polymers
Article
Eco-Friendly Fabrication of Highly Stable Silica Aerogel
Microspheres with Core–Shell Structure
Gao Cai, Haisong Ni, Xunzhang Li, Yangxin Wang *
Citation: Cai, G.; Ni, H.; Li, X.;
Wang, Y.; Zhao, H. Eco-Friendly
Fabrication of Highly Stable Silica
Aerogel Microspheres with
Core–Shell Structure. Polymers 2023,
15, 1882. https://doi.org/10.3390/
polym15081882
Academic Editor: Iolanda De Marco
Received: 23 February 2023
Revised: 6 April 2023
Accepted: 11 April 2023
Published: 14 April 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Polymers 2023, 15, 1882. https://doi.org/10.3390/polym15081882
and Huaixia Zhao *
College of Materials Science and Engineering, Nanjing Tech University, 30 South Puzhu Road, Pukou District,
Nanjing 211816, China
* Correspondence: yangxin.wang@njtech.edu.cn (Y.W.); zhaohx@njtech.edu.cn (H.Z.)
Abstract: Silica aerogel microspheres show great potential in various fields as fillings in different
materials. It is important to diversify and optimize the fabrication methodology for silica aerogel mi-
crospheres (SAMS). This paper presents an eco-friendly synthetic technique for producing functional
silica aerogel microspheres with a core–shell structure. Mixing silica sol with commercial silicone oil
containing olefin polydimethylsiloxane (PDMS) resulted in a homogeneous emulsion with silica sol
droplets dispersed in the oil. After gelation, the droplets were transformed into silica hydrogel or
alcogel microspheres and coated with the polymerization of the olefin groups. Microspheres with
silica aerogel as their core and polydimethylsiloxane as their shell were obtained after separation
and drying. The sphere size distribution was regulated by controlling the emulsion process. The
surface hydrophobicity was enhanced by grafting methyl groups onto the shell. The obtained silica
aerogel microspheres have low thermal conductivity, high hydrophobicity, and excellent stability. The
synthetic technique reported here is expected to be beneficial for the development of highly robust
silica aerogel material.
Keywords: aerogel spheres; core–shell structures; silicas; polysiloxanes; thermal insulation
1. Introduction
Silica aerogels are one kind of mesoporous amorphous material with many distinctive
characteristics, such as low bulk density, low thermal conductivity, low refractive index,
high porosity, and high specific surface area [1–5], which are derived from the nanoporous
network of interconnected primary particles. The voids in the network structure of silica
aerogels account for more than 90% of the whole volume. Although silica aerogels are
widely used in aerospace vehicles [6–8], civil buildings [9,10], clothes [11,12], environmental
purification materials [13], and drug delivery systems [14–17], their characteristics that are
not conducive to ductility lead to poor mechanical properties for silica aerogel monoliths.
This makes their direct use or hybridization with other materials difficult, which seriously
limits the application of silica aerogel in many fields [18–21]. Moreover, the repeated
modification process to transfer hydrophilicity to the hydrophobic surface of the silica
aerogel monolith is tedious and requires an extremely long processing time [22].
Instead, silica aerogel powders, e.g., microspheres or granules, as a new product
form, can make up for the poor mechanical performance of silica aerogel bulk when used
as fillings hybridized with other materials [23–27]. In addition, due to the tiny volume
of the silica aerogel powders, the modification and drying process is easier and faster,
which effectively decreases the fabrication time. A few silica aerogel powders have been
recently reported with various methods for rapid synthesis [22]. Pan et al. reported a
method to synthesize superhydrophobic (θ = 162◦ ) aerogel powders at ambient pressure
using a water-glass-based sol–gel method with a technological process of mechanical
crushing and filtration [28]. Bhagat et al. reported superhydrophobic silica aerogel powders
with simultaneous surface modification, solvent exchange, and sodium ion removal from
https://www.mdpi.com/journal/polymers
Polymers 2023, 15, 1882 2 of 11

hydrogels [29]. Lee et al. reported a fast synthesis technique for silica aerogel powders
by an emulsion polymerization method using water glass, n-hexane, and a surfactant
(Span80) [30]. Jiang et al. prepared an amine-grafted silica aerogel microsphere by dropping
the siliceous solution into a hot oil bath [31].
Although these methods successfully produced different SiO2 aerogel powders, there
are still some challenges, such as the imprecise control of the aerogel powder size in the
method of mechanical crushing and the one-step synergetic fabrication, and the strong
dependence on volatile and poisonous organic solvents in the emulsion method. The
method of dropping the siliceous solution into a hot oil bath is environmentally friendly
but only suitable for the preparation of big gel microspheres with a size in the millimeter
scale. It is thus still urgent to develop new methods for the efficient fabrication of silica
aerogel powders. The stability of the silica aerogel powders is another important challenge
for the development of the silica aerogel. Undecorated silica aerogel can be easily destroyed
once immersed in organic or inorganic solvents due to the high void volume fraction and
the relatively weak physical interaction between the nanoparticles. Most of the currently
reported silica aerogel spheres are modified with hydrophobic groups, which can efficiently
prevent water invasion to nanoporous structures. However, when these hydrophobic silica
aerogel spheres make contact with organic solvents, the nanoporous structures are filled
and destroyed. To date, very few studies involve silica aerogel spheres that are stable in
both water and organic solvents.
In this study, an eco-friendly and facile synthetic technique is reported that produces
functional silica aerogel microspheres (SAMS) with a core–shell structure. Droplets of silica
sol containing a gelation catalyst and polymerization initiators were obtained by mixing
silica sol with commercial silicone oil and olefin polydimethylsiloxane (PDMS) under
stirring. After gelation, the droplets were transformed into silica hydrogel or alcogel in the
form of microspheres, which were further coated by the subsequent polymerization of the
olefin groups on the polydimethylsiloxane. After separation and drying, the core–shell silica
aerogel microspheres were obtained. This method has the following advantages: 1. The
size distribution of the core–shell silica aerogel microspheres can be effectively regulated
by controlling the ratios of the silica sol to the silicone oil in the emulsion procedure.
2. The obtained microspheres with silica aerogel as their core and PDMS as their shell
show excellent stability in both water and organic solvents. 3. Various silica sources can
be used in the reported synthetic technique, e.g., water glass and TEOS. 4. The reported
synthetic technique uses silicone oil as the fabrication medium, which is environmentally
friendly. The specific synthetic technique reported here is expected to be beneficial for the
development and application of highly robust silica aerogels.

