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ICC3: Symposium 2A: Novel Chemical Processing; Sol-Gel and Solution-Based Processing IOP Publishing
IOP Conf. Series: Materials Science and Engineering 18 (2011) 032013 doi:10.1088/1757-899X/18/3/032013

Synthesis of New Flexible Aerogels from MTMS/DMDMS via

Ambient Pressure Drying

G Hayase, K Kanamori, K Kazuki and T Hanada

Department of Chemistry, Graduate School of Science, Kyoto University,
Kitashirakawa, Sakyo-ku, Kyoto, 606-8502, Japan.

E-mail: kanamori@kuchem.kyoto-u.ac.jp

Abstract. Although silica aerogel is expected to be the material for energy savings, the lack of
the strength prevents from commercial applications such as to low-density thermal insulators
and acoustic absorbents. To improve mechanical properties, methyltrimethoxysilane (MTMS)
and dimethyldimethoxysilane (DMDMS) are used as the co-precursor of aerogels in this study
because the network becomes flexible due to the relatively low cross-linking density and to the
unreacted methyl groups. Because of the strong hydrophobicity of MTMS/DMDMS-derived
condensates, phase separation occurs, which must be suppressed in aqueous sol to obtain
uniform and monolithic gel networks. We also employed surfactant n-
hexadecyltrimethylammonium chloride (CTAC) in starting compositions to control phase
separation during a 2-step acid/base sol-gel reaction. By changing the starting composition,
various microstructures of pores are obtained. In the uniaxial compression test, the aerogel
showed high flexibility and spring-back to the original shape after removing the stress.

1. Introduction
Silica aerogels have outstanding properties such as high optical transparency (> 90 %), high surface
areas (~ 1000 m2 g−1), low refractive indices (< 1.01), high thermal and acoustic insulation abilities,
and low dielectric constants [1]. Owing to these excellent properties, there are many applications on
the front of science [2], but only a limited number of commercial products are available because of
serious fragility of this material. For a wide application of aerogels, it is necessary to improve
mechanical properties and develop a new simple process without using super critical drying.
There has been a lot of research to improve the mechanical properties of silica aerogels and to
obtain aerogels without supercritical drying while maintaining the above-mentioned excellent
properties. Adding organoalkoxysilanes which have small organic functional groups such as methyl
group is one of the promising ways to improve the mechanical properties. Organic functional groups
make the internal surface hydrophobic, and this improves water resistance and shrinkage during drying,
comparing with TEOS- or water glass-derived silica aerogels [4-5]. Recent years some flexible
aerogels are reported by using a couple of organoalkoxysilanes as co-precursor [6-7].
We have reported aerogels prepared from methyltrimethoxysilane (MTMS) as the single precursor
and surfactant n-hexadecyltrimethylammonium salts (bromide denoted as CTAB and chloride as
CTAC) which are added to control phase separation, by a modified acid/base two-step sol-gel reaction
utilizing acetic acid and urea as catalysts. These aerogels are transparent and possess improved
mechanical properties (such as reversible shrinkage/reexpansion called spring-back) [8-10].


c 2011 Ceramic Society of Japan. 1
Published under licence by IOP Publishing Ltd
ICC3: Symposium 2A: Novel Chemical Processing; Sol-Gel and Solution-Based Processing IOP Publishing
IOP Conf. Series: Materials Science and Engineering 18 (2011) 032013 doi:10.1088/1757-899X/18/3/032013

In this study, we investigated the synthesis of more flexible aerogels from co-gelation systems of
MTMS and dimethyldimethoxysilane (DMDMS) with using CTAC as surfactant to further improve
the mechanical properties.

2. Experimental
Samples are denoted as “Bw-x-y-z” where “w”, “x”, “y” and “z” are the amount of MTMS (5−w mL)
and DMDMS (w mL), the amounts of CTAC (g), the concentration of acetic acid (mM) and the
amount of urea (g), respectively. The amount of aqueous acetic acid is fixed in 15 mL. For example,
in the composition of B2.0-0.8-5-5, 3.0 mL of MTMS, 2.0 mL of DMDMS, 0.80 g of CTAC, 5 mM of
acetic acid (as 15 mL of the aqueous solution), and 5.0 g of urea are included and its molar ratio
MTMS:DMDMS:water:acetic acid:urea = 3.0:2.0:1.2 × 102:6.4 × 10−1:1.2 × 101.
Aqueous acetic acid, CTAC and urea were dissolved in a glass sample tube, and then MTMS was
added and kept being stirred for 15 min for hydrolysis of MTMS. Subsequently DMDMS was added
and kept being stirred for another 15 min at room temperature to allow hydrolysis of DMDMS. The
resultant homogeneous solution was transferred to a closed vessel and kept at 60 °C for gelation and
aging for 4 d. During this process, urea is hydrolyzed to release ammonia which raises the solution pH.
The obtained wet gel was washed by the mixed solvents in three steps in every 8 h each at 60 °C to
remove unreacted chemicals for three times in each step; First with 50 vol % of 2-propanol in water,
and for second and third with pure 2-propanol). The alcogels were dried from supercritical carbon
dioxide at 80 °C and 14 MPa for 10 h in a custom-built autoclave (Mitsubishi Materials Techno Corp.,
Japan) to obtain aerogel samples.
Bulk density was obtained by weighing the sample of a known volume. Scanning electron
microscopy (SEM, JSM-6060S, JEOL Ltd., Japan) was employed to observe the pore structures in the
micrometers range. For measurements of mechanical properties, EZGraph (Shimadzu Corp., Japan)
was employed to perform the uniaxial compression test.

