molecules

Article
Silica Aerogel Monoliths Derived from Silica
Hydrosol with Various Surfactants
Dong Chen, Xiaodong Wang * , Wenhui Ding, Wenbing Zou, Qiong Zhu and Jun Shen *
School of Physics Science and Engineering & Shanghai Key Laboratory of Special Artificial Microstructure
Materials and Technology, Tongji University, Shanghai 200092, China; Dongchen326@163.com (D.C.);
Giacinta_hui@163.com (W.D.); zouwenbing@tongji.edu.cn (W.Z.); zhuqiong113@163.com (Q.Z.)
* Correspondence: xiaodong_wang@tongji.edu.cn (X.W.); shenjun67@tongji.edu.cn (J.S.);
Tel.: +86-2165982762 (X.W.); +86-2165982762 (J.S.)

Academic Editor: Carlos A. García-González




Received: 22 October 2018; Accepted: 30 November 2018; Published: 4 December 2018

Abstract: Owing to their ultra-low thermal conductivity, silica aerogels are promising thermal
insulators; however, their extensive application is limited by their high production cost. Thus,
scientists have started to explore low-cost and easy preparation processes of silica aerogels. In this
work, a low-cost method was proposed to prepare silica aerogels with industrial silica hydrosol and
a subsequent ambient pressure drying (APD) process. Various surfactants (cationic, amphoteric, or
anionic) were added to avoid solvent exchange and surface modification during the APD process.
The effects of various surfactants on the microstructure, thermal conductivity, and thermal stability of
the silica aerogels were studied. The results showed that the silica aerogels prepared with a cationic
or anionic surfactant have better thermal stability than that prepared with an amphoteric surfactant.
After being heated at 600 ◦ C, the silica aerogel prepared with a cationic surfactant showed the
highest specific surface area of 131 m2 ·g−1 and the lowest thermal conductivity of 0.038 W·m−1 ·K−1 .
The obtained low-cost silica aerogel with low thermal conductivity could be widely applied as a
thermal insulator for building and industrial energy-saving applications.

Keywords: silica hydrosol; aerogel; ambient pressure drying; surfactant

1. Introduction
Silica aerogels [1–6], as a kind of highly porous material, have shown great potential application
in energy-saving windows and doors [7], solar energy integration, and building energy efficiency [8,9]
due to their unique structure and properties such as low density (3–500 mg·cm−3 ), high porosity
(80–99.8%), low dielectric constant, and low thermal conductivity [2,10,11]. In particular, the pore size
of silica aerogel is smaller than the mean free path of air molecules. This, along with its tortuous solid
network, gives silica aerogel an ultra-low thermal conductivity [10,12]. Therefore, silica aerogel has
promising applications in building and industrial energy saving. However, the extensive application of
silica aerogel is limited by its high production cost. In general, silica aerogels are fabricated by means
of the hydrolysis and condensation of silicon alkoxides to obtain wet gels and subsequent drying to
remove the solvent [13,14]. Unfortunately, the raw materials (such as tetraethyl orthosilicate) used
for fabrication are expensive and the supercritical drying (SCD) process is expensive and complex.
To simplify the preparation process and reduce their costs, inexpensive silicon sources were adopted as
precursors to prepare silica aerogels, such as silica hydrosol [15] and water glass [16,17]. To avoid the
need for expensive equipment, SCD with high pressure and a long time consumption—the ambient
pressure drying (APD) method developed by Smith [18]—was successfully employed to facilitate
the drying process. However, the solvent exchange and surface modification involved in this APD
process are still laborious, costly, and time-consuming. Moreover, ambient pressure-dried aerogels

Molecules 2018, 23, 3192; doi:10.3390/molecules23123192 www.mdpi.com/journal/molecules

Molecules 2018, 23, 3192 2 of 11

usually show serious cracking due to the fragile structure of the gels. As we know, surfactants usually
can be divided into three categories: cationic, amphoteric, and anionic. The surface activity of the
surfactant plays an important role in acid or alkaline solution. On the one hand, the surfactants could
form a saturated adsorption layer on the surface of solvent which would reduce the surface tension
of the liquid and the pore structure of the silica aerogel would be well preserved after APD. On the
other hand, amphiphilic surfactant molecules could form micelles in solution with a hydrophobic core
stabilized by a hydrophilic shell [19,20]. Those hydrophilic micelles would attach to the surface of
silica particles and become embedded in the silica network through hydroxyl groups, which would
influence the structure of the silica aerogel. After being heated at an appropriate temperature, the
organic surfactants and micelles can be removed and the occupied space will be released to form more
pores in the silica aerogel. Here, organic surfactants and micelles act like a “pore-forming agent”.
Moreover, some recent works [21–24] on the effect of surfactants in silica aerogels have also reported.
In this work, we report a one-pot APD synthesis method to fabricate silica aerogel monoliths
from industrial silica hydrosol in an aqueous system. Compared with water glass, industrial silica
hydrosol is a better choice due to its relatively high purity; thus, no further ion exchange is required.
In addition, there is no hydrolysis process by using silica hydrosol as a precursor and it is not necessary
to accurately control the hydrolysis reaction rate. Solvent exchange and surface modification were
avoided by adding various surfactants. The surfactant, which serves as a functional additive, will
reduce the surface tension of the solvent and produce more nanopores after being heated at an
appropriate temperature. Various silica aerogel monoliths were obtained by the addition of various
surfactants under an acid–base two-step condition and subsequent APD process. The effect of types
of surfactants and heat treatment on the morphology, pore structure, thermal stability, and thermal
conductivity of the silica aerogels were investigated. Using a low-cost industrial silica hydrosol as the
raw material and water as the solvent, along with the convenient APD process, this method greatly
simplifies the preparation process and reduces the cost.