2. Materials and Methods

2.1. Materials and Methods
Water glass (WG) was supplied by Quechen Silicon Chemical Co., Ltd., Wuxi, China.
Glacial acetic acid (HAc), tetraethyl orthosilicate (TEOS), ammonia solution (AR), sodium
dodecyl sulfate (SDS), and ethanol absolute (EtOH) was purchased from Sinopharm Chemi-
cal Reagent Co., Ltd., Nanjing, China. Silicone oil PMX-200 (10 mPa.s) and triethoxymethyl-
silane (MTES) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.,
Shanghai, China. Hydrochloric acid (HCl) was purchased from Yonghua Chemical Co., Ltd.,
Suzhou, China. Olefin dimethylsiloxane (5000 mPa.s) was purchased from Dow Chemical
Company, Midland, MI, USA. Potassium persulfate (KPS) was purchased from Beijing In-
noChem Science & Technology Co., Ltd., Beijing, China. 2,20 -Azobis (2-methylpropionitrile)
(AIBN) was purchased from Shanghai Macklin Biochemical Co., Ltd., Shanghai, China.
DI water (W) was home-made. All chemicals were used as received without any further
purification. The morphology and particle size of the silica aerogel microspheres (SAMS)
were investigated using a scanning electron microscope (SEM, ZEISS 1530VP, Carl Zeiss
Microscopy Ltd., Cambridge, UK). Specific surface area and pore size distribution were
characterized by N2 adsorption/desorption test (BET, Quantachrome Autosorb-iQ ana-
Polymers 2023, 15, 1882 3 of 11

lyzer, Quantachrome Instruments, Boynton Beach, FL, USA). The core–shell structure of the
SAMS was studied using a fluorescence microscope (Nreeohy Y-E68, Shenzhen Nreeohy
Technology Co., Ltd., Shenzhen, China). The contact angle was measured using a con-
tact angle meter (JC2000C, Shanghai Zhongchen Digital Technology Equipment Co., Ltd.,
Shanghai, China). In order to better test the contact angle of aerogel particles, the aerogel
particles were compressed to the block plates with certain thicknesses and relatively flat
surfaces. The specimen was put on the instrument, and 5 µL deionized water was dropped
on the surface with a syringe at room temperature, and then we determined the contact
angle with a graphic method.

2.2. Fabrication of wg-SAMS-4.5/3.5/2.5

WG, W, and HAc were mixed with a mass ratio of 1.35:5:0.357 under room temperature
(25 ◦ C) to form a water glass solution, which was then dropped into the mixture of silicone
oil and olefin polydimethylsiloxane (PDMS) under strong mechanical stirring to form the
homogenous emulsion. The mass ratio of the water glass solution, olefin polydimethylsilox-
ane, and silicone oil was 4.5:1:1, 3.5:1:1, and 2.5:1:1 for the samples of wg-SAM-4.5/3.5/2.5,
respectively. The obtained emulsions were then gelated at room temperature (25 ◦ C) for
24 h to obtain spherical wet silica gels dispersed in the silicone oil. Silica gel spheres
were then washed with silicone oil, 2% SDS aqueous solution, and ethanol (EtOH) with
centrifugation, and then aged in EtOH for 48 h. The silica gel microspheres were then dried
with freeze–vacuum drying to obtain the SiO2 aerogel of wg-SAMS-4.5/3.5/2.5.

2.3. Fabrication of teos-SAMS-4.5/3.5/2.5

TEOS, EtOH, W, and HCl were mixed with a mass ratio of 2.632:6.314:0.9:0.044 at
50 ◦ C for 1 h to form a siliceous solution, into which was added a mass ratio of 0.136 of
ammonia solution (2 wt% in ethanol). The obtained siliceous solution was then dropped
into the mixture of silicone oil and olefin polydimethylsiloxane (PDMS) under strong
mechanical stirring to form the homogenous emulsion. The mass ratio of the siliceous
solution, olefin silicone oil, and silicone oil was 4.5:1:1, 3.5:1:1, and 2.5:1:1. The obtained
emulsions were then gelated at room temperature (25 ◦ C) for 24 h to obtain spherical wet
silica gels dispersed in the silicone oil. Silica gel spheres were then washed with silicone
oil, 2 wt% SDS aqueous solution, and EtOH with centrifugation, and then aged in EtOH for
48 h. The silica gel microspheres were then dried with freeze–vacuum drying to obtain the
SiO2 aerogel of teos-SAMS-4.5/3.5/2.5.

