Journal of Non-Crystalline Solids 410 (2015) 58–64

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Journal of Non-Crystalline Solids

journal homepage: www.elsevier.com/ locate/ jnoncrysol

Synthesis and characterization of silica aerogels dried under ambient

pressure bed on water glass
Song He a, Dongmei Huang b, Haijiang Bi a, Zhi Li a, Hui Yang a, Xudong Cheng a,⁎
a
State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230027, PR China
b
College of Quality and Safety Engineering, China Jiliang University, Hangzhou, Zhejiang 310018, PR China

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, we report the experimental results on the synthesis of water glass based silica aerogels, which were
Received 7 October 2014 dried under ambient pressure. Water glass was hydrolyzed and condensed in water using HCl as the catalyst.
Received in revised form 6 December 2014 To minimize shrinkage during drying process, N,N-dimethylformamide (DMF), acting as drying control chemical
Accepted 7 December 2014
additive (DCCA), was introduced. Before the ambient pressure drying, solvent exchange and surface modification
Available online xxxx
were completed. In order to get hydrophobic aerogel, trimethylchlorosilane (TMCS) was used to modify the hy-
Keywords:
drophilic hydrogel surface. Here a large amount of TMCS can be saved compared with that in single step solvent
Water glass; exchange/surface modification method. The effects of DMF on the physical and textural properties of the
Sol–gel process; resulting aerogels were investigated. When the molar ratio of Si in water glass to DMF is 2.23, the synthesized
Silica aerogel; silica aerogels have better properties. Characterized by FT-IR, SEM, BET, etc., the resulting aerogels have well-
Ambient pressure; developed mesoporous structure (mean pore size of ~ 15 nm) with super hydrophobicity (contact angle of
DMF 161°) and excellent absorption capacity of organic liquids.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
Silica aerogels are low density, translucent and thermal insulat-
ing material consisting of nanoparticle building blocks, networked
together to form an open, highly porous structure. They have a
large surface area (500–1500 m 2 /g), high porosity (80–99%) and
low bulk density (0.03–0.35 g/cm3). Due to these unusual proper-
ties, aerogels have attracted much attention for they have large po-
tential to be applied in many fields. Silica aerogels modified with methyl
(−CH3) groups can function very well in the sorption of organics, and
their adsorption capacities are 10 times higher than those of activated
carbon [1–3]. Silica aerogel beads (micron-sized) can easily be filled into
hollow spaces and provide high thermal resistance. Further, silica aerogels
can serve as thermal super-insulators in solar energy systems, refrigera-
tors, thermal flasks [4–6], internal confinement fusion (ICF) targets for
thermonuclear fusion reactions [7], very efficient catalysts and catalytic
supports [8,9]. The extremely low density and high surface area of
monolithic aerogels provide an opportunity to improve the performance
of various metal-oxide-based devices, including gas and bio-sensors, bat-
teries, heterogeneous catalysis devices, and low dielectric constant mate-
rials for integrated circuits (low-k dielectrics) [10–13]. Despite these
advantages, aerogels are still not routinely found in our daily life, because
they are fragile, collapse easily and difficult to prepare in a large-scale in-
dustrial production setting.
⁎ Corresponding author.
E-mail address: chengxd@ustc.edu.cn (X. Cheng).
Silica aerogels are produced by removing the entrapped solvent from
the wet gel while maintaining the integrity and high porosity of the gel.
Supercritical fluid drying and ambient pressure drying are the most com-
monly used drying methods. Several researchers have used supercritical
organic solvents for drying [3,10,11,14–18] to synthesize silica aerogel.
Generally, fluids under supercritical pressures have almost zero surface
tension. And this avoids the collapse and shrinkage caused by the surface
tension force associated with the removal of the fluid. However, supercrit-
ical drying, involving high pressures (5–10 MPa), requires more power
and high quality of manufacturing equipments.
Some researchers have prepared silica aerogel using tetraethoxysilane
(TEOS) under ambient pressure [19–21]. However TEOS is a rather
expensive organic reagent as precursor. To reduce the preparation cost
of silica aerogel, water glass has been chosen as a much cheaper precur-
sor. Based on water glass, aerogels have been synthesized by researchers
through sol–gel process to form a gel under ambient pressure drying
[22–26]. Sodium ion should be removed from the water glass solution
to improve the optical transmission of the final aerogel product [26].
The pore size distribution (PSD) is a key factor that judges and decides
the quality of silica aerogels. And the DCCA was studied to have the influ-
ence on PSD of silica aerogels [27]. Several researchers have investigated
the DCCA's effect with different agents [28–33] in recent years.
In this work, to obtain a well distributed pore structure, DMF, acted as
DCCA, has been introduced and its effect on the properties of water glass
based silica aerogel was studied, which has not been investigated before.
The aerogels with low density, low shrinkage and high porosity have been
obtained by adding appropriate DMF. The pore size distribution became

