APPLICATIONS OF AEROGEL- A POROUS SOLID MATERIAL

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. 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.

1.1 History

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

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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:

Aerogels had been largely forgotten when, in the late 1970s, the French government approached
Stanislaus Teichner at Universite Claud Bernard, Lyon seeking a method for storing oxygen and
rocket fuels in porous materials. There is a legend passed on between researchers in the aerogel
community concerning what happened next. Teichner assigned one of his graduate students the
task of preparing and studying aerogels for this application. However, using Kistler's method,
which included two time-consuming and laborious solvent exchange steps, their first aerogel
took weeks to prepare. Teichner then informed his student that a large number of aerogel
samples would be needed for him to complete his dissertation. Realising that this would take
many, many years to accomplish, the student left Teichner's lab with a nervous breakdown.
Upon returning after a brief rest, he was strongly motivated to find a better synthetic process.
This directly lead to one of the major advances in aerogel science, namely the application of sol-
gel chemistry to silica aerogel preparation. This process replaced the sodium silicate used by
Kistler with an alkoxysilane, (tetramethyorthosilicate, TMOS). Hydrolyzing TMOS in a solution
of methanol produced a gel in one step (called an "alcogel"). This eliminated two of the
drawbacks in Kistler's procedure, namely, the water-to-alcohol exchange step and the presence of
inorganic salts in the gel. Drying these alcogels under supercritical alcohol conditions produced
high-quality silica aerogels.

CHAPTER 2

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TYPES OF AEROGEL

The three most common types of aerogels are silica, carbon and metal oxides, but it's
silica that is most often used experimentally and in practical applications. When people talk
about aerogels, chances are they're talking about the silica type. Silica is not to be confused with
silicon, which is a semiconductor used in microchips. Silica is a glassy material often used for
insulation.

Silica Aerogel

The most common aerogels are blue for the same reason the sky is blue. The blue
color occurs when white light encounters the aerogel's silica molecules, which are larger than the
wavelengths of light. The aerogel scatters, or reflects, the shorter wavelengths of light more
easily than the longer ones. Because blue and violet light have the shortest wavelengths, they
scatter more than other colors of the visible spectrum. We see scattered wavelengths as color, and
since our eyes are more sensitive to blue wavelengths, we never see the violet ones.

Figure 1: Silica Aerogel

Carbon Aerogel

Unlike the smoky-blue silica aerogels, carbon-based Aerogels are black and feel
like charcoal to the touch. What they lack in looks, they make up for in high surface area

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and electrically conductive capabilities. These properties make carbon aerogels useful for
supercapacitors, fuel cells.

Figure 2: Carbon Aerogel

Metal oxide Aerogel

Metal oxide aerogels are made from metal oxides and are used as catalysts for
chemical transformations. They are also used in the production of explosives and carbon
nanotubes, and these aerogels can even be magnetic. What sets metal oxide aerogels such as iron
oxide and chromia apart from their more common silica cousins is their range of startlingly
bright colors. When made into an aerogel, iron oxide lends an aerogel in its trademark rust color.
Chromia aerogels appear deep green or blue. Each type of metal oxide results in an aerogel of a
slightly different color.

Figure 3: Metal oxide Aerogel

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CHAPTER 3

MANUFACTURING OF SILICA AEROGEL

Figure 4: Scheme of silica aerogel sol-gel synthesis by

condensation of silica alkoxide precursor on alcohols

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Forming a solution

A common way to synthesize gels at room temperature corresponds to a chemical

reaction implying metal alkoxides and water in an alcoholic solvent. The majority of silica
aerogels prepared utilizes silicon alkoxide precursors. The most common of these are
Tetramethyl orthosilicate (TMOS or Si(OCH3)4), and Tetraethyl orthosilicate (TEOS or
Si(OCH2CH3)4). However, many other alkoxides, containing various organic functional groups,
can be used to impart different properties to the gel. The first reaction is a hydrolysis which
induces the substitution of OR groups linked to silicon by silanol Si-OH groups. A condensation
reaction occurs when two silanol groups (Si-OH + HO-Si) react together to form Si-O-Si
(siloxane) bonds, which lead to the silica network formation.

The hydrolysis reaction replaces alkoxide groups (OR) with hydroxyl groups (OH).
Subsequent condensation reactions involving the silanol groups produce siloxane bonds
(SiOSi) plus the by-products alcohol (ROH) or water. Because water and alkoxysilanes are
immiscible, a mutual solvent such as alcohol is normally used as a homogenizing agent. The
final density of the aerogel depends on the concentration of silicon alkoxide monomers in the
solution. The balanced chemical equation for the formation of a silica gel is:

Si(OR)4 (liq.) + 2H2O (liq.) = SiO2 (solid)+ 4HOR (liq.)

Gelation

The stoichiometry of the reaction requires two moles of water per mole of alkoxysilane. In
practice, this amount of water leads to incomplete reaction, and weak, cloudy aerogels.
Therefore, most aerogel recipes use a higher water ratio than is required by the balanced equation
(anywhere from 4-30 equivalents).