2.4. Fabrication of wg-SAMS-4.5@PDMS

WG, W, KPS, and HAc were mixed with a mass ratio of 1.35:5:0.36:0.357 under room
temperature (25 ◦ C) to form a water glass solution, which was then dropped into the
mixture of olefin silicone oil and silicone oil under strong mechanical stirring to form the
homogenous emulsion. The mass ratio of the water glass solution, olefin silicone oil, and
silicone oil was 4.5:1:1. The obtained emulsions were then gelated at room temperature
(25 ◦ C) for 24 h to obtain spherical wet silica gels dispersed in the olefin silicone oil.
The emulsion containing silica gel microspheres was then heated at 60 ◦ C for 8 h for
polymerization of the olefin silicone oil forming polydimethylsiloxane (PDMS) coating
on the surface of the silica gel spheres, which were then washed with silicone oil, 2 wt%
SDS aqueous solution, and EtOH with centrifugation, and then put in EtOH for 48 h. The
PDMS-coated silica gel microspheres were dried by freeze–vacuum drying to form the
PDMS-wrapped SiO2 aerogel of wg-SAMS-4.5@PDMS.

2.5. Fabrication of teos-SAMS-4.5@PDMS

TEOS, EtOH, W, AIBN, and HCL (2 wt% in ethanol) were mixed in a mass ratio of
2.632:6.314:0.9:0.48:0.044 at 50 ◦ C for 1 h to form a siliceous solution, to which was added a
mass ratio of 0.136 ammonia solution (2% in ethanol) at room temperature. The obtained
siliceous solution was then dropped into the mixture of silicone oil and olefin silicone oil
Polymers 2023, 15, 1882 4 of 11

under strong mechanical stirring to form the homogenous emulsion. The mass ratio of the
siliceous solution, olefin silicone oil, and silicone oil was 4.5:1:1. The obtained emulsions
were then gelated at room temperature (25 ◦ C) for 24 h to obtain spherical wet silica gels
dispersed in the silicone oil. The emulsion containing silica gel microspheres was then
heated at 80 ◦ C for 10 h for polymerization of olefin silicone oil forming PDMS coating
on the surface of the silica gel spheres, which were then washed with silicone oil, 2 wt%
SDS aqueous solution, and EtOH with centrifugation, and then put in EtOH for 48 h. The
PDMS-coated silica gel microspheres were dried by freeze–vacuum drying to form the
PDMS-wrapped SiO2 aerogel of teos-SAMS-4.5@PDMS.

2.6. Fabrication of wg-SAMS-4.5@PDMS-Me

This fabrication process was similar to the fabrication of wg-SAMS-4.5@PDMS; the
only difference was that after the PDMS coating, MTES with a mass ratio of 7.16 was added
to the mixture, which was heated at 60 ◦ C for an extra 6 h. The silica gel spheres were then
washed with silicone oil, 2% SDS aqueous solution, and EtOH with centrifugation, and then
put in EtOH for 48 h. The modified silica gel microspheres were dried by freeze–vacuum
drying to form the wg-SAMS-4.5@PDMS-Me.

2.7. Fabrication of teos-SAMS-4.5@PDMS-Me

This fabrication process was similar to the fabrication of teos-SAMS-4.5@PDMS; the
only difference was that after the PDMS coating, MTES, W, and HCl (2 wt% in ethanol)
with a mass ratio of 8.95:10:5.5 were added to the mixture which was then heated at
60 ◦ C for another 6 h. The silica gel spheres were then washed with silicone oil, 2 wt%
SDS aqueous solution, and EtOH with centrifugation, and then put in EtOH for 48 h.
The modified silica gel microspheres were dried by freeze–vacuum drying to form the
teos-SAMS-4.5@PDMS-Me.

3. Results and Discussion

The fabrication of the silica aerogel microspheres coated with polydimethylsiloxane
(SAMS@PDMS) is presented in Figure 1. The whole process mainly includes micellization,
gelation, polymerization, and modification. Two kinds of cheap silicon sources, water
glass and tetraethyl orthosilicate (TEOS), were used to obtain the initial silica sol. When
dropping these two silica sols into the mixture of alkylene polydimethylsiloxane (PDMS)
and silicone oil under fierce stirring, silica sol droplets in the shape of microspheres formed
in the obtained water–oil emulsion. The regulation of the size distribution of the formed
silica sol droplets was explored by changing the ratios of the silica sol in the silicone oil
(Figure S1). Figure S2 summarizes the size distribution of the silica sol droplets with the
varying amount of silica sol in the silicone oil during the fabrication process. The results
show that the size of the silica sol microspheres is significantly affected by the ratios of the
silica sol in the dispersion phase. As the ratios of the silica sol in the silicone oil decrease,
the viscosity of the mixture emulsion decreases, which makes possible the existence of silica
sol microspheres with a large size. In addition, the choice of the silicon sources could also
obviously influence the size distribution of the silica sol microspheres in the emulsion stage.
The size of the microspheres of the silica sol with TEOS as the silica source is obviously
larger than with water glass as the silica source. Moreover, increasing the stirring time
could homogenize the size distribution of the silica sol microspheres in the emulsion.
We further explored the fabrication process and investigated the critical influencing fac-
tors in detail step by step. After the full gelation process, the obtained wet gel microspheres
were observed in situ under an optical microscope. As shown in Figures S3 and S4, the wet
gel microspheres have almost the same size distribution as that of the above-mentioned
silica sol. This demonstrates that during the gelation process the size and the shape of
the microspheres in the emulsion are well retained. The emulsion mixture containing the
wet gel spheres was then demulsified with SDS solution, followed by washing, centrifu-
gation, and freeze–vacuum drying, resulting in the pure aerogel SAMS. The SEM images
 Polymers 2023, 15, 1882 5 of 11

