Microporous and Mesoporous Materials 30 (1999) 267–273

Effect of methyltrimethoxysilane as a synthesis component

on the hydrophobicity and some physical properties of
silica aerogels
A. Venkateswara Rao *, D. Haranath
Air Glass Laboratory, Department of Physics, Shivaji University, Kolhapur 416004, India
Received 24 April 1998; received in revised form 8 September 1998; accepted 22 January 1999

Abstract

The effects of adding methyltrimethoxysilane (MTMS ) to the synthesis formulation on the hydrophobicity and
physical properties of silica aerogels are reported. The molar ratio of the methanol (MeOH ) solvent, water
(H O), and the ammonia (NH OH ) catalyst to tetramethoxysilane (TMOS ) precursor was fixed at
2 4
1TMOS:12MeOH:4H O:3.6×10−3NH OH throughout the experiment and the MTMS/TMOS molar ratio M was
2 4
varied from 0 to 1.55. After gelation, the alcogels were dried supercritically by high-temperature solvent extraction.
The hydrophobicity of the resulting aerogels was tested by measuring the water uptake by the aerogel as a function
of time, after putting them directly on the surface of water. It was found that for M<0.26 the aerogels were less
hydrophobic but more transparent (>90% in the visible range), whereas for M>1.03 the aerogels were more
hydrophobic but semi-transparent to opaque. Aerogels that possessed good hydrophobicity and transparency (~85%
in the visible range) were obtained with an M#0.70. An increase in the MTMS content in the gels shifted the pore
size distribution towards larger pore radii with a broad distribution. In order to determine the thermal stability of
the hydrophobic nature of the aerogels, they were heat-treated in air in the temperature range between 25 and 350°C.
It was found that below 280°C the aerogel samples showed hydrophobic properties, whereas above 280°C the
hydrophobicity vanished. This is due to the disappearance of the CH groups in the aerogels. The aerogels were
3
characterized by optical transmittance, pore size distribution, BET surface area and infrared spectroscopy measure-
ments. © 1999 Elsevier Science B.V. All rights reserved.

Keywords: Aerogels; Hydrophobicity; Optical transmittance; Pore size distribution; Specific surface area

1. Introduction aerogels with densities as low as 5 kg m−3 have

Silica aerogels [1] are extremely porous (>95%)
materials that are normally prepared by supercriti-
cal drying of silica alcogels. Typical porosities of
the aerogels are in the range 80 to 98% [2,3] and
* Corresponding author. Tel.: +91-231-655571;
fax: +91-231-656133.
been reported [3]. Because of their high porosities
and non-structured nature, aerogels possess very
interesting physical properties, such as a small
index of refraction (1.01 to 1.1) [4], a low elastic
modulus (<0.5 MPa) [5,6 ], a low sound velocity
(<100 m s−1) [7], a low thermal conductivity
(~0.01 W m−1 K−1) [8–10] and an excellent
accessibility of the inner surface through the open
porous network. Aerogels can be made as both

1387-1811/99/$ – see front matter © 1999 Elsevier Science B.V. All rights reserved.
PII: S1 3 8 7 -1 8 1 1 ( 9 9 ) 0 0 03 7 - 2
268 A. Venkateswara Rao, D. Haranath / Microporous and Mesoporous Materials 30 (1999) 267–273

Fig. 1. Schematic diagram showing hydrophilic and hydrophobic surfaces of silica aerogels.

transparent (>90%) and translucent to the visible
light, depending on the sol–gel processing condi-
tions, but they exhibit Rayleigh scattering in the
blue region. These properties of aerogels can be
utilized for thermal superinsulations in windows
and heat-storage systems, acoustic devices, lumi-
nescent solar systems, gas filters, catalysts or cata-
lyst supports [11–15]. Despite these interesting
properties and practical applications, the large-
scale use of silica aerogels has been limited because
of their sensitivity to moisture. The concentration
of water in the pores of the aerogels leads to
capillary pressures, which eventually destroy the
structure of the aerogels. The Si–OH groups pre-
sent in the aerogel structure are the main source
of hydrophilicity because they promote the adsorp-
tion of water. The replacement of Si–OH groups
by hydrolytically stable Si–R ( R=CH ) groups
3
inhibits the adsorption of water and, therefore,
results in hydrophobic aerogels that will be
unaffected by moisture ( Fig. 1). The hydrophobi-
city of the aerogels can be achieved by two meth-

