Materials and Design 191 (2020) 108640

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Materials and Design

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Preparation of silica aerogels with high temperature resistance and low

thermal conductivity by monodispersed silica sol
Huafei Cai a, Yonggang Jiang a,⁎, Jian Feng a,⁎, Sizhao Zhang b, Fei Peng a, Yunyun Xiao a,
Liangjun Li a, Junzong Feng a
a
Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073,
Hunan, PR China
b
China-Australia International Institute for Minerals, Metallurgy and Materials, Jiangxi University of Science and Technology, Nanchang 330013, Jiangxi, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• SiO2 aerogels with high temperature re-

sistance are prepared by controllable
particle size monodispersed silica sol.
• Thermal conductivity of SiO2 aerogels is
as low as 0.02723 W·m−1·K−1 despite
forming large particle structure.
• The aerogel large particle skeleton
structure can inhibit the viscous flow
between aerogel particles.
• Pore collapse caused by skeleton failure
can be obviously inhibited depending
on formed sturdy skeletons.

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

Article history: Silica aerogels with different particle size were prepared by monodispersed silica sol for the first time. The prop-
Received 11 November 2019 erties of the silica aerogels under normal and high temperature were systematically studied. Among the four dif-
Received in revised form 11 March 2020 ferent particle size aerogels, the SA-2 sample consisted of 20.31 ± 1.21 nm particles with narrow size distribution
Accepted 12 March 2020
had high temperature resistance and low thermal conductivity. Compared with the traditional acid-base two-
Available online 13 March 2020
step prepared silica aerogels, the monodisperse silica aerogels can significantly increase the temperature resis-
Keywords:
tance while maintaining a low thermal conductivity (0.02723 W·m−1·K−1). The sturdy skeleton structure
Silica aerogel formed by the interconnection of large particles can effectively inhibit the viscous flow between aerogel particles
Monodispersed and avoid pore collapse caused by skeleton failure which can maintain a stable structure until 900 °C and retain a
Temperature resistance relatively complete structure at 1000 °C with only about 35% volume shrinkage after 2 h heat treatment. At
Thermal conductivity 1100 °C, the viscous flow between aerogel particles and pore collapse cannot be effectively suppressed, and
Volume shrinkage the pure silica aerogels can only be used during a short period at 1100 °C. The results will be meaningful for
Viscous flow the design of super thermal insulation materials with high temperature resistance and low thermal conductivity.
© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

Silica aerogel is a unique ultra-light weight nanoporous material

with ultra-low density (~3 kg/m−3), high specific surface area
⁎ Corresponding authors. (~1200 m2/g), high porosity (~99%), and very low thermal conductivity
E-mail addresses: [email protected] (Y. Jiang), [email protected] (J. Feng). (~0.013 W/m·K) [1–6]. Because of these unique characteristics, they can

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2 H. Cai et al. / Materials and Design 191 (2020) 108640

