5.3 The Sol-Gel Transition

A sol can become a gel when the solid nanoparticles dispersed in it can join together to form
a network of particles that spans the liquid. This requires that the solid nanoparticles in the
liquid, which are constantly bouncing around in random directions because of temperature
(that is, they are undergoing Brownian motion), bump into each other and stick together when
they do. For some nanoparticles this is easy, almost automatic, since they contain reactive
surface groups that condense together to form bonds. For other nanoparticles, however, this
can be tricky and requires the addition of an additive to “glue” the particles together or
removal something from the particle surfaces so that they stick together when collide, either
by bonding together or by electrostatic forces (static electricity).
As a sol becomes a gel, its viscosity approaches infinity and finally becomes immobile (that it
is, it stops being able to flow and fill its container, although it might still wobble back and
forth). This transition from sol to gel is called gelation. The point in time when the particle
network extends across the entire volume of the liquid causing it to immobilize is called the
gel point. The time required for a gel to form after mixing stuff together to make the gel is
called the gel time.

5.5.4 Factors that Affect Sol-Gel Chemistry

Sol-gel chemistry tends to be particularly sensitive to the following parameters:

pH.
Any colloidal chemistry that involves water is sensitive to pH. In the case of silica gel
formation, this has to do with the hydrolysis step of the silica precursor that results in silanol
groups, which are what connect together to produce silica nanoparticles and eventually the
gel network. See the Silica Aerogel article under Flavors of Aerogel for more details.

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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 don’t 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 time–in 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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5.6 How Big Can an Aerogel Be Made?

Just as you can only bake a pie as big as your oven, you can only supercritically dry an
aerogel as large as your pressure vessel. This means one of three things–either you need
a big supercritical dryer, you limit yourself to making small aerogels, or you use a non-
supercritical drying technique (see below). Additionally, large continuous volumes (such
as cubes or spheres) are generally difficult to make since it takes exponentially longer for
solvent from the interior of the gel to diffuse out of the gel as the gel thickness
is increased. However, hollow cubes and spheres, flat plates and discs, and rods with
thicknesses less than two inches (5 cm), regardless of how big the gel’s other dimensions are,
can be easily made. This said, there are many techniques for preparing aerogel materials
called ambigels (often just referred to as aerogels) with subcritical drying techniques.
These materials typically have porosities of 50-95% and so they are usually (but not
always) a little less dense than supercritically-dried aerogels. Subcritical drying
techniques typically require specially- modified gels, in which the solid framework of the
gel is chemically changed so that liquid is less able to stick to it and thus exerts
only minimal stress on the gel upon evaporation. Additionally, the liquid in the pores
of the gel is frequently replaced with a liquid that has a low surface tension, such as pentane
or hexane, so that when the liquid is evaporated little capillary stress can result. Cabot
Corp.’s Nano gel aerogel granules are made through a subcritical drying technique.

5.7 STRUCTURE OF AEROGEL

Fig 5.4

High-porosity aerogel 3D Computer simulation of high 2D slice with strand

Porosity aerogel showing fractal like structure
Structure of the SiO2 clusters

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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.

6.1 THERMAL APPLICATIONS

Aerogels are good thermal insulators because they almost nullify the three methods of heat
transfer (convection, conduction, and radiation). They are good conductive insulators because
they are composed almost entirely from a gas, and gases are very poor heat conductors. Silica
aerogel is especially good because silica is also a poor conductor of heat (a metallic aerogel,
on the other hand, would be less effective). They are good convective inhibitors because air
cannot circulate through the lattice. Carbon aerogel is a good radiative insulator because
carbon absorbs the infrared radiation that transfers heat at standard temperatures. The most
insulative aerogel is silica aerogel with carbon added to it.

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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6.2 POROSITY AND SURFACE AREA APPLICATIONS

Due to their high porosity, their very large inner surface area (easily accessible because of the
open porosity), and the controllable dispersion of the active component, they are especially
active catalysts or catalytic substrates. There are numerous references of this application for
various aerogels and doped aerogels.

Moreover, the high porosity and large surface areas lead to applications as filters, absorbing
media for desiccation, filters, reinforcement agents, pigments, jellifying agents, waste
containment, encapsulation media, and pesticides.

The carbon aerogels have been used as electrodes capacitors in energy storage devices known
as double layer capacitor because they are electrically conductive with a very large surface
area. The stored energy in these devices can be released faster than conventional batteries
with high power densities. Thus, have potential application in electric vehicles,
microelectronics, and hydrogen fuel storage.

One of the promising new applications for aerogels is in a cost-effective purification process.
The carbon aerogel capacitive deionization process works by sending solutions with various
positively and negatively charged ions through an electrochemical cell consisting of
numerous electrodes containing carbon aerogels in the form of sheets. The aerogel process
can have a variety of uses ranging from extracting harmful contaminants from industrial
waste water to desalinizing seawater.