Fig. 2. Percentage of water absorbed by the aerogel versus time

for different MTMS/TMOS molar ratios: M=0, 0.26, 0.70 Fig. 3. Optical transmittance (%) of the aerogel as a function
and 1.03. of MTMS/TMOS ratio.
 A. Venkateswara Rao, D. Haranath / Microporous and Mesoporous Materials 30 (1999) 267–273
ods: (i) surface chemical modification of the
aerogels by gaseous reagents and (ii) surface modi-
fication of the colloidal particles by the incorpora-
tion of certain chemical additives in the alcosol
itself [16,17]. However, the former method
involves costly and complicated procedures and
the resulting aerogels are less hydrophobic.
Therefore, we have employed the latter method
and prepared transparent hydrophobic aerogels
using tris(hydroxymethyl ) amminomethane
( TAM ) and methyltrimethoxysilane (MTMS )
[18,19]. In the present paper, we present and
discuss the results on the effects of adding MTMS
to the synthesis formulation on the hydrophobicity
and some physical properties of silica aerogels.
2. Experimental details
2.1. Sample preparation
Under basic conditions, it has been found that
the hydrolysis rate of tetramethoxysilane ( TMOS)
is faster than that of MTMS [20]. So, in a mixture
containing TMOS and MTMS, TMOS is preferen-
tially hydrolysed in the early stages of the reaction,
during which MTMS acts as a co-solvent [21].
Therefore, the core of the primary particles will
not contain any alkyl group. The formation of a
three-dimensional solid SiO network is achieved
2 sured using a multiple-point nitrogen gas adsorp-
by the hydrolysis and polycondensation of metha-
nolic TMOS in the presence of the ammonia
(NH OH ) catalyst as per the following chemical
4 2
reaction:
MeOH
xSi(OCH ) +2xH O  xSiO +4xCH OH
34 2 2 3 and a single condensation point ( p/p =0.99) was
[NH4OH]
(1)
When a sufficient amount of TMOS gets
hydrolysed, the MTMS hydrolysis becomes faster
and proceeds as follows:
269
In this way the SiOH groups react towards the
formation of a permanently hydrophobic silica
aerogel surface.
In order to get transparent silica alco- and aero-
gels, the molar ratio of methanol (MeOH ) solvent,
water (H O) and the catalyst (NH OH ) to precur-
2 4
sor (TMOS ) was kept constant at
1TMOS:12MeOH:4H O:3.6×10−3NH OH, and
2 4
the molar ratio M of MTMS/TMOS was varied
from 0 to 1.55. The homogeneous alcosols thus
obtained were transferred to air-tight 90×
58×15 mm3 rectangular boxes and subjected to
gelation. After gelation, the alcogels were carefully
removed from the moulds and aged in an MeOH
bath for 5 days and then supercritically dried in
an autoclave to obtain hydrophobic aerogels. The
details of the supercritical drying process, including
the pre-pressure of N gas, heating and evacuation
2
rates etc., were given in our recent publications
[22,23].
2.2. Methods of characterisation
The hydrophobicity of the resulting aerogels
was tested by measuring the percentage of water
absorbed with time after putting them directly on
the surface of water. The optical transmittance of
the aerogels (sample thickness: 10 mm) was mea-
sured in the wavelength range 300–900 nm using
a Perkin–Elmer spectrophotometer (model no.
783). The pore size distribution (PSD) was mea-
tion BET surface area analyser (Micromeritics,
model ASAP 2000). The amount of N gas
adsorbed at various partial pressures (0.05<
p/p <0.3, N molecular cross-sectional area:
0 2
16.2 Å2) served to determine the BET surface area,
0
used to find the pore diameter. The PSDs were
calculated from the desorption isotherms. All the
experimental results are based on the statistical
average of five sets of identical experiments with
reproducibility greater than 95%.
(2)
270 A. Venkateswara Rao, D. Haranath / Microporous and Mesoporous Materials 30 (1999) 267–273
3. Results and discussion
3.1. Effect of MTMS/TMOS molar ratio on
hydrophobicity
In order to obtain monolithic, transparent and
hydrophobic silica aerogels, the MTMS/TMOS
molar ratio M was varied from 0 to 1.55 and its
effect on the hydrophobicity was studied. Several
authors [16,17,24,25] have studied the hydro-
phobic behaviour of aerogels, but they subjected
the aerogels to 90–96% humid atmospheres for
nearly 1 month. In the present study, the aerogels
prepared were put directly on the surface of water
in a glass beaker that was kept in a closed vessel