3. Results and discussion

3.1. Changes in Microstructures

In many cases, MTMS does not form uniform and monolithic gel network throughout the sol, due to
the high phase separation tendency in polar solvent, which is resulted from the strong hydrophobicity
arising from the methyl groups directly attached to the silicon atom. This tendency is higher for
DMDMS because of the two methyl groups on each silicon. In addition, cyclization reaction is known
to form stable rings and cages, which do not contribute to the monolithic gel formations in tri- and d-
functional alkoxysilanes. For such reasons, it was difficult to obtain monolithic aerogels from
MTMS/DMDMS as the co-precursor. However, with an employment of CTAC as surfactant in the
acid/base two-step process, since phase separation is effective suppressed and random networking is
promoted, the monolithic gel can be obtained. Adding only 0.20 g of CTAC in a starting composition,
flexible aerogels were obtained, but there was no obvious change in the micrometer-range structures
with increasing amount of CTAC. From this observation, while CTAC strongly suppresses phase
separation, the gel structure hardly changes.
Figure 1 shows changes in the microstructure by varying the ratio of MTMS/DMDMS. With w =
1.2 (MTMS 3.8 mL and DMDMS 1.2 mL) shown in (a), the gel is translucent and becomes opaque
with increasing w. With 1.2−1.6, the microstructure dramatically changed due to the increase in
hydrophobicity of the condensates. With w > 1.8, no clear change was observed, and no gelation
occurred when w > 2.5. Together with the results of CTAC-varied system mentioned above, there
presumably is an upper limit of hydrophobicity because the incorporation of DMDMS into the gel
networks is limited.

2
ICC3: Symposium 2A: Novel Chemical Processing; Sol-Gel and Solution-Based Processing IOP Publishing
IOP Conf. Series: Materials Science and Engineering 18 (2011) 032013 doi:10.1088/1757-899X/18/3/032013

(a) (b) (c)

2 µm 20 µm 20 µm

(d) (e)

20 µm 20 µm

Figure 1. SEM images of the samples prepared with varied amount of MTMS/DMDMS:
(a) 3.8 mL/1.2 mL (B1.2-0.8-5-5), (b) 3.6 mL/1.4 mL (B1.4-0.8-5-5), (c) 3.4 mL/1.6 mL
(B1.6-0.8-5-5), (d) 3.2 mL/1.8 mL (B1.8-0.8-5-5), and (e) 3.0 mL/2.0 mL (B2.0-0.8-5-5).

The concentration of urea also affected morphology (Figure 2). In the system with a small amount
of urea (B2.0-0.8-5-1), the microstructure of the obtained aerogel consists of spherical particles. With
increasing the amount of urea, the structure becomes more continuous and the thickness of the
networks becomes thinner because of the shorter gelation time with increasing amount of urea. It is
generally observed that the phase-separated structure becomes finer with shorter gelation because
there is a shorter time for phase-separated structure to be developed into larger scales.

(a) (b) (c)

20 µm 20 µm 20 µm

(d) (e) (f)

20 µm 20 µm 20 µm

Figure 2. SEM images of the samples prepared with varied amount of urea: (a) 1.0 g
(B2.0-0.8-5-1), (b) 2.0 g (B2.0-0.8-5-2), (c) 3.0 g (B2.0-0.8-5-3), (d) 4.0 g (B2.0-0.8-5-
4), (e) 5.0 g (B2.0-0.8-5-5), and (f) 6.0 g (B2.0-0.8-5-6).

3.2. Mechanical Properties

With w ~ 2.0, aerogels can be obtained by evaporative drying under ambient conditions because the
gels become more flexible and spongy against compressive stress exerted during evaporation of the

3
ICC3: Symposium 2A: Novel Chemical Processing; Sol-Gel and Solution-Based Processing IOP Publishing
IOP Conf. Series: Materials Science and Engineering 18 (2011) 032013 doi:10.1088/1757-899X/18/3/032013

solvent (Figure 3). For example, the dried sample B2.0-0.8-5-5 possesses low density (0.115 g cm−3)
and high flexibility. Figure 4 shows the result of the uniaxial compression test. The flexible aerogel
recovered from the compressed form in 80 % to the original shape almost completely after removing
the stress. The flexible behavior becomes better for the sample with higher fraction of DMDMS and
with more continuous skeletons. Compared to the flexible aerogels derived only from MTMS, the
maximum stress is only ~ 0.10 MPa for the MTMS/DMDMS-derived aerogel, which is about a
hundred times smaller than MTMS-derived aerogels. The MTMS/DMDMS-derived aerogels are
much softer than MTMS-derived aerogels due to the decreased cross-linking density.

Figure 3. Appearance of the Figure 4. A stress-strain curve

high flexible aerogel (B2.0- obtained by the uniaxial
0.8-5-5). compression test for the flexible
aerogel (B2.0-0.8-5-5).

4. Conclusion
In the two-step sol-gel process containing surfactant CTAC, highly flexible aerogels have been
obtained from the mixtures of MTMS and DMDMS. When the ratio of MTMS/DMDMS is 3.0
mL/2.0 mL, the flexible aerogel is obtained by evaporative drying under ambient conditions. While
the amount of CTAC does not affect the microstructure of the gels, no gelation occurs without this
surfactant. Concentration of urea is found to largely affect the aerogel morphology. The
concentration of urea alters microstructures of aerogels from aggregation of spherical particles to co-
continuous because pH in the second condensation step becomes higher, which accelerates gelation
relative to phase separation. Since the obtained flexible aerogels are soft and spongy with micrometer-
sized pores, these materials are suitable for acoustic insulation.

References
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[5] F Schwertfeger and D F M Schmidt 1998 J. Non-Cryst. Solids 225 24
[6] A Venkateswara Rao, Sharad D Bhagat, Hiroshi Hirashima and G M Pajonk 2006 Adv. Colloid
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Meador 2009 J. Mater. Chem. 19 9054
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