2. Experimental Section

2.1. Materials
Silica hydrosol (alkaline, 20 wt%) was purchased from Wuhan Zhifa Technology Co., Ltd. (Wuhan,
China). Hydrochloric acid, ammonia hydroxide, hexadecyl trimethyl ammonium bromide (CTAB,
cationic), and sodium dodecyl sulfate (SDS, anionic) were purchased from Sinopharm Chemical
Reagent Co., Ltd. (Shanghai, China). Lauramidopropyl betaine (RALUFON 414, amphoteric, 35 wt%)
was purchased from Shandong Yousuo Chemical Technology Co., Ltd. (Qingdao, China).

2.2. Preparation of Silica Aerogels with Surfactant

The silica wet gels were prepared from silica hydrosol by adding the surfactant (cationic,
amphoteric, or anionic) under an acid–base two-step catalytic condition, and the mixture was
subsequently dried through the APD process. Firstly, 10 mL of silica hydrosol and 30 mL of water
(molar ratio of SiO2 and water—1:44.3) were mixed together with vigorous stirring for 5 min. Then, a
small amount of surfactant and hydrochloric acid solution were successively added into the mixture to
keep the pH value within 2–5, and the mixture was stirred for 15 min at room temperature. Secondly,
an ammonia solution was added into the mixture to adjust the pH value to 8–9, and this was further
stirred for 15 min. The obtained mixture was aged in an oven at 50 ◦ C for 4 h. Finally, the aged gel was
ambient pressure-dried sequentially at 60 ◦ C for 2 days and at 75 ◦ C for 1 day. The optimal molar ratios
of the cationic (CTAB), anionic (SDS), and amphoteric surfactant (RALUFON 414) to SiO2 were 1:68.7,
1:21.7, and 1:14.9, respectively. In the optimization of the amount of surfactant, the as-prepared silica
aerogels have a low density, low thermal conductivity, high specific surface area, and little shrinkage.
A possible synthesis flowchart of silica aerogels prepared with a surfactant is presented in Figure 1a.
Molecules 2018, 23, x 3 of 11
Molecules 2018, 23, 3192 3 of 11
high specific surface area, and little shrinkage. A possible synthesis flowchart of silica aerogels
prepared with a surfactant is presented in Figure 1a.
Herein, the surfactant plays an important role in the construction of the network structure and
Herein, the surfactant plays an important role in the construction of the network structure and
APD process. For step 1, the surfactant molecules are dispersed randomly in the silica hydrosol
APD process. For step 1, the surfactant molecules are dispersed randomly in the silica hydrosol
system before the addition of the hydrochloric acid solution. When the pH value of the system is
system before the addition of the hydrochloric acid solution. When the pH value of the system is
kept within 2–5, the surfactant and silica particles in the matrix will rearrange randomly to form a
kept within 2–5, the surfactant and silica particles in the matrix will rearrange randomly to form a
saturated adsorption layer and silica network structure. Because they are amphipathic, the surfactant
saturated adsorption layer and silica network structure. Because they are amphipathic, the
molecules orient themselves with the hydrophobic part towards the surface and the hydrophilic part
surfactant molecules orient themselves with the hydrophobic part towards the surface and the
towards the aqueous phase. That is to say, the formed saturated adsorption layer can cover solvent
hydrophilic part towards the aqueous phase. That is to say, the formed saturated adsorption layer
molecules with a high
can cover solvent surface
molecules freeaenergy
with and then
high surface freereduce
energytheand surface tensionthe
then reduce of surface
the whole solution.
tension of
Furthermore, when the ammonia solution is added (step 2), the surface hydrophilic
the whole solution. Furthermore, when the ammonia solution is added (step 2), the surface surfactant micelles
formed by the
hydrophilic surfactant
surfactant molecules
micelles willby
formed attach to the surface
the surfactant of the will
molecules silicaattach
particles and
to the connect
surface with
of the
the silica
silica network
particles andstructure
connectbywith
hydroxyl groups
the silica [20], which
network accelerate
structure the gelation
by hydroxyl rate[20],
groups and develop
which
aaccelerate
new network structure. Photographs of the gel evolution during the preparation
the gelation rate and develop a new network structure. Photographs of the gel evolution of silica aerogels
with
duringthethe
surfactant are shown
preparation in Figure
of silica 1b. with
aerogels The silica cluster formed
the surfactant randomly
are shown in the aqueous
in Figure 1b. The system
silica
when
cluster formed randomly in the aqueous system when a certain amount of hydrochloric acid 8–9,
a certain amount of hydrochloric acid was added. After the pH value was adjusted within was a
homogeneous white wet gel was rapidly produced, as shown in the bottom
added. After the pH value was adjusted within 8–9, a homogeneous white wet gel was rapidly of Figure 1b. It should
be noted that
produced, the preparation
as shown of theofwhole
in the bottom Figurewet
1b. gel was completed
It should in only
be noted that the 30 min, indicating
preparation the fast
of the whole
gelation process of this method.
wet gel was completed in only 30 min, indicating the fast gelation process of this method.