containing water (a rigorous test for hydrophobi-
city) and the increase in weight of the samples
was measured with a microbalance (sensitivity
~10−6 g) as a function of time ranging from a
few minutes to several months.
Moreover, an increase of less than 2% in the
weight of the aerogels (due to the adsorption of
water) has been considered as indicating hydropho-
bicity, whereas an increase of more than 2% is
considered as indicating a hydrophilic material. In
the case of hydrophobic aerogels, no net increase
in weight was observed even after 6 months,
whereas the hydrophilic aerogels gently absorbed
water and sunk to the bottom of the beaker within
2 to 3 min. The hydrophilic aerogels adsorbed
nearly eight to ten times their own weight of water
within 10 min. Fig. 2 shows the percentage of water
adsorbed by the aerogel samples with time for the
four M values of 0, 0.26, 0.70 and 1.03. The
surface hydroxyl groups are responsible for the
hydrophilic nature of the silica network [26 ] by
physically absorbing polar molecules such as
water. Incorporation of MTMS in the gels results
in (partial ) dehydroxylation of the silica surface.
This further drastically changes the physical, as
well as the chemical, properties of the surface and
the bulk. It has been found that when M<0.26
this results in a more transparent (>90% to the
visible light) but less hydrophobic aerogel; when
M>1.03 this results in the most hydrophobic
but semi-transparent-to-opaque aerogels. Both
transparent (~85%) and reasonably good hydro-
phobic aerogels were obtained at M=0.70. At this
optimum M value almost all the surface hydroxyl
groups are replaced by methyl groups, thus result-
ing in a very good hydrophobicity.
3.2. Effect of MTMS/TMOS molar ratio on
optical transmittance and PSD
Fig. 3 shows the optical transmittance spectra
of four aerogel samples. An increase in MTMS
content considerably decreased the optical
transmittance and promoted the light scattering
nature of the aerogels. Initially, in the present
system, MTMS acts as a co-solvent to promote
hydrolysis and condensation of the TMOS [21].
However, after the formation of a good number
of primary particles, the hydrolysis of MTMS
proceeds faster and it condenses onto the primary
particles by reacting with surface hydroxyl groups.
A small increase in the MTMS content above the
optimum value (M#0.70) produces more hetero-
geneity in the pore structures, which in turn
decreases the optical transmittance of the aerogels.
This is due to the fact that, after removing all the
hydroxyl groups, the excess MTMS reduces the
concentration of TMOS, resulting in a low oxide
content in the final hydrolysed product; hence the
aerogels are mechanically weak in nature.
Practically no monolithic and mechanically stable
aerogel bodies were obtained for M>1.55.
The effect of the MTMS/TMOS molar ratio M
on the PSD of the aerogels for four different M
values is shown in Fig. 4. The PSDs are represented
as dV/d( log r) plots, so that the integrated area
under the plot corresponds to the pore volume. It
is clear from Fig. 4 that an increase in the MTMS
content in the starting mixture results in a shift of
the maximum in the pore radii distribution to
larger radii. A very narrow PSD is observed in the
aerogels with no or little MTMS content, whereas
the distribution becomes broader for higher
amounts of MTMS. Here the bulk density of
the aerogels had also decreased considerably.
Moreover, the inhomogeneity in the aerogel struc-
tured network and larger pore radii give rise to a
decrease in the optical transmittance. On the other
hand, a sharp and narrow PSDs indicate less
heterogeneity of the porosity and a good connectiv-
ity between the particles. It is also clear that the
 A. Venkateswara Rao, D. Haranath / Microporous and Mesoporous Materials 30 (1999) 267–273
Fig. 4. PSD of the aerogel samples for four MTMS/TMOS
molar ratios: M=0, 0.26, 0.70 and 1.03.
bulk density of the resulting aerogel depends solely
on the amount of MTMS used in the sol–gel
process.
3.3. Effect of MTMS/TMOS molar ratio on the
microstructure and specific surface area
It should be pointed out that the aerogels with
very high specific surface areas were prepared from
TMOS without any impurities or dopants used in
the system [27]. However, they cannot be com-
