Exploration of Sol-Gel Chemistry &

Subcritical Drying for the Preparation

of Aerogels

P. Shajesh*, S. Smitha, P. R. Aravind, P. Krishna Pillai,

K.G.K. Warrier

Materials & Minerals Division

Regional Research Laboratory (CSIR)
Trivandrum - 695 019
 Sol-Gel Chemistry:
Hydrolysis & Condensation
OC2H5 O
HO
- OH
OH HO
Si Si Si
OC2H5 O
C2H5O
OC2H5 O O
HO O
Si
+ Si Si O
H H2O Si O
O O
O OO
O O
Hydrolysis
Si
Si O
O
O O
O

HO HO OH
OH O
HO
Si HO
Si Si
OH Gel Network

OH OH OH

Condensation
Supercritical Drying
Monalisa
Subcritical Drying

TEOS +Isopropanol + H2O

Silica precursor sol

Silica Gel Rods

Aging in water

Solvent exchange

Silane aging

Solvent exchange

Drying
 Subcritical Drying

Aging system Surface Pore Av. Pore

area volume size ()
(m2/g) (cc/g)
Gel as prepared 610 0.27 17
Gel-water-ethanol 769 0.44 22

Gel-water-ethanol 1044 1.03 39

+ TEOS-ethanol

Gel-water-ethanol 1142 1.19 41

+ TEOS-ethanol +
ethanol
 Subcritical Drying

Solvent system Surface Pore Av. Pore

area volume size ()
(m2/g) (cc/g)
water 618 0.17 46
Ethanol 1085 0.97 35
Iso-propanol 1131 1.14 40
Methanol 984 0.88 35
n-Heptane 958 0.99 41
 Subcritical Drying

Effect of Calcination Surface Pore Av. Pore

Tem (C) area volume size ()
(m2/g) (cc/g)
200 850 0.35 16.7

300 716 0.32 18

400 402 0.20 20
600 220 -
800 < 0.5 0.01 13
Inorganic - Silica Composite
Aerogels

TEOS +Isopropanol + H2O

Silica precursor sol Boehmite sol

Silica Gel Rods Silica-Alumina gels

Aging in water

Solvent exchange

Silane aging

Solvent exchange

Drying
Inorganic Silica Composite
Aerogels

700 C 662 0.99 59

5 wt%
900C 398 0.79 80
Alumina
1200C 0 0 0
700 C 359 0.48 53
15wt%
900C 232 0.41 71
Alumina
1200C 88 0.15 72
700 C 246 0.31 50
25wt%
900C 156 0.24 62
Alumina
1200C 70 0.11 62
Organic Silica Hybrid
Aerogels
CH3O
O
CH3O Si O
CH3O

3-glycidoxypropyltrimethoxysilane

Organic part covalently linked to Silicon

Organic chain posses capacity to form hydrogen bonds or
polymerise to give a polyethylene like network
 Organic Silica Hybrid
Aerogels
O
O
O O
OH O Si O
OH
O

O
O Si O O O
O O Si O
O
O
O O O OH
O O
O
Exo

O Si O
O O
O
3%
Endo

O 20%

0 200 400 600

Temperature (C)
Organic Silica Hybrid
Aerogels
 Modified Sol-Gel for
Silica aerogel Microspheres

Emulsion TEOS +Isopropanol + H2O

(Surfactants)
Silica precursor sol

SiO2 Silica Gel Rods

microsphere
Aging in water

Solvent exchange

Silane aging

Solvent exchange

Drying
 Modified Sol-Gel for
Silica aerogel Microspheres
 Surface Modified Aerogels
200

150

100
endo exo

50

-50

Hydrophobic
-100
Hydrophilic
0 200 400 600 800 1000 1200
Temperature (C)
Surface Modified Aerogels
Prepared Aerogels
 Conclusions
Subcritical drying process was successfully used for the
preparation of aerogels
The sol-gel process could be modified to prepare
silica alumina composite aerogels with high pore
stability
Silica-glycidoxypropyltrimethoxysilane hybrid aerogels
were prepared by subcritical drying
Silica microspheres were prepared by sol-emulsion
technique
Hydrophobic aerogels were prepared by surface
modification and varying extent of hydrophobicity could
be demonstrated by varying the concentration of the
modifier
 Acknowledgements

Dr. K.G.K. Warrier

Prof. T. K. Chandrashekar

Defence Research & Development Organisation

Council of Industrial
Aravind P.&R.
Scientific ResearchSmitha S.