of SAMS prepared from different ratios of silica sol in silicone oil are shown in Figure 2.
The regulation of the size distribution of the silica aerogel microspheres shows the same
variation trend as that of the wet gel microspheres with varying ratios of the silica sol in
silicone oil during the fabrication process. When a 4.5 mL solution of water glass was
added to the dispersion phase of 1 mL of silicone oil in the fabrication process, the size
of the resulting SiO2 aerogel sphere was about 5 µm (Figure 2a). Keeping the volume of
the dispersion phase of the silicone oil unchanged, when the volume of the water glass
solution decreased to 3.5 mL and 2.5 mL, the size of the resulting SiO2 aerogel sphere
increased to about 8 µm and 15 µm, respectively (Figure 2b,c). It was clearly observed that
the mass ratio of the continuous phase and the dispersion phase is the most important
influence factor for the size distribution of the resulting aerogel sphere. In addition, with
the same ratios of the silica sol in silicone oil in the fabrication process, the size of the
aerogel microspheres with TEOS as the silica source was obviously larger than with water
glass as the silica source. When a 4.5 mL solution of TEOS was added to the dispersion
phase of 1 mL of silicone oil in the fabrication process, the size of the resulting SiO2 aerogel
sphere was about 14 µm (Figure 2d). Keeping the volume of the dispersion phase of the
silicone oil unchanged, when the volume of the TEOS solution decreased to 3.5 mL and
2.5 mL, the size of the resulting SiO2 aerogel sphere increased to about 19 µm and 26 µm,
respectively (Figure 2e,f). The same size regulation rule between the silica sol droplets and
the SiO2 aerogel spheres shows that the size of the aerogel microspheres could be regulated
ymers 2023, 15, x FOR PEER REVIEW by controlling the formation process of the emulsion. Moreover, the size distribution of the 5 o
wet gel microspheres and the corresponding aerogel microspheres is similar, which means
that the microstructure of the SiO2 nanoparticles is well retained during the drying process
(Figures S4 and S5).

Figure 1. Schematic representation of the fabrication process and the core–shell structure of the
PDMS-coated
Figure SiO2 representation
1. Schematic aerogel microspheres
of (SAMS@PDMS).
the fabrication process and the core–shell structure of
PDMS-coated SiO2 aerogel microspheres (SAMS@PDMS).

We further explored the fabrication process and investigated the critical influenc
factors in detail step by step. After the full gelation process, the obtained wet gel mic
spheres were observed in situ under an optical microscope. As shown in Figures S3 a
S4, the wet gel microspheres have almost the same size distribution as that of the abo
mentioned silica sol. This demonstrates that during the gelation process the size and
Polymers 2023, 15, x FOR PEER REVIEW 6 of 12

Polymers 2023, 15, 1882 6 of 11

means that the microstructure of the SiO2 nanoparticles is well retained during the drying
process (Figures S4 and S5).

Figure 2. SEM
SEMimages
imagesofof
pure silica
pure aerogel
silica spheres
aerogel spheresof wg-SAMS-4.5 (a), wg-SAMS-3.5
of wg-SAMS-4.5 (b), wg-
(a), wg-SAMS-3.5 (b),
SAMS-2.5 (c), teos-SAMS-4.5
wg-SAMS-2.5 (d), (d),
(c), teos-SAMS-4.5 teos-SAMS-3.5 (e), (e),
teos-SAMS-3.5 andand
teos-SAMS-2.5 (f). (f).
teos-SAMS-2.5

N22 adsorption–desorption
adsorption–desorption isothermsisotherms of of the SiO22 aerogel
aerogel microspheres are shown in
Figure S6. The isotherms
isotherms for for SAMS
SAMS display
display type
type IV IV isotherms
isotherms with with H1
H1 hysteresis
hysteresis loops.
loops.
The noticeable saturation adsorption platforms demonstrate that there are no macropores
in the SAMS,
SAMS,whichwhichisissupported
supportedbybytheirtheir pore
pore sizesize distribution
distribution curves.
curves. TheTheporepore
size size
dis-
distribution
tribution curvescurvesof ofthethe SAMS
SAMS also
also showthat
show thatthe
thepores
poresareareconcentrated
concentrated in in the
the 2–15 nm
range. The results demonstrate
demonstrate that that the silica source used in the fabrication process has
the most obvious
the most obvious influence
influence on the nanostructures
on the nanostructures of the aerogel
of the aerogel microspheres.
microspheres. The The specific
specific
surface areas of all three samples of wg-SAMS-4.5/3.5/2.5 obtained
surface areas of all three samples of wg-SAMS-4.5/3.5/2.5 obtained with water glass as the with water glass as
the silica source in fabrication are more than 970 m 2 g−1 , which are obviously larger than
silica source in fabrication are more than 970 m g , which are obviously larger than the
2 −1

