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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 produced by removing the entrapped solvent from
the wet gel while maintaining the integrity and high porosity of the gel.
Silica aerogels are low density, translucent and thermal insulat- Supercritical fluid drying and ambient pressure drying are the most com-
ing material consisting of nanoparticle building blocks, networked monly used drying methods. Several researchers have used supercritical
together to form an open, highly porous structure. They have a organic solvents for drying [3,10,11,14–18] to synthesize silica aerogel.
large surface area (500–1500 m 2 /g), high porosity (80–99%) and Generally, fluids under supercritical pressures have almost zero surface
low bulk density (0.03–0.35 g/cm3). Due to these unusual proper- tension. And this avoids the collapse and shrinkage caused by the surface
ties, aerogels have attracted much attention for they have large po- tension force associated with the removal of the fluid. However, supercrit-
tential to be applied in many fields. Silica aerogels modified with methyl ical drying, involving high pressures (5–10 MPa), requires more power
(−CH3) groups can function very well in the sorption of organics, and and high quality of manufacturing equipments.
their adsorption capacities are 10 times higher than those of activated Some researchers have prepared silica aerogel using tetraethoxysilane
carbon [1–3]. Silica aerogel beads (micron-sized) can easily be filled into (TEOS) under ambient pressure [19–21]. However TEOS is a rather
hollow spaces and provide high thermal resistance. Further, silica aerogels expensive organic reagent as precursor. To reduce the preparation cost
can serve as thermal super-insulators in solar energy systems, refrigera- of silica aerogel, water glass has been chosen as a much cheaper precur-
tors, thermal flasks [4–6], internal confinement fusion (ICF) targets for sor. Based on water glass, aerogels have been synthesized by researchers
thermonuclear fusion reactions [7], very efficient catalysts and catalytic through sol–gel process to form a gel under ambient pressure drying
supports [8,9]. The extremely low density and high surface area of [22–26]. Sodium ion should be removed from the water glass solution
monolithic aerogels provide an opportunity to improve the performance to improve the optical transmission of the final aerogel product [26].
of various metal-oxide-based devices, including gas and bio-sensors, bat- The pore size distribution (PSD) is a key factor that judges and decides
teries, heterogeneous catalysis devices, and low dielectric constant mate- the quality of silica aerogels. And the DCCA was studied to have the influ-
rials for integrated circuits (low-k dielectrics) [10–13]. Despite these ence on PSD of silica aerogels [27]. Several researchers have investigated
advantages, aerogels are still not routinely found in our daily life, because the DCCA's effect with different agents [28–33] in recent years.
they are fragile, collapse easily and difficult to prepare in a large-scale in- In this work, to obtain a well distributed pore structure, DMF, acted as
dustrial production setting. DCCA, has been introduced and its effect on the properties of water glass
based silica aerogel was studied, which has not been investigated before.
⁎ Corresponding author. The aerogels with low density, low shrinkage and high porosity have been
E-mail address: chengxd@ustc.edu.cn (X. Cheng). 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 59

uniform. Besides, much less amount of TMCS was used to completely Spectroscopy (FT-IR) (Nicolet 8700, Thermo Fisher Scientific, USA), which
modify the gel compared with previous research [34]. 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
2. Experimental procedure powders, mixed with KBr and pressed to form a sample pellet for FT-IR
measurements.
2.1. Sample preparation To measure the absorption capacity of the silica aerogels, the
samples were immersed into various types of solvents/oils. The absorp-
Silica aerogels were prepared by a single-step sol–gel process tion process was very fast and generally reached equilibrium within a
followed by ambient pressure drying. The precursor used for prepara- few minutes. Then the soaked samples were taken out and weighed
tion of hydrogels was water glass (wt: 34%, QDSS (Qingdao Dongyue after the aerogel surface was blotted using a filter paper to remove excess
Sodium Silicate CO., Ltd, China), Na2O::SiO2 = 1::3.33). Other agents surface solvent/oil [35]. The absorption capacity (Q) was calculated from
including hydrochloric acid (HCl), DMF, ethanol (EtOH), n-hexane and the mass gain using Eq. (2),
trimethylchlorosilane (TMCS) were purchased from SCRC (Sinopharm
Chemical Reagent CO., Ltd, China). ðW−W 0 Þ
Q ð%Þ ¼  100% ð2Þ
Water glass was diluted with deionized water. The hydrolysis was ρL V 0
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 where W0 and W are the weights of aerogels before and after absorption
and the pH is about 6.2. The hydrolysis reaction led to the formation of respectively, V0 is the aerogel volume, and ρL is the density of absorbed
silicic acid with the probable byproduct of NaCl. The gelation occurred solvent/oil. The weight measurements of the aerogels with absorbed oil
within 15 min. were carried out quickly to avoid evaporation of the solvent/oil.