6.3 OPTICAL PROPERTY APPLICATIONS

Aerogel is transparent when its microstructural components are very small compared with the
wavelength of light. Transparent aerogels, together with their exceptional thermal insulation
ability, have been considered for use as super-insulating sheets in double walled window
systems because help considerably to reduce thermal losses in windows.
Translucent aerogels have been proposed to improve the efficiency of solar thermal energy
storage devices. Moreover, the ultra-low density aerogels can be used as lightweight mirror
backings. Aerogels have been used to prepare ultra-pure, full-density silica glass by sintering
at temperatures below the melting temperature of silica. Silica aerogels with silicon exhibits
strong photo-luminescence (luminescence stimulated by visible or ultraviolet radiation).
Silica aerogel, doped with radioactive tritium and phosphor, makes an efficient radio-
luminescent light source. There is also evidence for quantum confinement in nanoparticle-
loaded silica aerogels for producing blue light emission.

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Fig 6.2: Rayleigh scattering of LASER beam by

silica aerogel

6.4 ACOUSTICAL AND MECHANICAL APPLICATIONS

Aerogels may also have acoustic and mechanical applications. Because of their unusual
structure, aerogels have low sound velocities, as low as 30 meters per second.
Another important acoustic property of aerogel is its mechanical impedance. The impedance
is the product of density and the sound velocity of the material. Since both are low, silica
aerogel has the lowest impedance of all solid material. This allows the aerogels to be used for
coupling sound waves in air to a transducer (device that converts energy from one form to
another), this may be useful either to generating or detecting sound. Therefore, they should be
efficient ultrasonic devices as acoustic impedance matching, and sound absorption (anechoic
chambers) Aerogels have also been proposed as a shock absorbing material. One of the
earliest experiments was to measure shock compression in silica aerogels. The low density of
the silica aerogel allowed more internal energy could be deposited in it.

6.5 ELECTRICAL AND ELECTRONIC APPLICATIONS

Silica aerogel is an electrical insulator with a low dielectric constant, k (k is the measure of
the ability of a material to store electrical potential energy under the influence of an electric
field). The velocity of signal propagation in a chip is dependent on the dielectric constant of
the surrounding electrical insulation. The lower the dielectric constant, the higher the
velocity. Therefore, thin aerogel films are almost ideal dielectrics for ultra-fast integrated
circuits.
The bulk aerogels can be used for microwave electronics and high voltage insulators. The
pure carbon aerogels are quite electrically conductive, so they have applications as electrodes
for batteries, fuel cells, and capacitors. Other metal oxide aerogels have been made, which
exhibit super-conducting behavior, thermoelectric behavior, and piezoelectric properties

6.6 SPACE APPLICATIONS

Aerogels have already captured cosmic dust while on the European Retrieval Carrier
(EURECA) satellite and in Space Shuttle experiments , and will capture cemetery’s dust in
NASA's STARDUST project. Lightweight silica aerogels have also been proposed as a
contaminant collector, to protect space mirrors from volatile organics.

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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.

AEROGEL SAMPLE COLLECTOR

Comet and interstellar particles are collected in ultra-low density aerogel. More than 1,000
square centimeters of collection area is provided for each type of particle (cometary and
interstellar). The collector tray contains ninety blocks of aerogel in a metal grid. The
appearance of the grid has been likened to an ice cube tray; the round collector is about the
size of a tennis racket. When the spacecraft flew past the comet, the impact velocity of the
particles in the coma as they were captured was 6100 meters per second, up to nine times the
speed of a bullet fired from a rifle. Although the captured particles were each smaller than a
grain of sand, high-speed capture could have altered their shape and chemical composition —
or vaporized them entirely.
Stardust capsule with aerogel collector deployed to collect the particles without damaging
them, a silicon-based solid with a porous, sponge-like structure is used in which 99.8 percent
of the volume is empty space. Aerogel is 1,000 times less dense than glass, another silicon-
based solid. When a particle hits the aerogel, it buries itself in the material, creating a carrot-
shaped track up to 200 times its own length, as it slows down and comes to a stop — like an
airplane setting down on a runway and braking to reduce its speed gradually. Since aerogel is
mostly transparent — a property earning it the nickname "solid smoke" or "blue smoke" —
scientists will use these tracks to find the tiny particles.
The aerogel was packed in a Sample Return Capsule (SRC) which was released from the
spacecraft just before reentry, for a separate landing on a parachute, while the rest of the
spacecraft fired its engines, putting it into orbit around the sun.

Fig 6.3: Interstellar Particles trapped in the

collector

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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 a research report published by spherical insights &
consulting, the global aerogel size to grow from $ 982 million in 2022 to $ 2976 million by 2032 at a
compound annual growth rate of 11.7% . A number of industries have shown active interest in
the material and applications have been extend to the automotive, oil and gas, constructions,
scryogenics, 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 hasn’t 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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7.2 Publication Trend

Going by the patent publication trend, the first few year from the 2013 right till the 2018 saw
consistent activity around the innovation of aerogels with an average of about 400-500patents
published each year. From the year 2018 onwards the publications started to rise rapidly from
about 800 published in 2018 to over 1300 upto 2022. The last 5 years have been the most
remarkable clearly displaying just how significant aerogels can be for the future.

Fig 7.2.1: Number of journals published on Aerogel as a main topic

Fig 7.2.2: Figure shows key players of Aerogel

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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 today’s 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 So journer 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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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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