Figure 1.
Figure 1. (a)
(a) Synthesis
Synthesis flowchart
flowchartof
ofsilica
silicaaerogels
aerogelsprepared
preparedwith
withsurfactant.
surfactant.(b)
(b)Photographs
Photographsofof the
the gel
gel evolution
evolution during
during the the preparation
preparation of silica
of silica aerogels
aerogels withwith surfactant.
surfactant.

In
In order
order to
to simply
simply distinguish silica aerogels
distinguish silica aerogels prepared
preparedwithwithdifferent
differentsurfactants
surfactantsandandheating
heating
temperatures,
temperatures, samples prepared
prepared with
with different
differentprocesses
processeswere
weredenoted
denotedusing
usingdifferent
differentsymbols.
symbols.S-1,S-1,
S-2,
S-2, and
andS-3
S-3represent
representthe
theas-prepared
as-preparedaerogels
aerogelswith CTAB
with CTAB (cationic), RALUFON414
(cationic), RALUFON414 (amphoteric),
(amphoteric),and
SDS
and (anionic), respectively.
SDS (anionic), S-1-200
respectively. (S-1-400
S-1-200 and S-1-600),
(S-1-400 S-2-200
and S-1-600), (S-2-400
S-2-200 and S-2-600),
(S-2-400 and S-3-200
and S-2-600), and
S-3-200 (S-3-400
(S-3-400 and S-3-600)
and S-3-600) refer torefer to aerogels
silica silica aerogels after treatment
after heat heat treatment ◦ C, °C,
at 200
at 200 ◦ C,°C,
400400 andand ◦ C°C
600600 for
3for
h, 3respectively.
h, respectively.

2.3.
2.3. Characterization
The
The bulk
bulk density of aerogels
aerogels was
was determined
determined by M/V,where
by ρρ ==M/V, whereMMandandVVarearethe
themass
massandand
volume
volume ofofthetheaerogels, respectively.
aerogels, TheThe
respectively. morphology of the
morphology ofsamples was characterized
the samples by a scanning
was characterized by a
electron
scanningmicroscope (SEM, S-4800).
electron microscope TheS-4800).
(SEM, functional
Thegroups of silica
functional aerogels
groups were characterized
of silica aerogels wereby
Fourier transform
characterized infrared
by Fourier spectroscopy
transform (FTIR,
infrared TENSOR 27).
spectroscopy TheTENSOR
(FTIR, weight loss
27).ofThe
silica aerogels
weight loss was
of
silica by
tested aerogels
using anwas tested by
SDT-1960 using instrument.
universal an SDT-1960The universal instrument. The Nisotherms
N2 adsorption–desorption 2 adsorption–
of the
desorption
samples wereisotherms
measuredofbythea Nsamples were measured analyzer
2 adsorption–desorption by a N2 (TriStar
adsorption–desorption
3000). The specificanalyzer
surface
areas (SSAs) and the pore size distributions were then derived from the adsorption branch using the
 3.1. Bulk Density and Room-Temperature Thermal Conductivity
The bulk density and thermal conductivity of silica aerogels heated at different temperatures
are shown in Figure 2. It was observed that the bulk density and thermal conductivity were first
reduced and then rose up with increasing heat treatment temperature. As shown in Figure 2a, all the
as-prepared
Molecules 2018, 23,aerogels
3192 possess the highest bulk density because of the existence of organic 4 of 11
components. The samples heated at 400 °C (S-1-400, S-2-400, and S-3-400) showed the lowest bulk
densities of 238, 251, and 242 mg∙cm−3, which was due to the elimination of organic components
Brunauer-Emmett-Teller (BET) method and the Barrett-Joyner-Halenda (BJH) method, respectively.
from the surfactant. When the heat treatment temperature further increased to 600 °C, the
The thermal conductivity
densification was evaluated
of the microstructure by a HotofDisk
and collapse thermal
the pores of constants analyzerwould
aerogels normally (TPS 2500).
result in a
relatively higher bulk density. We can clearly see that the density of the S-2 sample increased to 298
3. Results and Discussion
mg∙cm−3 after heat treatment at 600 °C. However, the densities of S-1 and S-3 samples exhibited
3.1. Bulkno
almost change,
Density andwhich was attributed
Room-Temperature to theirConductivity
Thermal smaller shrinkage and better integrity.
The thermal conductivity of a material is often correlated with its density [12]. As shown in
The bulk density and thermal conductivity of silica aerogels heated at different temperatures are
Figure 2b, the variation tendency of the thermal conductivity of the aerogels was in accordance
shown
with thein Figure
change2.ofIttheir
was observed that the
density levels. Thebulk density
lowest and thermal conductivity
room-temperature were first reduced
thermal conductivity values
and then rose up with increasing heat treatment temperature. As shown
of S-1, S-2, and S-3 were 0.035, 0.034, and 0.039 W∙m ∙K after heat treatment at 400 °C,
−1 −1 in Figure 2a, all the as-prepared
aerogels possess
respectively. the highest
After further bulk
heat density
treatmentbecause
at 600of°C,
the the
existence of organic components.
room-temperature The samples
thermal conductivity
heated at 400 ◦ C (S-1-400, S-2-400, and S-3-400) showed the lowest bulk densities of 238, 251, and
values of S-1-400 and S-3-400 showed almost no change, which was the same as the density
242 −3 , which was due to the elimination of organic components from the surfactant. When the
mg·cmHowever,
variance. the thermal conductivity of S-2 increased from 0.034 to 0.078 W∙m−1∙K−1, which
heat
was mainly ascribed to thefurther
treatment temperature collapse increased to 600 ◦ C,
of the skeleton thedensification
and densificationofofthe themicrostructure.
microstructure An and
collapse of the pores of aerogels normally would result in a relatively higher
appropriate heat treatment temperature can effectively remove the residual organic compounds bulk density. We can
clearly seedestructing
that the density of the S-2 sampleofincreased mg·cm
to 298These − 3 after heat treatment ◦ C.
without the porous structure the aerogels. results illustrate that theattype
600 of
However,
surfactantthe and densities of S-1 and
heat treatment S-3 sampleshave
temperature exhibited almosteffect
an obvious no change,
on thewhich wasand
density attributed
thermalto
their smaller shrinkage
conductivity of the silicaand better integrity.
aerogels.