be applied in many various fields, such as environmental protection composites with pure silica aerogels as matrix is obvious lower
[7–9], adsorption catalysis [10–12], energy saving in construction than that of those doped with heterogeneous elements silica
[13–15] and super thermal insulation [16,17]. As thermal insulation ma- aerogels. [30,52] Therefore, it is necessary to find a more effective
terials, SiO2 aerogels can effectively inhibit solid and gaseous heat con- way to maintain the excellent performance of the silica aerogel
duction because of the amorphous slender skeleton and unique while increasing the temperature resistance of the silica aerogel. Sil-
nanometer-sized pore structure, which make them widely used as ica aerogels exhibit similar sintering behavior for heat treatment be-
high efficiency thermal insulation in various fields up to 800 °C fore 900 °C [53,54]. The silica aerogel will shrink obviously and the
[18–21]. However, the shrinkage and deformation of silica aerogels aerogel particles will fuse together obviously during the initial
above 800 °C which caused by the particle agglomeration and pore col- stage of the heating process. After a period of heat treatment, the sil-
lapse during the sintering process will seriously limits their application ica aerogel particles will no longer grow up obviously and the aerogel
at higher temperature. The conventional pure silica aerogels have about will not shrink obviously again with the prolongation of heat treat-
20% volume shrinkage at 800 °C within 0.5 h and has about 50% volume ment time [21]. According to the sintering behavior of silica aerogels,
shrinkage at 900 °C within 0.5 h [22–25]. Therefore, it attracts many it can be predicted that increasing the secondary silica aerogel parti-
scholars to study the methods to improve the heat resistance of silica cle size may contribute to an improvement in the temperature toler-
aerogels at high temperature. ance and reduce shrinkage of the silica aerogel in that temperature
Silica aerogels are typical amorphous porous materials with three- range while maintaining the pure silica aerogel characteristics. At
dimensional reticular structure formed by the interconnection of present, there are no reports on the preparation and properties of
aerogel particles, and the sintering behavior of silica aerogels is primar- different particle size silica aerogels with high temperature resis-
ily caused by viscous flow [26–28]. At high temperature, the silica tance and low thermal conductivity.
aerogel particles will flow viscously under the action of high surface ten- In this work, silica aerogels with different particle size were designed
sion, which will lead to the neck formation and fusion of aerogel parti- and prepared by monodispersed silica sol for the first time.
cles; and the aerogel particles will grow and the pores will collapse Monodispersed silica sol has the characteristics of single particle shape
with prolonged heating, leading to the decrease of the specific surface and narrow particle size distribution, and it can effectively reduce the
area and the macroscopic shrinkage and deformation. In order to im- number of small particles in silica aerogel, reduce the sintering driving
prove the temperature resistance of silica aerogels, it is necessary to in- force and inhibit the shrinkage of silica aerogel at high temperature.
hibit the viscous flow of aerogels at high temperature. Although the By studying the properties of different particle size silica aerogels, the
viscous flow can be effectively suppressed by adding reinforcement formulation of silica aerogel with high temperature resistance and low
such as fibers [21,29–31], it is also significant to improve the tempera- thermal conductivity was determined. In addition, the sintering behav-
ture resistance of the silica aerogel itself. At present, the main method ior and temperature resistance mechanism of the silica aerogels were
to improve the temperature resistance of silica aerogels is to add high also systematically studied.