http://dx.doi.org/10.1016/j.jnoncrysol.2014.12.011
0022-3093/© 2014 Elsevier B.V. All rights reserved.
 S. He et al. / Journal of Non-Crystalline Solids 410 (2015) 58–64
uniform. Besides, much less amount of TMCS was used to completely
modify the gel compared with previous research [34].
2. Experimental procedure
2.1. Sample preparation
Silica aerogels were prepared by a single-step sol–gel process
followed by ambient pressure drying. The precursor used for prepara-
tion of hydrogels was water glass (wt: 34%, QDSS (Qingdao Dongyue
Sodium Silicate CO., Ltd, China), Na2O::SiO2 = 1::3.33). Other agents
including hydrochloric acid (HCl), DMF, ethanol (EtOH), n-hexane and
trimethylchlorosilane (TMCS) were purchased from SCRC (Sinopharm
Chemical Reagent CO., Ltd, China).
Water glass was diluted with deionized water. The hydrolysis was
carried out with the participation of HCl (5 M), before which DMF was
added to the solution. The sol was stirred for 1 min in room temperature
and the pH is about 6.2. The hydrolysis reaction led to the formation of
silicic acid with the probable byproduct of NaCl. The gelation occurred
within 15 min.
To age and remove the sodium, the gel was soaked with enough
deionized water in a beaker, which was put in 45 °C water bath in 10 h.
The water was removed by filtration. Ethanol was added into the gel to
exchange water within the pores of hydrogel twice in 12 h and the etha-
nol was replaced by n-hexane in 6 h. The whole exchange process was
carried out in 45 °C water bath and the solvent was removed by filtration.
The surface chemical modification of the gel was carried out by
adding the silylating mixture of TMCS: hexane with the volume ratio
of 15% to the gel under the condition of 45 °C water bath in 12 h.
Then the silylated gel was dried in ambient pressure at 60 °C for 2 h
and finally dried at 100 °C to get aerogel. The aerogel was weighted
every 2 h to make sure that the aerogel was dried completely.
2.2. Characterization
The bulk density of the aerogel sample was calculated by measuring
its mass to volume ratio. The porosity of the aerogels was calculated
using the following formula:
 