Figure2.2.(a)
Figure (a)Bulk
Bulkdensity
densityand
and(b)
(b) room-temperature
room-temperature thermal
thermal conductivity
conductivity of of silica
silica aerogels
aerogels before
before and
and after heat treatment at different temperatures.
after heat treatment at different temperatures.

3.2. Morphology
The thermalof conductivity
Silica Aerogelsof a material is often correlated with its density [12]. As shown in
FigureFigure
2b, the3 variation tendency
presents the imagesofofthe thermal
silica conductivity
aerogels prepared of the different
with aerogels was in accordance
surfactants with
before and
the change of their density levels. The lowest room-temperature thermal conductivity
after heat treatment at 600 °C. It was observed that the color of S-1 and S-3 samples changed from values of S-1,
S-2, andtoS-3 were 0.035,after
0.034, 0.039 W·m
andtreatment − 1 − 1
·K °Cafter ◦
beige pure white heat at 600 for 3heat
h, treatment
which wasatdue400 toC,decomposition
respectively. After
of
further heat treatment at 600 ◦ C, the room-temperature thermal conductivity values of S-1-400 and
S-3-400 showed almost no change, which was the same as the density variance. However, the thermal
conductivity of S-2 increased from 0.034 to 0.078 W·m−1 ·K−1 , which was mainly ascribed to the collapse
of the skeleton and densification of the microstructure. An appropriate heat treatment temperature
can effectively remove the residual organic compounds without destructing the porous structure of
the aerogels. These results illustrate that the type of surfactant and heat treatment temperature have
an obvious effect on the density and thermal conductivity of the silica aerogels.

3.2. Morphology of Silica Aerogels

Figure 3 presents the images of silica aerogels prepared with different surfactants before and after
heat treatment at 600 ◦ C. It was observed that the color of S-1 and S-3 samples changed from beige to
pure white after heat treatment at 600 ◦ C for 3 h, which was due to decomposition of residual organic
groups. An obvious cracking occurred on the S-2 sample, while S-1 and S-3 still retained a complete
Molecules 2018, 23, x 5 of 11
Molecules 2018, 23, 3192 5 of 11

residual organic groups. An obvious cracking occurred on the S-2 sample, while S-1 and S-3 still
retained
shape. The a complete
retentionshape.
of S-1Theandretention of S-1 and
S-3 was derived S-3the
from waseffective
derivedcondensation
from the effective condensation
of Si-O-Si with the
of Si-O-Siofwith
addition the addition
the cationic of theCTAB
surfactant cationic surfactant
or the anionic CTAB or the
surfactant SDS.anionic surfactant
The effective SDS. The
condensation
effective
resulted in condensation
an enhancement resulted
in theinnetwork
an enhancement
of the silicainaerogels,
the network
which of the also
would silicamake
aerogels,
them which
able to
would also make them able to withstand high temperatures. The linear shrinkage
withstand high temperatures. The linear shrinkage of the monolithic silica aerogels was calculated of the monolithic to
silica
evaluateaerogels was calculated
the thermal to evaluate
stability. After dryingthe via thermal
APD, thestability. After monoliths
silica aerogel drying viaprepared
APD, the silica
with all
aerogel monoliths
surfactants prepared
exhibited low linearwithshrinkage
all surfactants
without exhibited
cracking.low Thelinear shrinkage
linear shrinkageswithout
of S-1,cracking.
S-2, and
The linear8%,
S-3 were shrinkages
12%, andof10%,S-1, respectively.
S-2, and S-3 After
were further
8%, 12%, andtreatment
heat 10%, respectively. ◦ After
at 600 C for 3 h,further
S-1 andheat
S-3
treatment at 600 °C for 3 h, S-1 and S-3 still showed low linear shrinkage without
still showed low linear shrinkage without cracking, whereas S-2 was fractured. The low shrinkage cracking, whereas
S-2 was the
during fractured. The low
APD process shrinkage
is also during
beneficial the preparation
for the APD process ofislarge-sized
also beneficial for theaerogels
monolithic preparation
and
of large-sized
mass monolithic aerogels and mass production.
production.

Figure
Figure 3.
3. Photographs
Photographsof ofsilica
silicaaerogels
aerogels prepared
prepared with
with different
different surfactants
surfactants before
before and
and after
after heat
heat
treatment at 600 °C
◦ (∆L represents the linear shrinkage of obtained samples).
treatment at 600 C (∆L represents the linear shrinkage of obtained samples).