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. 3. Results and discussion
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- Silica hydrogels were prepared by a single-step sol–gel process of
nol was replaced by n-hexane in 6 h. The whole exchange process was deionized water (DI·H2O) diluted water glass in the presence of acid
carried out in 45 °C water bath and the solvent was removed by filtration. (hydrochloric acid) catalyst, as shown in the following reactions:
The surface chemical modification of the gel was carried out by
Hydrolysis : Na2 SiO3 þ H2 O þ 2HCl→SiðOHÞ4 þ 2NaCl ð3Þ
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.
Condensation : SiðOHÞ4 þ ðOHÞ4 Si→ðOHÞ3 Si–O–SiðOHÞ3 þ H2 O: ð4Þ
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
When the liquid contained in the pores of hydrogel vaporised, the
every 2 h to make sure that the aerogel was dried completely.
capillary pressure which can lead to pore collapse is occurred. It can
be calculated with the following equation:
2.2. Characterization
p ¼ 2σcosθ=r ð5Þ
The bulk density of the aerogel sample was calculated by measuring
its mass to volume ratio. The porosity of the aerogels was calculated where p is capillary pressure, σ is surface tension of solvent, θ is contact
using the following formula: angle and r represents the capillary radius. To minimize the capillary
  pressure, the solvent exchange and surface modification process is
ρ necessary. Through comparison (Table 1), ethanol and n-hexane were
porosity ¼ 1− a  100% ð1Þ
ρs chosen to be the exchange solvents, respectively. TMCS was the surface
silylation reagent and the chemical reaction in the surface modification
where ρa is the bulk density of aerogel and ρs is the skeleton density of process is as follows:
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 ðCH3 Þ3 SiCl þ ≡ Si–OH→ ≡ Si–O–SiðCH3 Þ3 þ HCl: ð6Þ
Atomic Emission Spectroscopy (ICP-AES).
The contact angle measurements were performed using a KSV After gelation, measured by ICP-AES, the weight content of sodium
(Helsinki, Finland) CAM 200 contact angle goniometer at ~ 20 °C. The in the hydrogel is 1.24%, while it sharply decreased to 0.02% after the
thermal stability of aerogel sample was studied by the thermal gravi- DI·H2O washing process. So the DI·H2O washing is an effective way to
metric and differential thermal analysis (TG-DTA) using SDT Q600 (TA remove the sodium in the hydrogel. To determine the volume ratio
Instruments, USA). TG-DTA can also help to determine the oxidation of the solvent DI water to water glass, a series of experiments setting
temperature of –CH3 group contained in the aerogel, that is, the temper- the volume ratio from 1 to 5 with increment of 1 were conducted, in
ature up to which the silica aerogel samples retain its hydrophobicity. which enough TMCS was added to the system to modify the gel. The
The hydrophobic nano-porous silica aerogels with a weight of 6 mg porosity is presented in Fig. 1. It is clear that when the volume ratio is
were heat-treated in air, from room temperature (25 °C) up to 800 °C, 3, the obtained aerogels have the highest porosity. And thus the volume
with a controlled heating rate of 10 °C·min−1. ratio of DI water to water glass is fixed 3.
The microstructure and morphology of the aerogels were studied
using Field Emission Scanning Electron Microscope (FESEM) (SIRION 200, Table 1
FEI, USA). The specific surface areas were determined by nitrogen sorp- Surface tension of several solvents at 20 °C [36].
tion isotherms with standard Brunauer–Emmett–Teller (BET) analysis Solvent Surface tension (10−3 N·m−1)
(Tristar II 3020 M, Micromeritics Instrument Corporation, USA). The cu-
Isopropanol 21.7
mulative pore volume was calculated from the N2 adsorption–desorption n-Hexane 18.4
profiles. The average pore diameters and pore size distributions (PSD) Acetone 23.7
were estimated by the Barrett–Joyner–Halenda (BJH) method (Tristar II Ethanol 22.8
3020 M, Micromeritics Instrument Corporation, USA). The surface chem- Ethylene glycol 48.4
Water 72.7
ical modification of aerogels was studied using Fourier Transform Infrared
60 S. He et al. / Journal of Non-Crystalline Solids 410 (2015) 58–64

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
Fig. 1. Porosity of silica aerogel with no DMF.