ρ necessary. Through comparison (Table 1), ethanol and n-hexane were
porosity ¼ 1− a  100%
ρs
where ρa is the bulk density of aerogel and ρs is the skeleton density of
the silica aerogels. Generally the value of ρs is 2.2 g/cm3. The content of
sodium in the aerogel was measured by Inductively Coupled Plasma
Atomic Emission Spectroscopy (ICP-AES).
The contact angle measurements were performed using a KSV
(Helsinki, Finland) CAM 200 contact angle goniometer at ~ 20 °C. The
thermal stability of aerogel sample was studied by the thermal gravi-
metric and differential thermal analysis (TG-DTA) using SDT Q600 (TA
Instruments, USA). TG-DTA can also help to determine the oxidation
temperature of –CH3 group contained in the aerogel, that is, the temper-
ature up to which the silica aerogel samples retain its hydrophobicity.
The hydrophobic nano-porous silica aerogels with a weight of 6 mg
were heat-treated in air, from room temperature (25 °C) up to 800 °C,
with a controlled heating rate of 10 °C·min−1.
The microstructure and morphology of the aerogels were studied
using Field Emission Scanning Electron Microscope (FESEM) (SIRION 200,
FEI, USA). The specific surface areas were determined by nitrogen sorp-
tion isotherms with standard Brunauer–Emmett–Teller (BET) analysis
(Tristar II 3020 M, Micromeritics Instrument Corporation, USA). The cu-
mulative pore volume was calculated from the N2 adsorption–desorption
profiles. The average pore diameters and pore size distributions (PSD)
were estimated by the Barrett–Joyner–Halenda (BJH) method (Tristar II
3020 M, Micromeritics Instrument Corporation, USA). The surface chem-
ical modification of aerogels was studied using Fourier Transform Infrared
59
Spectroscopy (FT-IR) (Nicolet 8700, Thermo Fisher Scientific, USA), which
gave information about various chemical bonds, such as O\H, C\H, and
Si\O\Si. For this purpose, the silica aerogels were ground into refined
powders, mixed with KBr and pressed to form a sample pellet for FT-IR
measurements.
To measure the absorption capacity of the silica aerogels, the
samples were immersed into various types of solvents/oils. The absorp-
tion process was very fast and generally reached equilibrium within a
few minutes. Then the soaked samples were taken out and weighed
after the aerogel surface was blotted using a filter paper to remove excess
surface solvent/oil [35]. The absorption capacity (Q) was calculated from
the mass gain using Eq. (2),
ðW−W 0 Þ
Q ð%Þ ¼  100% ð2Þ
ρL V 0
where W0 and W are the weights of aerogels before and after absorption
respectively, V0 is the aerogel volume, and ρL is the density of absorbed
solvent/oil. The weight measurements of the aerogels with absorbed oil
were carried out quickly to avoid evaporation of the solvent/oil.
3. Results and discussion
Silica hydrogels were prepared by a single-step sol–gel process of
deionized water (DI·H2O) diluted water glass in the presence of acid
(hydrochloric acid) catalyst, as shown in the following reactions:
Hydrolysis : Na2 SiO3 þ H2 O þ 2HCl→SiðOHÞ4 þ 2NaCl ð3Þ
Condensation : SiðOHÞ4 þ ðOHÞ4 Si→ðOHÞ3 Si–O–SiðOHÞ3 þ H2 O: ð4Þ
When the liquid contained in the pores of hydrogel vaporised, the
capillary pressure which can lead to pore collapse is occurred. It can
be calculated with the following equation:
p ¼ 2σcosθ=r ð5Þ
where p is capillary pressure, σ is surface tension of solvent, θ is contact
angle and r represents the capillary radius. To minimize the capillary
pressure, the solvent exchange and surface modification process is
ð1Þ
chosen to be the exchange solvents, respectively. TMCS was the surface
silylation reagent and the chemical reaction in the surface modification
process is as follows:
ðCH3 Þ3 SiCl þ ≡ Si–OH→ ≡ Si–O–SiðCH3 Þ3 þ HCl: ð6Þ
After gelation, measured by ICP-AES, the weight content of sodium
in the hydrogel is 1.24%, while it sharply decreased to 0.02% after the
DI·H2O washing process. So the DI·H2O washing is an effective way to
remove the sodium in the hydrogel. To determine the volume ratio
of the solvent DI water to water glass, a series of experiments setting
the volume ratio from 1 to 5 with increment of 1 were conducted, in
which enough TMCS was added to the system to modify the gel. The
porosity is presented in Fig. 1. It is clear that when the volume ratio is
3, the obtained aerogels have the highest porosity. And thus the volume
ratio of DI water to water glass is fixed 3.
Table 1
Surface tension of several solvents at 20 °C [36].
Solvent Surface tension (10−3 N·m−1)
Isopropanol 21.7
n-Hexane 18.4
Acetone 23.7
Ethanol 22.8
Ethylene glycol 48.4
Water 72.7
60 S. He et al. / Journal of Non-Crystalline Solids 410 (2015) 58–64
Fig. 1. Porosity of silica aerogel with no DMF.
The hydrophilic surface of hydrogel network became hydrophobic for
the formation of alkoxytrimethylsilane (`Si\O\Si(CH3)3) (Eq. (6)). The
surface modification of the gels was studied by measuring the contact