The gel point is the time at which the network of linked oxide particles spans the container
holding the sol. At the gel point, the sol becomes a gel. This two-phase material, a solid part and
a liquid part, consists of shaped solid exhibiting specific properties.

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The solid part is formed by the three-dimensional network of linked oxide particles. The liquid
part (the original solvent of the sol and a small amount of water) fills the free space surrounding
the solid part. The liquid and solid parts of a gel occupy the same apparent volume.

As condensation reactions progress the gel will gain rigidity. At this point, the gel is usually
removed from its mould. However, the gel must be kept covered by alcohol to prevent
evaporation of the liquid contained in the pores of the gel. Evaporation causes severe damage to
the gel and will lead to poor quality aerogels..

The balanced chemical equation for the formation of a silica gel from TEOS is:

Si(OCH2CH3)4 (liq.) + 2H2O (liq.) = SiO2 (solid) + 4HOCH2CH3 (liq.)

Aging and Soaking

At the gel point the silica backbone of the gel contains a significant number of unreacted
alkoxide groups. Sufficient time must be given for the strengthening of the silica network. This
can be enhanced by controlling the pH and water content of the covering solution. Common
aging procedures for base catalyzed gels typically involve soaking the gel in an alcohol/water
mixture of equal proportions to the original sol. The gels are soaked in this solution for up to 24
hours. This step, and all subsequent processing steps, is diffusion controlled. Diffusion is
affected by the thickness of the gel. Then, the time required for each processing step increases
dramatically as the thickness of the gel increases. After aging the gel, all water still contained
within its pores must be removed prior to drying. This is simply accomplished by soaking the gel
in pure alcohol several times until all the water is removed. Again, the length of time required for
this process is dependent on the thickness of the gel. Any water left in the gel will not be
removed by supercritical drying, and will lead to an opaque, white, and dense aerogel.

Chapter II shows that variations in synthesis conditions (for example, ratio H2O/Si, the catalyst
type and concentrations, the type of solvent, temperature and pressure of supercritical drying)
cause modifications in the structure and properties of the obtained silica aerogels. Thus, porous
structure of silica aerogels strongly depends on preparation and drying parameters.

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Drying procedure of aerogel

An aerogel results from a supercritical drying process. This is where the liquid
within the gel is removed, leaving only the linked silica network. The difference between
classical drying and supercritical drying is shown in Figure From point 1 to 5, (purple arrow) the
liquid is depressurized isothermally (classical drying). Consequently, we can say that xerogels
refer to gels dried at temperature close to room temperature and under atmospheric pressure. The
supercritical drying is performed inside an autoclave, which allows to overpass the critical point
(PC, TC) of the solvent, as shown in Figure (Path 1-2-3-4-5); or by prior solvent exchange with
liquid CO2 followed by supercritical CO2 venting (lower temperature drying).

The supercritical fluid is a substance that is above its critical pressure and critical temperature; it
possesses some properties in common with liquid (density, thermal conductivity) and some in
common with gas (fills its container, does not have surface tension). A more detailed description
of supercritical fluids can be found in Annex I). Strong inorganic solids are commonly dried
using alcohol (or acetone) as solvent or dried using CO2 as solvent.

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Figure 5: Scheme of the pressure and temperature variation on the solvent phase diagram
during a gel supercritical drying process.

The shaded area represents the supercritical region (SCF), where C is the critical point, Tr
represents the triple point, and 1 to 5 are random points in the phase diagram.

Under ambient conditions, during the evaporation of the solvent, a liquid-vapor interface is
formed within the pores of the gel. The surface tension of the liquid creates a concave meniscus
in each capillary. By evaporation, the meniscus recedes and the compressive force on the wall of
the pores produces the collapse of the initial gel framework, or shrinkage. A liquid-vapor
interface or the presence of a liquid in equilibrium with the vapor is only observed below the
critical temperature and pressure of the solvent. Above the critical point the liquid no longer
existed. Supercritical fluid is a gaseous like-phase, so the liquid meniscus and its interfacial
tension would not form in these conditions.

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Figure 6: The liquid-vapor interface formed in the gel

Capillary during drying

Using the high temperature drying procedure some problems may arise from the combination of
high pressures and high temperatures (methanol critical parameters: Pc=81 bar, Tc=240C) , i.e.
flammability of the solvents. Alternatively, supercritical drying with CO2 has been developed by
substituting, under pressure, alcohol in the gel by liquid carbon dioxide and then drying the
aerogel with carbon dioxide at supercritical conditions. CO2 is of particular interest due to its
low critical temperature (31C), non-flammability, and non-toxicity. The process results in a
reduction of the temperature and pressure required for drying aerogels.

3.1 Catalysts

The kinetics of the above reaction is impractically slow at room temperature, often
requiring several days to reach completion. For this reason, acid or base catalysts are added to
the formulation. The amount and type of catalyst used play key roles in the microstructural,
physical and optical properties of the final aerogel product .