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
The hydrophilic surface of hydrogel network became hydrophobic for upward 200 °C resulted from the condensation of hydroxyl that existed
the formation of alkoxytrimethylsilane (`Si\O\Si(CH3)3) (Eq. (6)). The in the surface aerogel. While as to the well modified aerogel, the weight
surface modification of the gels was studied by measuring the contact loss before 100 °C may be results from the evaporation of residual sol-
angle of water droplets on the silica aerogel surface under various molar vent and water molecules.
ratios of TMCS to pore water (denoted as N). As shown in Fig. 2, the con- To study the effect of DMF on the properties of silica aerogel, the
tact angle reached to 161° at N = 0.0311, which indicated a super hydro- molar ratio of Si to DMF was set as 3.34, 2.23, 1.11 and 0.83, corresponding
phobicity of the silica aerogel. And with the further increase of N, the to samples B2, B3, B4 and B5 respectively. The sample B1 was synthesized
contact angle almost remains the same (Table 2). N is set 0.0311 which without DMF.
is much smaller than that used in single step solvent exchange/surface The gelation time and physical properties of the silica aerogel are
modification [34]. listed in Table 3. The specific surface area of the sample is as high as
The super hydrophobicity of aerogel was attributed to the attach- 680 m2/g which is much larger than the ones without DMF [22,25,26].
ment of –Si(CH3)3 groups to the gel surface, which can be confirmed The polarity of DMF is relatively strong. The hydrogen bonds will form
by the Fourier Transform Infrared Spectroscopy (FT-IR) analysis, as between hydroxyls (− OH) in orthosiliconic acid and DMF molecules
shown in Fig. 3. It is evident that apart from the Si–O–Si (absorption which would impede the polycondensation of Si(OH)4. The condensa-
peak at about 470 cm− 1 and 1060 cm− 1 [37]), the modified silica tion rate slowed down and the gelation process lasted longer, just as
aerogels show strong absorption peaks at about 850 cm − 1 and shown in Table 3.
1260 cm− 1, which respectively correspond to the terminal Si–CH3 Fig. 5 shows that the silica aerogels' bulk density and volume shrink-
groups [37]. The presence of these two absorption peaks in the age affected by the gelation time apparently. Either for the bulk density
FTIR spectra confirms the attachment of –Si–CH3 groups from the or volume shrinkage, the U-shaped curve can be clearly seen with the
TMCS to the silica aerogel surface, indicating that the surface modi- increase of gelation time. When there is no DMF, the Si(OH)4 molecules
fication of the aerogels was successful. In addition, it is clear that the condensed quickly and disordered. While DMF was introduced, hydrogen
intensity of the bonds at ~ 3450 and ~ 1650 cm − 1 of –OH groups bond will be formed between hydroxyls in Si(OH)4 and DMF molecules,
were decreased but not disappeared after surface modification [2, then the condensation should be processed between the hydroxyls
37–40]. On one hand, the amount of Si–OH groups decreased after which were not hydrogen bonded with DMF. In this way, it can be consid-
modified by TMCS (Eq. (6)), leading to a weaker absorption intensi- ered that the condensation was conducted in some well-organized way.
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). 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 water quickly (Fig. 8a). Presented in Fig. 8b, the absorption capacity of
free hydroxyls (not hydrogen bonded with DMF) in Si(OH)4 in an the silica aerogels were measured using ethanol, n-hexane and gasoline,
ordered way. And the clusters or pore sizes become homogeneous. For respectively. Silica aerogels of 1 cm3 can absorb more than 0.9 ml organ-
B4 and B5, excess DMF resulted in much hydroxyls that hydrogen bond- ic liquids. Compared with the silica aerogels using TEOS as precursor [2],
ed with DMF, which will condense with each other under high energy the absorption capacity of the sample B3 in this study is obviously
condition, such as water bath or ambient pressure drying. The existed higher. The aerogels' absorption efficiency increased significantly.
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 4. Conclusion
Fig. 7d and e.
After being modified by TMCS, methyl groups were attached to the Super hydrophobic ( = 161°) and oleophylic silica aerogels were
surface, and the silica aerogels are hydrophobic and oleophylic. Thus successfully synthesized under ambient pressure using single step sol–
the silica aerogels can absorb organic liquids, such as n-hexane from gel polymerization of water glass. The volume ratio of deionized water
S. He et al. / Journal of Non-Crystalline Solids 410 (2015) 58–64 63

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.

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