temperature resistance components like metallic oxides [32]. The high
temperature resistance components such as Al2O3 [33–37], ZrO2 2. Experimental details
[38–40], Y2O3 [41] and TiO2 [42–44] can inhibit the viscous flow and
particle growth by forming the aerogel skeleton together with silica, 2.1. Materials
thus maintaining the nanoporous structure and improving the temper-
ature resistance of aerogel. Among the high temperature components, Tetraethoxysilane (TEOS; analytical reagent (AR) grade), ethanol
Al2O3 is the most widely used applied. Feng et al. [35] prepared Al2O3- (EtOH; AR grade), and ammonia (25 wt%; AR grade) were purchased
SiO2 aerogel with different Si/Al ratios, and found that the Al2O3-SiO2 from Shanghai Aladdin Biochemical Technology Co., Ltd. (China). Note
aerogel will form an intermediate state different from the pure silica that the water used in all the experiments is deionized water, and all
aerogel and pure alumina structure at the optimal ratio, which can ef- of the reagents in this study were used as received without further
fectively inhibit the viscous flow between the aerogel particles and purification.
pore collapse, therefore, it can maintain intact skeleton and high surface
area after heat treatment. Zu et al. [40] prepared ZrO2-SiO2 aerogel by 2.2. Methods
sol-gel method, and the addition of ZrO2 inhibited the viscous flow
and particle growth of aerogel particles, therefore, it showed high ther- (1) Preparation of monodispersed silica sol
mal stability and can maintain a 172 m2/g specific area after heat treat-
ment at 1000 °C; but the aerogel still exhibited obvious volume
shrinkage because the partial fusion of particles and collapse of pores In this paper, the mono-dispersed silica sol was synthetized via a
formed by slender skeleton. Zhang et al. [41] prepared Y2O3-SiO2 modified Stöber method reported by Cai et al [55], in which TEOS was
aerogel with high structural stability and high surface area, and it can used as precursor, ethanol as solvent, ammonia as catalyst and deion-
maintain a 643.79 m2/g specific area after heat treatment at 900 °C. ized water as hydrolyzing agent. First, water, ethanol and ammonia
The higher thermal stability of Y2O3-SiO2 aerogel than pure SiO2 aerogel were mixed and heated to a specified temperature. Second the TEOS
(138.7 m2/g) is attributable to the high-temperature resistance of Y2O3 was heated to a specified temperature. Then the TEOS and the compo-
which effectively inhibit the viscous flow between the aerogel particles. nent solvent are poured simultaneously and rapidly into a beaker
But the aerogel skeleton is too slender which may cause severe pore col- heated in a constant temperature water bath in order to ensure unifor-
lapse over 900 °C. In addition, there is also many researches devoted to mity of mixing, and the original monodispersed silica sol was obtained
improving the temperature resistance of silica aerogels by adding het- by stirring for 24 h. Finally, after vacuum concentration and solvent re-
erogeneous components [45–50]. placement by ethanol, the monodispersed silica sol with high concen-
Although the temperature resistance of silica aerogels can be im- tration (18–20 wt%) and a single ethanol solvent system was
proved effectively by adding high temperature resistant compo- obtained. The specific parameters were shown in Table 1.
nents, the composition and structure of silica aerogels will be
significantly changed by adding high temperature resistant compo- (2) Preparation of silica aerogel samples
nents. The thermal conductivity of aerogels will obviously increase
after doping caused by the addition of high thermal conductivity
doped solid phase and the change of pore structure [31–33,51]. The silica aerogel was prepared by the following steps: (1) place the
Under the same conditions, the thermal conductivity of the monodispersed silica sol in a 50 °C water bath for gelling; (2) age the
 H. Cai et al. / Materials and Design 191 (2020) 108640 3