angle of water droplets on the silica aerogel surface under various molar
ratios of TMCS to pore water (denoted as N). As shown in Fig. 2, the con-
tact angle reached to 161° at N = 0.0311, which indicated a super hydro-
phobicity of the silica aerogel. And with the further increase of N, the
contact angle almost remains the same (Table 2). N is set 0.0311 which
is much smaller than that used in single step solvent exchange/surface
modification [34].
The super hydrophobicity of aerogel was attributed to the attach-
ment of –Si(CH3)3 groups to the gel surface, which can be confirmed
by the Fourier Transform Infrared Spectroscopy (FT-IR) analysis, as
shown in Fig. 3. It is evident that apart from the Si–O–Si (absorption
peak at about 470 cm− 1 and 1060 cm− 1 [37]), the modified silica
aerogels show strong absorption peaks at about 850 cm − 1 and
1260 cm− 1, which respectively correspond to the terminal Si–CH3
groups [37]. The presence of these two absorption peaks in the
FTIR spectra confirms the attachment of –Si–CH3 groups from the
TMCS to the silica aerogel surface, indicating that the surface modi-
fication of the aerogels was successful. In addition, it is clear that the
intensity of the bonds at ~ 3450 and ~ 1650 cm − 1 of –OH groups
were decreased but not disappeared after surface modification [2,
37–40]. On one hand, the amount of Si–OH groups decreased after
modified by TMCS (Eq. (6)), leading to a weaker absorption intensi-
ty of –OH. However, on the other hand, when conducting FT-IR mea-
surement, silica aerogel samples were ground into refined powders,
mixed with KBr and pressed to form sample pellet. KBr can easily
absorb H2 O in the air whose –OH can also cause absorption peak
at ~ 3450 and ~ 1650 cm− 1.
The modified silica aerogel is hydrophobic for the surface modifica-
tion in which process –CH3 groups are attached to the gel surface. When
heated in a circumstance of high temperature, pyrolysis will happen to
Fig. 2. Water droplet placed on water glass-based silica aerogel surface (N = 0.0311).
Table 2
Contact angle of silica aerogels under various molar ratios of TMCS to pore water.
N 0 0.0104 0.0207 0.0313 0.0415
Contact angle (°) 83 106 135 161 160
the –CH3 groups. In this study, the aerogels were heated in a furnace at a
range of temperatures from 25–800 °C in air to further investigate the
thermal stability.
The TG/DTA curve of synthesized silica aerogel is illustrated in Fig. 4.
It can be observed that for modified aerogels, there presents an obvious
exothermic peak at a temperature of ~400 °C, while as to the unmodi-
fied ones, no obvious exothermic peak can be seen. The –CH3 groups
in the modified aerogels are oxidized at ~ 400 °C [41] and resulted in
the sharp decrease in the gravity curve. Not alkylated by TMCS, there
are considerable amount of hydroxyl (− OH) which is hydrophilic in
the surface of unmodified aerogels, and thus much free water in the
air was absorbed by the unmodified aerogels. The pronounced weight
loss of unmodified silica aerogel before 200 °C owed to the evaporation
of free water absorbed by the unmodified aerogels. And the weight loss
upward 200 °C resulted from the condensation of hydroxyl that existed
in the surface aerogel. While as to the well modified aerogel, the weight
loss before 100 °C may be results from the evaporation of residual sol-
vent and water molecules.
To study the effect of DMF on the properties of silica aerogel, the
molar ratio of Si to DMF was set as 3.34, 2.23, 1.11 and 0.83, corresponding
to samples B2, B3, B4 and B5 respectively. The sample B1 was synthesized
without DMF.
The gelation time and physical properties of the silica aerogel are
listed in Table 3. The specific surface area of the sample is as high as
680 m2/g which is much larger than the ones without DMF [22,25,26].
The polarity of DMF is relatively strong. The hydrogen bonds will form
between hydroxyls (− OH) in orthosiliconic acid and DMF molecules
which would impede the polycondensation of Si(OH)4. The condensa-
tion rate slowed down and the gelation process lasted longer, just as
shown in Table 3.
Fig. 5 shows that the silica aerogels' bulk density and volume shrink-
age affected by the gelation time apparently. Either for the bulk density
or volume shrinkage, the U-shaped curve can be clearly seen with the
increase of gelation time. When there is no DMF, the Si(OH)4 molecules
condensed quickly and disordered. While DMF was introduced, hydrogen
bond will be formed between hydroxyls in Si(OH)4 and DMF molecules,
then the condensation should be processed between the hydroxyls
which were not hydrogen bonded with DMF. In this way, it can be consid-
ered that the condensation was conducted in some well-organized way.
Fig. 3. FTIR spectra of the synthesized water glass based silica aerogels.
 S. He et al. / Journal of Non-Crystalline Solids 410 (2015) 58–64 61