The
The microstructure
microstructure of of silica
silica aerogels
aerogels was
was characterized
characterizedby by SEM,
SEM, asas shown
shown in in Figure
Figure 4.4. There
There isis
no doubtthat
no doubt thataerogels
aerogelsare are
highlyhighly
porous porous solid materials
solid materials with three-dimensional
with three-dimensional network
network structures.
structures.
For the S-1For andthe S-3S-1 and S-3silica
samples, samples, silicacan
hydrosol hydrosol
form a can form gel
uniform a uniform
networkgel in network
the presencein the
of
presence
CTAB-water of CTAB-water
or SDS-water. or SDS-water.
As expected As[21],
expected
it could [21],
beitseen
could bethe
that seen that theofpresence
presence of the
the surfactant
surfactant
impacts the impacts the microstructure
microstructure of the as-prepared
of the as-prepared silica aerogels silica aerogels significantly.
significantly. The results fromThe Vareda
results
from Vareda andetMaximiano
and Maximiano al. suggested et al. suggested
that that a rearrangement
a rearrangement of the microstructure
of the microstructure of the final
of the final material was
material
due to the was due to effect
porogen the porogen
of eacheffect of each
surfactant insurfactant in the condensation
the condensation and gelationand gelation
steps. As cansteps. As
be seen
can
from bethe
seen
SEMfrom the SEM
images, images,
S-1 and S-1 and S-3
S-3 exhibited exhibited
typical typical interconnected
interconnected network
network structures structures
consisting of
consisting of silica
silica particles particles
in different in However,
sizes. different sizes.
S-2 showsHowever, S-2 shows
a coarsened a coarsened
structure structure
and observable and
clusters.
observable
The formation clusters. The formation
of clusters was due toof theclusters was due
accumulation to the
without accumulation
effective without of
interconnection effective
Si-O-Si
interconnection
in the presence of the Si-O-Si in the presence
surfactant RALUFON of the
414.surfactant
This result RALUFON 414.the
indicates that This result indicates
amphoteric that
surfactant
the amphoteric
RALUFON surfactant
414 can RALUFON
greatly interfere with414
the can greatly
network interfere
formation and with the lower
induce network formation
crosslinking and
among
induce lowerdue
the particles crosslinking among activity
to the excessive the particles
in thedue to theprocess.
gelation excessive activity in the gelation process.
The
The thermal
thermal stability
stability of
of silica
silica aerogels
aerogels prepared
prepared with with different
different surfactants
surfactants was
was also
also evaluated
evaluated
by
by means
means ofof the
the change
change inin the
the microstructure
microstructure beforebefore andand after
after heat
heat treatment
treatment atat 600 ◦
600 °C.C. For
For both
both the
the
Molecules 2018,23,
Molecules2018, 23, 3192
x 6 of
6 of 1111

S-1-600 and S-3-600 samples, the gel network retained a uniform structure because the
S-1-600 and S-3-600 microstructure
high-crosslinking samples, the gel was
network retained
strong a uniform
enough structure the
to withstand because the high-crosslinking
high-temperature heat
microstructure was strong enough to withstand the high-temperature heat treatment.
treatment. It was also clearly observed that the morphology of S-2 changed from a particulate It was also
clearly
structureobserved that the morphology
to a coarsened of S-2 changed
and dense structure from
after heat a particulate
treatment at 600structure to awas
°C, which coarsened
caused byand
dense structure after heat treatment at 600 ◦ C, which was caused by the low connectivity between
the low connectivity between the silica particles. The appropriate surfactant activity allows more
the silica particles.
condensation, whichThe appropriate
results surfactant
in the high activity allows
interconnection morehydrosol
of silica condensation, which
particles. results in
Conversely,
the highsurfactant
excess interconnection of silica
activity hydrosol
potentially particles.the
suppresses Conversely,
network excess surfactant
formation, whichactivity
leads potentially
to lower
suppresses
crosslinking. the network formation, which leads to lower crosslinking.

Figure 4. SEM images

Figure 4. images of
of silica
silica aerogels
aerogels prepared
prepared with
with different
differentsurfactants
surfactantsbefore
beforeand
andafter
afterheat
heat
treatment
treatment at 600◦°C
at 600 C. .

3.3.
3.3. Chemical
Chemical Composition
Composition of of Silica Aerogels
Silica Aerogels
In
In order
orderto tostudy
studythe
thechemical
chemicalstructure
structureofofthe thesilica
silicaaerogels
aerogelsbefore
before and
and after heat
after treatment,
heat treatment,the
samples were also characterized with FTIR spectroscopy. As shown in Figure
the samples were also characterized with FTIR spectroscopy. As shown in Figures 5a–c, the spectra 5a–c, the spectra of S-1,
S-2, andS-2,
of S-1, S-3 and
are allS-3very
are similar,
all veryindicating that they that
similar, indicating feature
theysimilar
featurechemical
similar structures that are formed
chemical structures that
by the use of different surfactants. The broad peak near 3438 cm −1 and the small band near 1629 cm−1
are formed by the use of different surfactants. The broad peak near 3438 cm and the small band −1

correspond to−1 the Si-OH absorption peak [25]. The absorption −1 is due to the
near 1629 cm correspond to the Si-OH absorption peak [25]. Thepeak near 1114
absorption peakcm near 1114 cm−1 is
asymmetrical stretch vibration of Si-O-Si, while the peak at 801 cm − 1 is the result of the symmetrical
due to the asymmetrical stretch vibration of Si-O-Si, while the peak at 801 cm is the result of the −1