the surface
surface areas
areas of of
thethe samplesofofteos-SAMS
samples teos-SAMSofof745.49
745.49 m m22gg−1−,1 which
, whichwere
were obtained
obtained with
with
TEOS
TEOS as the silica source. Similarly, the mean pore diameters of SAMS with different silica
as the silica source. Similarly, the mean pore diameters of SAMS with different silica
sources
sources areare also
also different
different (Table
(TableS1).
S1).
In
In order to obtain the core–shellstructure,
order to obtain the core–shell structure, thetheinitiators
initiators were
were induced
induced intointo
thethe
emulsion
emul-
system
sion system during the fabrication process to trigger the polymerization of the group
during the fabrication process to trigger the polymerization of the alkylene alkylene in
the polydimethylsiloxane framework, which was coated on the
group in the polydimethylsiloxane framework, which was coated on the surface of the surface of the microspheres
of the wet silica
microspheres gel.wet
of the Forsilica
the gel.
different
For the silicon sources,
different silicon water
sources,glass and glass
water TEOS, theTEOS,
and inor-
ganic and organic initiators potassium persulfate and 2,2 0 -azobis (2-methylpropionitrile)
the inorganic and organic initiators potassium persulfate and 2,2′-azobis (2-methylpropi-
(AIBN) were used, respectively. AIBN and potassium persulfate were added to the alcohol
onitrile) (AIBN) were used, respectively. AIBN and potassium persulfate were added to
solution of TEOS and the aqueous solution of water glass, respectively. After the gela-
the alcohol solution of TEOS and the aqueous solution of water glass, respectively. After
tion process, the emulsion mixtures were heated to trigger the polymerization of olefin
the gelation process, the emulsion mixtures were heated to trigger the polymerization of
polydimethylsiloxane, thus coating the wet silica gel spheres and forming the core–shell
structure. After the subsequent demulsification, washing, and separation by centrifugation
Polymers 2023, 15, x FOR PEER REVIEW 7 of 12

Polymers 2023, 15, 1882 olefin polydimethylsiloxane, thus coating the wet silica gel spheres and forming the core– 7 of 11
shell structure. After the subsequent demulsification, washing, and separation by centrif-
ugation and freeze–vacuum drying, the SiO2 aerogel microspheres of wg-SAMS-
4.5@PDMS and teos-SAMS-4.5@PDMS were obtained.
and freeze–vacuum drying, the SiO2 aerogel microspheres of wg-SAMS-4.5@PDMS and
Fluorescence optical microscopy was used to explore the core–shell structure of the
teos-SAMS-4.5@PDMS were obtained.
PDMS-wrapped silica aerogel microspheres of wg-SAMS-4.5@PDMS and teos-SAMS-
Fluorescence optical microscopy was used to explore the core–shell structure of the
4.5@PDMS. Before the fluorescent imaging, these two PDMS-wrapped silica aerogel mi-
PDMS-wrapped silica aerogel microspheres of wg-SAMS-4.5@PDMS and teos-SAMS-
crospheres were immersed in an aqueous solution of a fluorescent dye for a few days to
4.5@PDMS. Before the fluorescent imaging, these two PDMS-wrapped silica aerogel mi-
let the dye molecules diffuse into the PDMS coating completely. The chemical structure
crospheres were immersed in an aqueous solution of a fluorescent dye for a few days to
of the fluorescent dye was a water-soluble sodium salt of N,N′-Di (2-succinic acid)-
let the dye molecules diffuse into the PDMS coating completely. The chemical structure of
perylene-3,4,9,10-tetracarboxylic bisimide. The perylene structure made it compatible
the fluorescent dye was a water-soluble sodium salt of N,N0 -Di (2-succinic acid)-perylene-
with the polydimethylsiloxane
3,4,9,10-tetracarboxylic bisimide.(PDMS) networkstructure
The perylene but incompatible with the inorganic
made it compatible sil-
with the poly-
ica. Therefore, the dye molecule could pass through the PDMS matrix
dimethylsiloxane (PDMS) network but incompatible with the inorganic silica. Therefore, and stain the shell
structure, separating
the dye molecule thepass
could PDMS shell from
through the silica
the PDMS coreand
matrix in the imaging
stain process.
the shell As shown
structure, separat-
ining
Figure
the PDMS shell from the silica core in the imaging process. As shown in Figure 3,show
3, these two samples of wg-SAMS-4.5@PDMS and teos-SAMS-4.5@PDMS these
astwo
solid spheres
samples ofunder white-light irradiation
wg-SAMS-4.5@PDMS (Figure 3a,c), while obvious
and teos-SAMS-4.5@PDMS showcore–shell struc-
as solid spheres
tures
under were observedirradiation
white-light under irradiation
(Figure with
3a,c),awhile
blue light of 480
obvious nm (Figure
core–shell 3b,d). It were
structures is diffi-
ob-
cult for the dye molecule to enter inorganic SiO 2 aerogels, so there is no fluorescence emis-
served under irradiation with a blue light of 480 nm (Figure 3b,d). It is difficult for the dye
sion even under
molecule to enter theinorganic
irradiationSiOof blue light. The PDMS shell can be clearly distinguished
2 aerogels, so there is no fluorescence emission even under
from the SiO aerogel core because
the irradiation of blue light. The PDMS
2 of the fluorescence
shell emission.
can be clearly The formation
distinguished from the of SiO
the2
PDMS shells on the SiO aerogel core was further demonstrated by the FT-IR
aerogel core because of the fluorescence emission. The formation of the PDMS shells on the
2 spectra anal-
ysis
SiO(Figure S7).
2 aerogel core was further demonstrated by the FT-IR spectra analysis (Figure S7).