Fig. 5. Effect of gelation time on bulk density and volume shrinkage of silica aerogels.
Fig. 4. TG/DTA curves in air atmosphere for the water glass based silica aerogel.

And the formed hydrogel would have relatively uniform pore and particle The microstructure of the aerogels can be seen in the scanning elec-
size. On the other hand, the hydrogen bond will be destroyed by high tron microscope images in Fig. 7, in which the aerogels' highly branched
energy, like high temperature water bath, 60 °C and 100 °C ambient pres- polymeric structure can be evidently observed. The pore sizes in sample
sure drying. Then the free hydroxyls, which were not condensed during B1 distribute in a rather broad range, while the PSD of sample B3 is
the condensation process, would condense and destroy the existed gel the most uniform one among the five. For B1, the high condensation
microstructure. Therefore, when DMF is in excess (B4, B5), there would rate resulted in nonuniform pore size of hydrogel, and the difference
be considerable amount of hydroxyls that take part in the condensation, of capillary pressure caused by ambient pressure drying collapse the
which can destroy the existed uniform pore structure. The difference of pores. Thus some extremely big pores formed (Fig. 7a). As to B2 and
pores' size increases, so does the capillary pressure during ambient dry- B3, the PSDs gradually turn to uniform. For the addition of DMF resulted
ing. Thus the pores will collapse. The aerogel's shrinkage aggravates and
its density rises.
The pore size distributions of the samples are presented in Fig. 6a. It
can be seen that for all the samples, most of the pores are distributed in
the size of ~230 Å. However, samples B4 and B5 have the broadest pore
size distribution (PSD) (17 Å–1700 Å) among the five samples. As to B1,
the pore volume peaks are not so distinct which means pores within a
certain diameter interval largely coexist. There is a pronounced peak
at a diameter of ~ 230 Å in the PSD curve of B3 and the pore volumes
of other diameters are relatively small. Thus the PSD is the most uniform
one. As mentioned above, the gelation time for sample B1 is the shortest.
Condensation processed in a fast way and nonuniform network formed.
When evaporated under ambient pressure, the big difference of capillary
pressure operated on the pores made the pore structure collapse. Howev-
er, when a moderate amount of DMF was added during the preparation
process, the aerogels' PSDs have been apparently changed which is
much narrower. When excess DMF was added, hydroxyls' hydrogen
that bonded with DMF molecules would condense during high tempera-
ture water bath or ambient drying, and the existed pore structure would
be destroyed. Fig. 6b compares the N2 sorption isotherms obtained from
the silica aerogel samples. All the isotherms in Fig. 6b represent a type
IV isotherm [42] (in the BDDT classification) with H3 type hysteresis
loop [43,44], which indicates that they are a kind of material con-
taining mesopores. The adsorption–desorption cycles of the given
isotherms show a hysteresis loop in the high relative pressure re-
gion, which is generally attributed to the capillary condensation oc-
curring in the mesopores [44].