stretching vibration of Si-O-Si [25–28]. Moreover, theMoreover,

absorption −1 are
symmetrical stretching vibration of Si-O-Si [25–28]. thepeaks aroundpeaks
absorption 2800–3000
around cm2800–
assigned
3000 cm−1toare the stretching
assigned vibrations
to the stretching of vibrations
C-H [25,26,29].of C-HAfter heat treatment
[25,26,29]. 200 ◦ C for
After heatattreatment 3 h, °C
at 200 the
absorption − 1
for 3 h, the absorption peaks near 2800–3000 cm decrease, and almost disappear after further heatat
peaks near 2800–3000 cm decrease, and
−1 almost disappear after further heat treatment
400 ◦ C for 3 h, indicating the decomposition of organic compositions from the surfactants.
treatment at 400 °C for 3 h, indicating the decomposition of organic compositions from the
A set of representative photographs of silica aerogels prepared with SDS are shown in Figure 5d–f.
surfactants.
The color ◦ C, and
A setofof the silica aerogels
representative changed of
photographs from beige
silica to brown
aerogels afterwith
prepared heatSDStreatment
are shown at 200
in Figures
then ◦ C. This color evolution also demonstrates that the
5d–f.toThepure white
color after
of the heataerogels
silica treatment at 400from
changed beige to brown after heat treatment at 200 °C,
organic
and then compositions
to pure white in silica aerogels
after heat gradually
treatment at 400decomposed
°C. This colorwithevolution
the increase alsoofdemonstrates
the heat treatment
that
temperature, which agrees with
the organic compositions the results
in silica aerogelsofgradually
the FTIR spectra.
decomposed with the increase of the heat
treatment temperature, which agrees with the results of the FTIR spectra.
Molecules 2018, 23, 3192 7 of 11
Molecules 2018, 23, x 7 of 11

Figure5.5.FTIR
Figure FTIRspectra
spectraof of
thethe
silica aerogels:
silica (a) S-1,
aerogels: (a) (b)
S-1,S-2,
(b)and
S-2,(c)and
S-3 (c)
before
S-3 and afterand
before heatafter
treatment
heat
200 ◦ C and
attreatment 400 ◦°C
at 200 C, and
respectively. (d–f) Representative
400 °C, respectively. photographs photographs
(d–f) Representative of silica aerogels prepared
of silica with
aerogels
sodium dodecyl sulfate (SDS) before and(SDS)
after before
heat treatment ◦ C and 400 ◦ C, respectively.
prepared with sodium dodecyl sulfate and afteratheat
200 treatment at 200 °C and 400 °C,
respectively.
3.4. Thermogravimetric Analysis (TGA) of Silica Aerogels
3.4. Thermogravimetric
Figure 6 shows theAnalysis
weight (TGA) of Silica
loss curves of Aerogels
silica aerogels prepared with various surfactants before
and after
Figureheated at different
6 shows temperatures.
the weight loss curvesAs of
exhibited in Figure
silica aerogels 6a, the weight
prepared loss of S-1,
with various S-2, and
surfactants
S-3 could be divided into three regions: 25~200 ◦ C, 200~400 ◦ C, and 400~700 ◦ C. The first region
before and after heated at different temperatures. As exhibited in Figure 6a, the weight loss of S-1,
with a small weight loss of 2.6% was caused by the evaporation of the solvent, the second region
S-2, attributed
was and S-3 could be decomposition
to the divided into three regions:components,
of organic 25~200 °C, 200~400
and the°C, andregion
third 400~700 °C.due
was Thetofirst
the
region with aofsmall
dehydration Si-OH.weight loss of 2.6%
As presented was caused
in Figure by and
6a, S-1 the evaporation of the solvent,
S-2 have a higher organic the second
component
decomposition temperature
region was attributed to the(about 220 ◦ C) than
decomposition S-3 (about
of organic 170 ◦ C), which
components, and theindicates the better
third region was thermal
due to
stability of CTAB and RALUFON 414 as compared to SDS. The weight loss curves of
the dehydration of Si-OH. As presented in Figure 6a, S-1 and S-2 have a higher organic component silica aerogels
prepared with various surfactants after heated at different temperatures are shown in Figure 6b–d. It is
decomposition temperature (about 220 °C) than S-3 (about 170 °C), which indicates the better
observed that there are still a lot of weight losses between 200 and 400 ◦ C for silica aerogels after heat
thermal stability of CTAB and RALUFON 414 as compared to SDS. The weight loss curves of silica
treatment at 200 ◦ C due to the decomposition of residual organic components. Neglect of the small
aerogels
weight prepared
loss betweenwith25 andvarious
100 ◦ Csurfactants
caused by theafter heated at of
evaporation different temperatures
the adsorbed are shown
water, there in
are almost
Figure
no weight6b-d. It is observed
changes that thereafter
of silica aerogels are still
heatatreatment
lot of weight losses
at 400 ◦
and between 200 and
600 C. These 400 °C
results for silica
confirm that
organic
aerogels after heat treatment at 200 C due to the decomposition of residual organic components.at
components from surfactants o in all samples were removed completely after being heated
400 ◦ C, which is consistent with the FTIR results.
Neglect of the small weight loss between 25 and 100 °C caused by the evaporation of the adsorbed
water, there are almost no weight changes of silica aerogels after heat treatment at 400 and 600 oC.
These results confirm that organic components from surfactants in all samples were removed
completely after being heated at 400 °C, which is consistent with the FTIR results.
Molecules 2018, 23, 3192 8 of 11
Molecules 2018, 23, x 8 of 11