Figure 3. Optical microscope images of the core–shell structure of PDMS-wrapped SiO2 aerogel
Figure 3. Optical microscope images of the core–shell structure of PDMS-wrapped SiO2 aerogel mi-
microspheres of wg-SAMS-4.5@PDMS (a,b) and teos-SAMS-4.5@PDMS (c,d) under white light (a,c) and
crospheres of wg-SAMS-4.5@PDMS (a,b) and teos-SAMS-4.5@PDMS (c,d) under white light (a,c)
blue light (b,d) (480 nm), respectively. Photographs of water droplets on the samples of wg-SAMS-
and blue light (b,d) (480 nm), respectively. Photographs of water droplets on the samples of wg-
4.5@PDMS (e) and(e)
SAMS-4.5@PDMS teos-SAMS-4.5@PDMS (f). SEM images
and teos-SAMS-4.5@PDMS (f). SEMof methyl-modified PDMS-wrapped
images of methyl-modified PDMS-SiO2
aerogel microspheres of wg-SAMS-4.5@PDMS-Me (g) and teos-SAMS-4.5@PDMS-Me
wrapped SiO2 aerogel microspheres of wg-SAMS-4.5@PDMS-Me (g) and teos-SAMS-4.5@PDMS-Me (h). Photographs
of water
(h). dropletsof
Photographs onwater
the samples of on
droplets wg-SAMS-4.5@PDMS-Me (i) and teos-SAMS-4.5@PDMS-Me
the samples of wg-SAMS-4.5@PDMS-Me (j).
(i) and teos-SAMS-
4.5@PDMS-Me (j).
The special framework of PDMS also influences the hydrophobicity of the SAMS@PDMS
samples. As shown in Figure 3e,f, the water contact angles of wg-SAMS-4.5@PDMS and
teos-SAMS-4.5@PDMS are 114.63◦ and 133.40◦ , respectively. The hydrophobicity is just
on the middle level compared with the superhydrophobic material. This is due to the
obvious hydrophilicity of the Si-O-Si in the main chain of PDMS, which decreases the
 4.5@PDMS and teos-SAMS-4.5@PDMS are 114.63° and 133.40°, respectively. The hydro-
phobicity is just on the middle level compared with the superhydrophobic material. This
is due to the obvious hydrophilicity of the Si-O-Si in the main chain of PDMS, which de-
creases the hydrophobicity of the methyl group on the side chain of PDMS. In order to 8 of 11
Polymers 2023, 15, 1882
enhance the hydrophobicity performance of the SAMS@PDMS, further methylation was
performed on the PDMS coating. During the fabrication procedure, after the polymeriza-
tion of the olefin polydimethylsiloxane
hydrophobicity of the methylon thegroup
surface of the
on the sideSiO 2 wet
chain gel, the
of PDMS. In coated
order toSiO 2
enhance the
sphere was separated by centrifugation.
hydrophobicity performanceTheofobtained SiO2 aerogel
the SAMS@PDMS, sphere
further was then
methylation wasdis-
performed
on the
persed in the ethanol PDMS coating.
solution of MTES During the fabrication
to modify the PDMS procedure,
surfaceafterwith
the polymerization
the methyl of the
olefin polydimethylsiloxane on the surface
group. The obtained wg-SAMS-4.5@PDMS-Me and teos-SAMS-4.5@PDMS-Me of the SiO 2 wet gel, the coated
bothSiO 2 sphere was
main-
separated by centrifugation. The obtained SiO2 aerogel sphere was then dispersed in the
tained their sphere shape very well (Figure 3g,h). Notably, the hydrophobicity of these
ethanol solution of MTES to modify the PDMS surface with the methyl group. The obtained
two methyl-modified samples was obviously
wg-SAMS-4.5@PDMS-Me enhanced to superhydrophobicity
and teos-SAMS-4.5@PDMS-Me both maintained levels
their sphere
with a more than 150° water contact angle (Figure 3i,j).
shape very well (Figure 3g,h). Notably, the hydrophobicity of these two methyl-modified
The porous nanostructure of the silica
samples was obviously aerogel
enhanced endows it superthermal
to superhydrophobicity levels with a more than 150◦
insulation.
However, the purewaterSiO2contact
aerogelangle (Figure 3i,j).
is usually sensitive to solvents. Once the solvents enter
the pores, the evaporation of the solvents canofdestroy
The porous nanostructure the silicatheaerogel endows it superthermal
nanostructure which is com- insulation.
However, the pure SiO2 aerogel is usually sensitive to solvents. Once the solvents enter
posed of connectedthe SiO 2 particles, making the related material lose its thermal insulation.
pores, the evaporation of the solvents can destroy the nanostructure which is com-
In our study, water andofhexane
posed connectedwere
SiO2chosen tomaking
particles, estimate the the stability
related materialoflose
theitsSAMS
thermalandinsulation.
SAMS@PDMS to organicIn our study, water and hexane were chosen to estimate the stability of the 4a,
and inorganic solvents, respectively. As shown in Figure SAMS and
when we put the pure SiO2 aerogel
SAMS@PDMS sample
to organic of teos-SAM-4.5
and inorganic in water and
solvents, respectively. As in hexane
shown for 54a, when
in Figure
we put the pure SiO aerogel sample of teos-SAM-4.5 in water
days, the sizes of the aerogel microspheres in both cases sharply reduced, which is caused
2 and in hexane for 5 days,
the sizes of the aerogel microspheres in both cases sharply reduced, which is caused by the
by the destruction of the porous nanostructures during the immersion and drying process.
destruction of the porous nanostructures during the immersion and drying process. No-
Notably, when thetably,
PDMS-wrapped aerogel sample of teos-SAMS-4.5@PDMS was put in
when the PDMS-wrapped aerogel sample of teos-SAMS-4.5@PDMS was put in water
water and in hexane, the
and in SiO2 the
hexane, aerogel maintained
SiO2 aerogel its sphere
maintained its sphereshape
shape very wellwith
very well with un-
unchanged size
changed size distribution (Figure 4b).
distribution (Figure 4b).