Table 3
Gelation time and physical properties of the silica aerogel samples.

Sample Molar ratio Gelation Specific Pore Average pore

of Si:DMF time (min) surface area volume diameter (Å)
(m2/g) (cm3/g)

B1 ∞ 0.8 469 1.8 156

B2 3.34 2.3 551 2.3 136
B3 2.23 6.1 680 2.8 131
B4 1.11 10.5 583 3.3 136
Fig. 6. a) Pore size distribution and b) N2 adsorption–desorption isotherms of water glass
B5 0.83 11.2 565 2.2 138
based silica aerogel samples.
62 S. He et al. / Journal of Non-Crystalline Solids 410 (2015) 58–64

a. B1 b. B2

c. B3 d. B4

e. B5
Fig. 7. Scanning electron microscope images of aerogel samples.

in the formation of hydrogen bond, which made the condensation of
free hydroxyls (not hydrogen bonded with DMF) in Si(OH)4 in an
ordered way. And the clusters or pore sizes become homogeneous. For
B4 and B5, excess DMF resulted in much hydroxyls that hydrogen bond-
ed with DMF, which will condense with each other under high energy
condition, such as water bath or ambient pressure drying. The existed
pores, particles or clusters would be destroyed by the second condensa-
tion. The particles or clusters are larger and the pores are not uniform in
Fig. 7d and e.
After being modified by TMCS, methyl groups were attached to the
surface, and the silica aerogels are hydrophobic and oleophylic. Thus
the silica aerogels can absorb organic liquids, such as n-hexane from
water quickly (Fig. 8a). Presented in Fig. 8b, the absorption capacity of
the silica aerogels were measured using ethanol, n-hexane and gasoline,
respectively. Silica aerogels of 1 cm3 can absorb more than 0.9 ml organ-
ic liquids. Compared with the silica aerogels using TEOS as precursor [2],
the absorption capacity of the sample B3 in this study is obviously
higher. The aerogels' absorption efficiency increased significantly.
4. Conclusion
Super hydrophobic ( = 161°) and oleophylic silica aerogels were
successfully synthesized under ambient pressure using single step sol–
gel polymerization of water glass. The volume ratio of deionized water
 S. He et al. / Journal of Non-Crystalline Solids 410 (2015) 58–64
Fig. 8. A layer of n-hexane labeled by Oil Red O on top of the water was absorbed by a piece of silica aerogel within 40 s; b) comparison of absorption capacity with other material.
to water glass was fixed at 3 and the proper molar ratio of TMCS to pore
water was studied and set to be 0.0311, which is much lower than pre-
vious research. The TG/DTA analysis revealed that the aerogels retain
their hydrophobic nature up to a maximum temperature of 400 °C.
The DMF was added to slow down the condensation speed and obtain
a uniform distribution of the aerogel pores. However, excess DMF can
speed the condensation to a certain extent and the distribution of
pores and particles is not so nice. When the molar ratio of Si to DMF is
2.23, the obtained aerogels have better properties: relatively low bulk
density (0.089 g/cm3), large surface area (680 m2/g) and high pore vol-
ume (3.3 cm3/g). The aerogels' absorption capacity of organic liquids is
relatively high: more than 0.9 ml of organic liquids (ethanol, n-hexane
and gasoline) can be absorbed by per cubic centimeter of as-prepared
silica aerogel.
Acknowledgment
The research is partly supported by the fund (No.HZ2012-KF03) in
State Key Laboratory of Fire Science, University of Science and Technol-
ogy of China.
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