Figure 6.
Figure 6. Weight loss curves
curves ofof the
the silica
silica aerogels:
aerogels: (a)
(a)S-1,
S-1,S-2,
S-2,and
andS-3;
S-3;(b)
(b)S-1-200,
S-1-200,S-1-400,
S-1-400,and
and
S-1-600; (c)
S-1-600; (c)S-2-200,
S-2-200,S-2-400,
S-2-400,and
and S-2-600,
S-2-600, thethe curve
curve of S-2-600
of S-2-600 is almost
is almost overlapped
overlapped withofthat
with that of
S-2-400;
S-2-400;
(d) (d) S-3-400,
S-3-200, S-3-200, and
S-3-400, and S-3-600.
S-3-600.

3.5.
3.5. Pore
Pore Structures
Structures of
of Silica Aerogels
Silica Aerogels
The
The N adsorption-desorptionisotherms
N22 adsorption-desorption isothermsand andpore poresizesizedistributions
distributionsofofsilica silicaaerogels
aerogelsprepared
prepared
with
withvarious
varioussurfactants
surfactantsare areshown
shownin inFigure
Figure7.7.All Allthetheisotherms
isothermsofofsilica
silicaaerogels
aerogelsrepresent
representaaType TypeIV
isotherm with an H3 type hysteresis loop, which is the characteristic
IV isotherm with an H3 type hysteresis loop, which is the characteristic of mesoporous materials of mesoporous materials [30,31].
The detailed
[30,31]. The pore
detailedstructure parameters
pore structure are presented
parameters in Table 1.inAfter
are presented APD,
Table. the specific
1. After APD, surface areas
the specific
of the silica
surface aerogels
areas prepared
of the silica with prepared
aerogels various surfactants
with various were almost thewere
surfactants same, ranging
almost thefrom
same, 134 m2 ·g−1
ranging
to 141134
from m2 ·mg−2∙g
1 .−1As shown2in−1the inset pore-size distribution in Figure 7 and Table 1, the silica aerogel
to 141 m ∙g . As shown in the inset pore-size distribution in Figure 7 and Table 1,
prepared 3 · g−1 )
the silica with
aerogel CTAB (S-1) had
prepared larger
with CTAB average
(S-1) pore size (24.7
had larger nm) and
average porelarger pore volume
size (24.7 nm) and(1.07
largercmpore
than
volume the (1.07
silica cmaerogels prepared
3∙g−1) than withaerogels
the silica RALUFON 414 (S-2)
prepared withand SDS (S-3),414
RALUFON respectively.
(S-2) and After being
SDS (S-3),
heated at 400 ◦After
respectively. C, thebeing
specific surface
heated areas
at 400 °C, of the
all silica
specificaerogels
surfacelargely
areasincreased
of all silicadueaerogels
to the removal
largelyof
increased
organic due to theand
surfactants removal of organic
the opening surfactants
of more pores. As and the opening
mentioned of more
above, pores. As mentioned
the amphiphilic surfactant
above, the would
molecules amphiphilicform surfactant
micelles inmolecules
the solution would with form micelles in the
a hydrophobic solution
core stabilizedwithbya hydrophobic
a hydrophilic
core stabilized
shell, and thoseby a hydrophilic
hydrophilic shell, will
micelles and attach
those hydrophilic
to the surface micelles
of silicawill attach to
particles andthe surface
embed in of the
silica network
silica particles through
and embed in thegroups.
hydroxyl silica network
These act through hydroxyl
as a “pore forming groups.
agent” These
after act
beingas aremoved
“pore
forming
by agent” afterThe
heat treatment. being removed
removal by heat treatment.
of organic surfactantsThe wasremoval of organicby
also confirmed surfactants
the FTIR wasspectraalsoin
confirmed by the FTIR spectra in Figure 5. It is noted that
Figure 5. It is noted that the silica aerogel prepared with RALUFON 414 (S-2) possessed a much the silica aerogel prepared with
RALUFON
higher 414 (S-2)
SSA (378 −1 ) than S-1
m2 ·gpossessed a much
(264 m 2 ·g−1 )SSA
higher and(378 ·g−1 )S-1
m2∙g−1m) 2than
S-3 (247 after(264 m2∙gheated
being at 400 ◦ C.
−1) and S-3 (247

m ∙g ) after
2 −1
However, thebeing heatedstructure
nano-pore at 400 °C.ofHowever, the nano-pore
S-2 was collapsed structure
and its network of was
S-2 was collapsed
coarsened and
after its
being
network was coarsened after being heated at 600 °C, as shown in Figure
heated at 600 C, as shown in Figure 4, which led to a significant loss of SSA. After heating at 600 ◦ C,
◦ 4, which led to a significant
lossSSA
the of SSA. After
of S-2 heating at decreased
dramatically 600 °C, theto SSA 22 ofm2S-2·g−dramatically
1 and the pore decreased
volume to 22 m2∙g−1 and
accordingly the poreto
decreased
volume 3 accordingly
− 1 decreased to 0.02 cm 3 ∙g −1 . By contrast, the silica aerogels
0.02 cm ·g . By contrast, the silica aerogels S-1 and S-3 maintained high SSAs of 131 and 107 m2 ·g−1 , S-1 and S-3 maintained
high SSAs ofwhich
respectively, 131 and 107 m2that
indicates ∙g−1, they
respectively,
had betterwhich thermal indicates
stabilitythat
than they
S-2.had better thermal
Combined with the stability
thermal
than S-2. Combined with the thermal conductivities exhibited in Figure 2b, the silica aerogel
Molecules 2018, 23, 3192 9 of 11
Molecules 2018, 23, x 9 of 11