Figure 4. (a) SEM images and the size distribution statistics data of the pure SiO2 aerogel microspheres
Figure 4. (a) SEM images and the size distribution statistics data of the pure SiO2 aerogel micro-
of teos-SAMS-4.5 at different states: intact sample (i), dried sample after immersion in water for
spheres of teos-SAMS-4.5 at different states: intact sample (i), dried sample after immersion in water
5 days (ii), and dried sample after immersion in hexane for 5 days (iii). (b) SEM images of the PDMS-
for 5 days (ii), and dried sample after immersion in hexane for 5 days (iii). (b) SEM images of the
wrapped silica aerogel microspheres of teos-SAMS-4.5@PDMS at different states: intact sample (i),
PDMS-wrapped silica aerogel microspheres
dried sample after immersion of teos-SAMS-4.5@PDMS
in water for 5 days (ii), andatdried
different states:
sample after intact sam-in hexane
immersion
ple (i), dried samplefor
after immersion
5 days inshow
(iii). Insets water
thefor
size5 distribution
days (ii), and dried
of the sample
aerogel after immersion in
microspheres.
hexane for 5 days (iii). Insets show the size distribution of the aerogel microspheres.
In order to explore the protective effectiveness of the PDMS shell for the nanoporous
In order to explore theofprotective
structure the SiO2 aerogel powders,of
effectiveness we compared
the the thermal
PDMS shell for theinsulation
nanoporous performance
of the pure SiO2 aerogel samples and the PDMS-wrapped aerogel samples before and
structure of the SiO2 aerogel powders, we compared the thermal insulation performance
after the solvent treatment. Before the solvent treatment, the thermal conductivity of teos-
of the pure SiO2 aerogel samples and the PDMS-wrapped aerogel samples before and after
SAMS and teos-SAMS@PDMS was 0.01976 (W/m·k) and 0.01985 (W/m·k), respectively.
the solvent treatment. Beforeconductivity
The thermal the solvent treatment,and
of wg-SAMS the thermal conductivity
wg-SAMS@PDMS was 0.02105of (W/m
teos- ·k) and
0.02188 (W/m·k), respectively. As shown in Figure 5a,b, the intact samples of teos-SAMS-
Polymers 2023, 15, x FOR PEER REVIEW 9 of 12

Polymers 2023, 15, 1882 SAMS and teos-SAMS@PDMS was 0.01976 (W/m·k) and 0.01985 (W/m·k), respectively. 9 of 11
The thermal conductivity of wg-SAMS and wg-SAMS@PDMS was 0.02105 (W/m·k) and
0.02188 (W/m·k), respectively. As shown in Figure 5a,b, the intact samples of teos-SAMS-
4.5 and teos-SAMS-4.5@PDMS have similar thermal insulation, as do the samples of wg-
4.5 and teos-SAMS-4.5@PDMS have similar thermal insulation, as do the samples of wg-
SAMS-4.5 and wg-SAMS-4.5@PDMS, which demonstrates that the PDMS shell does not
SAMS-4.5 and wg-SAMS-4.5@PDMS, which demonstrates that the PDMS shell does not
decrease the thermal insulation of the aerogel particles. We then compared the recycled
decrease the thermal insulation of the aerogel particles. We then compared the recycled
teos-SAMS-4.5, wg-SAMS-4.5@PDMS, and teos-SAMS-4.5@PDMS at the same heating
teos-SAMS-4.5, wg-SAMS-4.5@PDMS, and teos-SAMS-4.5@PDMS at the same heating state
state for 70 min to test their thermal insulation performance. Figure 5c,d show that the
for 70 min to test their thermal insulation performance. Figure 5c,d show that the thermal
thermal insulation of the recycled aerogel samples of teos-SAM-4.5 decreases obviously
insulation of the recycled aerogel samples of teos-SAM-4.5 decreases obviously compared
compared with the intact sample, which is supposed to raise from the breaking down of
with the intact sample, which is supposed to raise from the breaking down of the porous
the porous structure of the aerogel. After treatment with water and n-hexane, the thermal
structure of the aerogel. After treatment with water and n-hexane, the thermal conductivity
conductivity
of teos-SAMSofwasteos-SAMS was 0.08437
0.08437 (W/m ·k) and(W/m·k) and 0.06285
0.06285 (W/m (W/m·k), respectively,
·k), respectively, while
while the thermal
the thermal conductivity of wg-SAMS@PDMS and teos-SAMS@PDMS
conductivity of wg-SAMS@PDMS and teos-SAMS@PDMS remained unchanged. Notably, remained un-
changed. Notably, the recycled PDMS-wrapped aerogel samples
the recycled PDMS-wrapped aerogel samples of teos-SAMS-4.5@PDMS and wg-SAMS- of teos-SAMS-
4.5@PDMS
4.5@PDMS and wg-SAMS-4.5@PDMS
can retain the same thermalcan retain the
insulation same
level thermal
as that insulation
of the level as
intact sample, that
which
of the intact sample, which demonstrates that the PDMS shell could effectively
demonstrates that the PDMS shell could effectively help maintain the integrity of the help main-
tain thestructure
porous integrity of
of the
the SiO
porous structure
aerogel core.of the SiO2 aerogel core.
2