Table 1
Preparation parameters and properties of the mono-dispersed silica sol.

Sample TEOS concentration (mol/L) R (H2O/TEOS) NH3 concentration (mol/L) Temperature (°C) Sol particle size (nm)

1 0.4 60 0.10 75 6.98 ± 0.79

2 0.4 60 0.15 75 13.29 ± 1.08
3 0.4 60 0.20 75 18.36 ± 1.71
4 0.4 60 0.25 75 23.73 ± 2.05

samples for two days at 50 °C after gelling, (3) dry the samples with eth- The volume shrinkage (η) of silica aerogels was characterized by the
anol supercritical drying (265 °C, 7 MPa), and (4) heat the samples at change of volume density at different temperatures:
500 °C for 2 h in an air atmosphere to remove the organic residue. The
preparation procedure of the monodispersed silica aerogels was
shown in Fig. 1. V2 ρ
η ¼ 1− ¼ 1− 1 ð2Þ
The monodisperse silica samples used for property characterization V1 ρ2
and test were randomly sampled at three different positions of mono-
disperse aerogels to reduce the experimental error caused by the chance
wherein, V1 is the original volume of silica aerogel; V2 is the volume
of sampling. The silica aerogel samples used for high temperature char-
of silica aerogel after heat treatment; ρ1 is the original bulk density of
acterization were heat treated in a muffle furnace. The aerogel samples
silica aerogel; and ρ2 is the bulk density of silica aerogel after heat
were divided into very small pieces and placed flat on the bottom of the
treatment.
crucible. When the furnace temperature began rising to the required
The microstructure of the samples was observed by using a high-
temperature, the crucible containing silica aerogel samples was quickly
resolution field emission (SEM Zeiss Sigma 500, Carl Zeiss Co. Ltd.,
placed in the furnace and heated for the desired time. Subsequently, the
Germany), and three different regions were selected for observation
samples were taken out directly and air cooled, and the heat treatment
to ensure that the typical morphology of monodisperse silica was
of silica aerogels was complete.
presented. The sample was fixed on the sample table with conduc-
The bulk density of the samples before and after heating was mea-
tive adhesive; the metal (Pt) spraying time was 180 s, and the volt-
sured by using Archimedes method. During the bulk density test, the
age was 20 kV. The size distribution of silica aerogel particles
test conditions must keep consistent, and it needed to repeat the exper-
before and after heat treatment was measured by Image J software,
iment five times and take the average value to determine the final
and the particle size was determined by the diameter of the aerogel
results.
particle circumferential circle, and no less than 100 particles were
First, the mass of the silica aerogel samples was determined to be m1.
selected to the particle size measurement. The thermal conductivity
In a water-filled beaker placed on an electronic microbalance electronic
of silica aerogels was carried out on a Hot Disk 2500 thermal constant
balance, a cylinder with holes and was placed vertically into the beaker,
analyzer, the samples were measured for three times and then the
with everything being submerged in the water. The weight was re-
standard deviation was calculated. The thermal properties of the
corded as m2 (buoyancy of the empty container). After removing the
samples were analyzed by thermogravimetric analyzer-differential
container, it was dried, and the silica aerogel was loaded into it. Then,
scanning calorimeter (TG-DSC, SDTQ600, TA Co. Ltd., USA) from
the filled container was immersed in the water and the weight was re-
25 °C to 1200 °C with a 10 °C/min heating rate in air. The chemical
corded as m3 (the total buoyancy of the container and silica aerogels). It
surface groups on the silica aerogel samples were measured by Fou-
should be noted that the samples were hydrophilic due to the oxidation
rier transform infrared spectrometer (FT-IR, Nicolet avatar 360, Ni-
of the organic groups. Therefore, samples should be modified by hydro-
colet Co. Ltd., USA) using pressed KBr pellets, and the wavenumber
phobic treatment before being placed in the water container. The hy-
measurement rage was 4000 cm−1–400 cm−1. The specific surface
drophobic treatment process of the samples was according to the
area of the silica aerogel samples was determined from the adsorp-
procedure reported by Feng et al [56]. The bulk density of the silica
tion isotherm using Brunauer-Emmett-Teller (BET) theory in a sur-
aerogel sample can be obtained by:
face and porosity analyzer (ASAP 2460, Micromeritics Co. Ltd., USA)
at N2 environment. The pore size distribution of the silica aerogel
m1
ρa ¼ ρ O ð1Þ samples was derived from desorption branches of the isotherms by
m3 −m2 H2
applying Barret-Joyner-Halenda (BJH) model. The crystal structure
of silica aerogels was analyzed by Bruker D8 Advance X-ray diffrac-
wherein, ρa is the density of silica aerogel (kg/m3); and ρH2O is the den- tion instrument (Cu Kα ray, 40 kV); the scanning speed was
sity of distilled water, (1.003 g/cm3, 25 °C, 1 atm). 0.2°s−1, and the scanning range is 10°–80°.

Fig. 1. Preparation procedure of the monodispersed silica aerogels.