Acid catalysts can be any protic acid, such as HCl. Base-catalysis usually uses ammonia, or
ammonia buffered with ammonium fluoride. Aerogels prepared with acid catalysts often show
more shrinkage during supercritical drying and may be less transparent than base catalyzed

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aerogels. The microstructural effects of various catalysts are harder to describe accurately, as the
substructure of the primary particles of aerogels can be difficult to image with electron
microscopy. All have small (2-5 nm diameter) particles that are generally spherical or egg-
shaped. With acid catalysis, however, these particles may appear less defined than those in base-
catalyzed gels.

3.2 Two-Step Aerogels

Typical acid or base catalyzed gels are often classified as "single-step" gels,
referring to the "one-pot" nature of this reaction. A more recently developed approach uses pre-
polymerized TEOS as the silica source. Pre-polymerized TEOS is prepared by heating an ethanol
solution of TEOS with a sub-stoichiometric amount of water and an acid catalyst. The solvent is
removed by distillation, leaving a viscous fluid containing higher molecular weight silicon
alkoxy-oxides. In a second step, this material is redissolved in ethanol and reacted with
additional water under basic conditions until gelation occurs. Gels prepared in this way are
known as "two-step" acid-base catalyzed gels. Pre-polymerized TEOS is available commercially
from Silbond Corp.

These slightly different processing conditions impart important changes to the final aerogel
product. Single-step base catalyzed aerogels are typically more brittle than two-step aerogels.
Moreover, two-step aerogels have a smaller and narrower pore size distribution and are often
optically clearer than single-step aerogels.

CHAPTER 4

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PHYSICAL PROPERTIES OF SILICA AEROGEL

Property Value Comments

Apparent density 0.003-0.5 g/cm3 Most common density is

0.1g/cm3(air=0.001g/cm3)

As determined by nitrogen
Inner surface area 500-1500 m2/g adsorption/desorption. (A cubic
centimeter of an aerogel has about the
same surface area as one soccer field)

Index of refraction 1.007-1.24 Very low for solid material (nair= 1.004)

Thermal tolerance Up to 700 C Shrinkage begins slowly at 700 C,

increases with increasing temperature.
Melting point is ~1200C

Youngs modulus 0.1-300 MPa Very small (<104) compared to dense

silica

Dielectric constant 1.1 For density of 0.1 g/cm3, very low for a
solid material (kair= 1)

Acoustic impedance 104 Kg/m2.s Determined using ultrasonic methods al

KHz frequency.

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Sound velocity 20-800m/s 100 m/s for density of 0.07 g/cm3, one of
through the medium the lowest velocities for a solid material

Optical property Transmittance>90% Transparent-blue haze

(630nm)
Very low thermal conductivity. 2 cm slab
Thermal conductivity 0.02 W/mK (20C) provides the same insulation as 30 panes
of glass

4.1World Record Held by 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)

CHAPTER 5

PRODUCTS OF AEROGEL AND

ITS APPLICATIONS

Products Nominal Thermal Nominal Density Maximum Use Applications

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Thicknes Conductivity In Temperature

s in mm in g/cc in
mW/ C
m-K

Sub-ambient
Cryogel Z 5-10 17 0.16 125 and cryogenic
pipelines,
vessels and
equipment
Sub-ambient
Cryogel 5-10 17 0.16 200 including
refrigerated
X201
appliances,
cold storage
and aerospace
Ambient
Spaceloft 5-10 16.5 0.16 250 temperature
walls, floors
and roofs in
commercial,
residential
and
institutional
building
Medium to
Spaceloft 5-10 14.5 0.16 250 high temp
offshore oil
subsea
pipelines
High
Pyrogel 5-10 21 0.20 650 temperature
steam pipes,
XTE
vessels and
equipment,
and aerospace
and defense
systems
High
Pyrogel 10 21 0.20 650 temperature
steam

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XTF pipes, vessels

and
equipment,
aerospace and
defense
systems, fire
barriers and
welding
blankets

CHAPTER 6

FUTURE WORK AND CONCLUSION

6.1 Future work

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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.

6.2 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 StarDust
spacecraft, and in the hundreds of other possible products and applications, the "unobtainium"
once only dreamed about may finally be just around the corner.

REFERENCES

1. Magda Moner i Gerona in :Phd thesis on SILICA AEROGELS: SYNTHESIS AND

CHARACTERIZATION (university of Barcelona)

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2. C.J. Brinker, G.W. Sherer, Sol-Gel Science. Physics and Chemistry of SolGel
Processing, Academic Press, New York, 1990

3. N. H. M. Yunos, H. Hamdan, and L. S. Ling, Piperine loaded silica aerogel and

silica xerogel as NANO-enabled drug delivery system, World Appl. Sci. J, vol. 9, no.
9, pp. 6-16, 2010.

4. Brinker CJ, Scherer GW (1990) Sol-Gel Science. The Physics and Chemistry of Sol-Gel
Processing. Academic Press, New-York

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