Figure 5. (a) Infrared images

images of
of the
the intact
intact powders
powders of of teos-SAMS-4.5
teos-SAMS-4.5 (1),(1), teos-SAMS-4.5@PDMS
teos-SAMS-4.5@PDMS (2), (2),
wg-SAMS-4.5
wg-SAMS-4.5 (3), and wg-SAMS-4.5@PDMS (4) on the hot surface. (b) The
(3), and wg-SAMS-4.5@PDMS (4) on the hot surface. (b) The surface temperature
surface temperature
curve
curve as
as aa function
function of
of time for SAMS
time for SAMS and and SAMS@PDMS.
SAMS@PDMS. (c) (c) Infrared
Infrared images
images ofof the
the solvent-treated
solvent-treated
powders of teos-SAMS-4.5 (1-water and 1-hexne), teos-SAMS-4.5@PDMS (2-water and 2-hexane),
powders of teos-SAMS-4.5 (1-water and 1-hexne), teos-SAMS-4.5@PDMS (2-water and 2-hexane), and
and wg-SAMS-4.5@PDMS (4-water and 4-hexane) on the hot surface. 1-water and 1-hexne: teos-
wg-SAMS-4.5@PDMS (4-water and 4-hexane) on the hot surface. 1-water and 1-hexne: teos-SAMS-4.5
SAMS-4.5 powder after immersion in water and in hexane for 5 days, respectively; 2-water and 2-
powderteos-SAMS-4.5@PDMS
hexne: after immersion in water and in
powder hexane
after for 5 days,
immersion respectively;
in water 2-waterfor
and in hexane and5 2-hexne: teos-
days, respec-
SAMS-4.5@PDMS powder after immersion in water and in hexane for 5 days,
tively; 4-water and 4-hexne: wg-SAMS-4.5@PDMS powder after immersion in water and in hexanerespectively; 4-water
and5 4-hexne:
for wg-SAMS-4.5@PDMS
days, respectively. powderinsulation
During the thermal after immersion
test, the in waterpowders
aerogel and in hexane forin
were put 5 glass
days,
respectively. During the thermal insulation test, the aerogel powders were put in glass petri dishes
without lids, which were put on the hot face for 70 min before imaging. (d) Surface temperature
curve as a function of time for solvent-treated SAMS and SAMS@PDMS.
Polymers 2023, 15, 1882 10 of 11

4. Conclusions
In summary, we have reported a facile synthetic technique to produce functional silica
aerogel microspheres with a core–shell structure. Water glass and tetraethyl orthosilicate
were used as the precursors of the silica aerogels. The silica sol was firstly gradually added
into the mixture of commercial silicone oil and olefin polydimethylsiloxane under strong
stirring, resulting in a homogeneous emulsion with droplets of silica sol in the silicone oil.
During the subsequent sol–gel process, the droplets of silica solution were transformed into
hydrogel or alcogel microspheres, which were further coated by the subsequent polymer-
ization of the olefin groups on the polydimethylsiloxane. After centrifugal separation and
freeze–vacuum drying, the core–shell microspheres were obtained. The size distribution of
the core–shell silica aerogel microspheres was effectively regulated. The surface hydropho-
bicity was further enhanced by grafting the methyl group onto the shell of the silica aerogel
microspheres. The obtained silica aerogel microspheres have low thermal conductivity,
superhydrophobicity, and excellent stability. The reported synthetic technique is expected
to offer a new fabrication strategy for highly robust silica aerogel.

Supplementary Materials: The following supporting information can be downloaded at: https://www.
mdpi.com/article/10.3390/polym15081882/s1, Figure S1: optical images of the silica sol microdroplets;
Figure S2: size distribution of silica sol microdroplets; Figure S3: optical images of the silica wet gel
microspheres; Figure S4: size distribution of silica wet gel microspheres; Figure S5: size distribution of silica
aerogel microspheres; Figure S6: adsorption–desorption isotherms of silica aerogel microspheres; Figure S7:
FTIR spectra curves of aerogel specimens; Table S1: physical properties of silica aerogel microspheres of
wg-SAMS-4.5, wg-SAMS-3.5, wg-SAMS-2.5, and teos-SAMS-4.5.
Author Contributions: Conceptualization, Y.W. and H.Z.; data curation, G.C. and H.N.; investigation,
G.C.; methodology, X.L. and Y.W.; supervision, Y.W. and H.Z.; writing—original draft, G.C. and
H.Z.; writing—review and editing, Y.W. and H.Z. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded by the Natural Science Foundation of Jiangsu Higher Education
Institutions of China under award number 21KJB430029, National Natural Science Foundation of
China under award number 21704012, and Startup Fund for Scientific Research from Nanjing Tech
University and the Priority Academic Program Development of Jiangsu Higher Education Institutions
(PAPD). This research received no external funding.
Institutional Review Board Statement: Not applicable.
Data Availability Statement: Data will be made available on request.
Conflicts of Interest: The authors declare no conflict of interest.

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