conductivities
prepared withexhibited in Figure 2b,
the amphoteric the silica(S-2)
surfactant aerogel prepareda with
possessed higherthe amphoteric
SSA and lower surfactant (S-2)
thermal
possessed a higher SSA and lower thermal conductivity than the silica aerogels
conductivity than the silica aerogels prepared with the cationic surfactant (S-1) and anionicprepared with the
cationic surfactant (S-1)being
and anionic ◦
surfactant (S-3) after heatedsurfactant
at 400 °C. (S-3)
Theafter being
silica heatedprepared
aerogels at 400 C.with
The silica aerogels
the cationic
prepared
surfactantwith
(S-1)the cationic
and surfactant
anionic (S-1)
surfactant andhad
(S-3) anionic
bettersurfactant (S-3) hadthan
thermal stability better
thethermal stability
silica aerogel
prepared
than withaerogel
the silica the amphoteric
preparedsurfactant (S-2).
with the amphoteric surfactant (S-2).

Figure7.7. N
Figure N22 adsorption–desorption
adsorption–desorption isotherms
isothermsand
andpore-size
pore-sizedistributions
distributionsofofsilica
silicaaerogels:
aerogels:(a)(a)S-1,
S-1,
(b)S-2
(b) S-2and
and(c)
(c)S-3
S-3before
before and
and after
after heat ◦
heat treatment at 400 °CC and
and 600 ◦
600 °C,C,respectively.
respectively.

Table 1. Pore structures of silica aerogels prepared with various surfactants before and after heat
Table 1. Pore structures of silica aerogels prepared with various surfactants before and after heat
treatment ◦ C and 600 ◦ C, respectively.
treatmentat
at400
400 °C and 600 °C, respectively.
Sample Specific Surface
Specific Area (SSA) (m2 ·g−1 )
Surface Average Pore Size (nm) Pore Volume (cm3 ·g−1 )
Sample Average Pore Size (nm) Pore Volume (cm3·g−1)
S-1 Area (SSA) (m 2·g−1)
141 24.7 1.07
S-1-400
S-1 141 264 24.7 35.7 1.07 1.49
S-1-600
S-1-400 264 131 35.7 36.1 1.49 1.02
S-2
S-1-600 131 141 36.1 13 1.02 0.64
S-2-400 378 9.6 1.6
S-2 141 13 0.64
S-2-600 22 3.3 0.02
S-2-400
S-3 378 134 9.6 14 1.6 0.69
S-2-600
S-3-400 22 247 3.3 17.5 0.02 0.99
S-3
S-3-600 134 107 14 25.1 0.69 0.99
S-3-400 247 17.5 0.99
S-3-600 107 25.1 0.99
4. Conclusions
In summary, low-cost silica aerogels were prepared with industrial silica hydrosol and a
4. Conclusions
subsequent ambient pressure drying (APD) process. Solvent exchange and surface modification
In summary, low-cost silica aerogels were prepared with industrial silica hydrosol and a
during the APD process were avoided by the addition of various surfactants (cationic, amphoteric, and
subsequent ambient pressure drying (APD) process. Solvent exchange and surface modification
anionic). The pore structure of the silica aerogels was well preserved after APD thanks to the addition
during the APD process were avoided by the addition of various surfactants (cationic, amphoteric,
of surfactants that reduced the surface tension of the liquid. Moreover, organic surfactants and micelles
and anionic). The pore structure of the silica aerogels was well preserved after APD thanks to the
Molecules 2018, 23, 3192 10 of 11

were removed to release more pores after the mixture was heated at 400 ◦ C. The silica aerogel prepared
with the amphoteric surfactant (RALUFON 414) possesses a higher SSA (378 m2 ·g−1 ) and lower
thermal conductivity (0.034 W·m−1 ·K−1 ) than the silica aerogels prepared with the cationic (CTAB)
and anionic surfactants (SDS) after heat treatment at 400 ◦ C. However, the silica aerogels prepared
with the cationic (CTAB) and anionic surfactants (SDS) exhibited a better thermal stability than that
prepared with the amphoteric surfactant (RALUFON 414). After being heated at 600 ◦ C, the silica
aerogel prepared with CTAB maintained a high SSA of 131 m2 ·g−1 and a low thermal conductivity of
0.038 W·m−1 ·K−1 , respectively. This low-cost and easily mass-produced silica aerogel with a high SSA,
low thermal conductivity, and good thermal stability could be widely applied as a thermal insulator
for building and industrial energy-saving applications.

Author Contributions: J.S., X.W., and D.C. conceived and designed the experiments; D.C. and Q.Z. performed
the experiments; D.C., W.Z., and W.D. analyzed the data; J.S. and X.W. contributed reagents/materials/analysis
tools; D.C., X.W., and W.Z. wrote the paper; D.C., X.W., and W.Z. revised the paper; all authors approved the final
version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: This work was financially supported by the National Key Research and Development
Program of China (2017YFA0204600), the National Natural Science Foundation of China (11874288), and the
Fundamental Research Funds for the Central Universities from Tongji University.
Conflicts of Interest: The authors declare no conflict of interest.

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