pared with the gels discussed in this paper, because
co-hydrolysis of MTMS and TMOS proceeds one
after the other and thus results in slightly different
microstructures. By introducing organic groups
( like CH , C H , etc.) into the aerogel network,
3 2 5
the radius of the primary particles and the cluster
radii are hardly affected, but the surface smooth-
ness of the particles is considerably altered. This
is because the particles are primarily formed by
the hydrolysis and condensation of TMOS,
whereas the MTMS units subsequently hydrolyse
and condense on the particle surfaces.
Fig. 5 shows the variation of the specific surface
area of the aerogels with the MTMS/TMOS molar
ratio. The specific surface area of the aerogels
remained almost constant up to around M=0.80
271
Fig. 5. Specific surface area of the aerogel versus the
MTMS/TMOS molar ratio.
and then started to decrease considerably. This is
because, up to the optimum amount, the MTMS
is consumed by the removal of surface hydroxyl
groups attached to the silicon atoms, whereas an
excess of MTMS severely hinders the surface
smoothness of the particles and results in a
decrease in specific surface area. Our results are
consistent with the structural data obtained by
Schubert et al. [28] from the BET and SAXS
measurements.
3.4. Effect of thermal treatment on the
hydrophobicity
In order to study the thermal stability, hydro-
phobic aerogels were heat-treated in air at different
temperatures ranging from 25 to 350°C. When
heated below 280°C the samples showed hydro-
phobic properties, whereas upon heating above
280°C the hydrophobicity slowly vanished. The IR
spectra (Fig. 6) obtained below this critical tem-
perature (280°C ) show peaks around 3000 cm−1
that correspond to C–H bonds. When the sample
is heated above 280°C, weakening of the C–H
bond signals takes place. Since the heating of the
aerogels was performed in air, oxidation may occur
leading to removal of the CH groups under CO
3 2
272 A. Venkateswara Rao, D. Haranath / Microporous and Mesoporous Materials 30 (1999) 267–273
Fig. 6. IR spectra of the hydrophobic aerogels heated to
different temperatures: (a) 150°C, (b) 280°C and (c) 280°C
for 2 h.
formation. Fig. 6 shows the IR spectra of the
aerogel samples heated up to 280 °C and heated
for 2 h at that temperature. It is clearly seen that
the intensity of the C–H vibration peak decreases
with time. Hence, it can be concluded that 280°C
is the approximate temperature above which the
hydrophobic samples become hydrophilic. For all
practical applications of hydrophobic aerogels as
transparent window insulation materials ( TWIM )
or any other desirable applications [29], hydro-
phobic aerogels prepared by using M#0.70 are
thermally stable up to ~280°C, which is higher
than the normal conditions.
4. Conclusions
Monolithic, transparent (~85% to visible light)
and hydrophobic silica aerogels with negligible
volume shrinkage were successfully prepared by
using an MTMS/TMOS molar ratio M#0.70. For
M<0.26 the result was more transparent (>90%)
but less hydrophobic aerogels, whereas for
M>1.03 the result was cracked, opaque but more
hydrophobic aerogels. A good compromise was
achieved for the aerogels prepared using M#0.70.
An increase in the MTMS content decreased the
optical transmittance and shifted the PSD towards
larger pore radii. The specific surface area of the
aerogels was found to decrease with an increase in
the MTMS content. The hydrophobic aerogels are
thermally stable up to a temperature of ~280°C.
Above this temperature the hydrophobicity van-
ishes due to the disappearance of the CH groups
3
by oxidation.
Acknowledgements
The financial support received from the
University Grants Commission ( UGC ),
Government of India, New Delhi, under the
research project [No. F.10-32/93(SR-I )] on ‘Silica
Aerogels’ is gratefully acknowledged. The authors
sincerely thank the referees for their valuable sug-
gestions and corrections, which have considerably
improved the quality of the manuscript. The
authors thank Dr R. Chidambaram, Chairman,
Atomic Energy Commission, Government of
India, and Dr S.K. Sikka, Group Director, Solid
State and Spectroscopy Group, Bhabha Atomic
Research Centre, Mumbai, India, for their kind
help in getting the research projects on ‘Aerogels’.
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