4 H. Cai et al. / Materials and Design 191 (2020) 108640

3. Results and discussion silica aerogel samples exhibited a mesoporous structure according to
the classification of the International Union of Pure and Applied Chem-
3.1. Microstructure and properties of the silica aerogels istry [62]. With the increase of silica aerogel particles, the specific sur-
face area of aerogel decreased as shown in Table 2. The specific
The microstructure of silica aerogels with different particles was surface area of SA-1aerogels with small particles was not very high for
shown in Fig. 2. The silica aerogels prepared by mono-dispersed silica the multi-particle stack. Fig. 3 (b) showed the distribution of the silica
sol had a typical three-dimensional nanoporous structure. Compared aerogel diameter pore size with different particle size. It can be seen
with the traditional acid-base two-step prepared aerogels (The diame- that the silica aerogels with different particle size had a wide pore size
ter of aerogel particles is generally less than 5 nm) [57–61], the aerogel distribution and almost the same most probable diameter around
prepared by monodispersed silica sol had larger particles with narrow 34.33 nm. Besides, there were some small size pores formed by the ir-
size distribution. The skeleton of the SA-1 aerogel sample prepared by regular stack of aerogel particles. With the increase of silica aerogel par-
small particle size mono-dispersed silica sol consisted of many stacked ticles, the average pore size of aerogel decreases gradually as shown in
and aggregated nanoparticles having a 13.59 ± 0.87 nm average parti- Table 2, and the average pore size were all in the mesoporous range.
cle size, which seem to be more likely to form large pores. The skeleton Table 2 showed the physical properties of silica aerogels with differ-
of the SA-2, SA-3 and SA-4 aerogel samples was formed by the intercon- ent particle size. It can be seen that the bulk density of the different par-
nection of individual particles with 20.31 ± 1.21, 28.64 ± 2.06 and ticle size silica aerogels prepared by the monodispersed silica sol with
34.61 ± 2.43 nm average particle size respectively (Table 2). It can be the same solid content was almost the same. Silica aerogels prepared
observed that when the particle size of the monodispersed silica sol by monodispersed silica sol at the same density had low thermal con-
was increased, the skeleton structure of the aerogel was changed from ductivity (0.02681–0.03176 W·m−1·K−1, 25 °C). With the increase of
the multi-particle stack into single particle connected to each other. In silica aerogel particles, the thermal conductivity increases gradually.
addition, with the increase of aerogel particles, macropores were more This is mainly due to the decrease of the specific surface area and aver-
likely to appear in the pore structure of aerogels. age pore size.
Fig. 3 (a) showed the nitrogen sorption isotherms the silica aerogels Density was a key parameter that reflected the structure of the silica
with different particle size. It can be seen that the curve shape of the aerogel during heat treatment. When heated after a short period of time

Fig. 2. SEM images of silica aerogels and TEM images of mono-dispersed silica sol (inset) with different particle size.

Table 2
The physical properties of silica aerogels with different particle size.

Sample Aerogel particle size Bulk density Thermal conductivity Surface area most probable aperture Average pore size
(nm) (g·cm−3) (W·m−1·K−1) (m2·g−1) (nm) (nm)

SA-1 13.59 ± 0.87 0.217 0.02681 295.67 37.06 28.34

SA-2 20.31 ± 1.21 0.206 0.02723 286.63 34.33 25.41
SA-3 28.64 ± 2.06 0.213 0.02962 219.71 34.33 33.91
SA-4 34.61 ± 2.43 0.221 0.03176 209.15 34.33 39.00
 H. Cai et al. / Materials and Design 191 (2020) 108640 5

Fig. 3. Nitrogen sorption isotherms (a) and size distribution (b) of silica aerogels with different particle sizes.

(0.5 h), as shown in Fig. 4 (a), there was no significant increase in the composed of small particles. The volume shrinkage of silica aerogels
density of the aerogels until 1000 °C; when the temperature was raised was relatively small (within 15%) until 900 °C after 2 h heat treatment
to 1100 °C, the density of the aerogels increased especially the SA-1 as shown in Fig. 4 (c) and (d). The silica aerogels except the SA-1 sample
sample composed of small particles; and when the temperature rises had less than 20% volume shrinkage at 1000 °C after 0.5 h heat treat-
further to 1200 °C, the density of aerogel increased significantly, and ment and had less than 40% volume shrinkage at 1000 °C after 2 h
there is no obvious difference in the density of each sample. When heat treatment. When the temperature rose to 1100 °C, the silica
heated after a long period of time (2 h), as shown in Fig. 4 (b), it can aerogels except the SA-1 sample had less than 40% volume shrinkage
be seen that the density of silica aerogel samples did not increased sig- after 0.5 h heat treatment but exceeded 80% volume shrinkage after
nificantly until 1000 °C, but increased obviously at 1100 °C; and the den- 2 h. The volume shrinkage of silica aerogels would exceed 80% in 0.5 h
sity of the silica aerogel was close to compact density when the heat treatment at 1200 °C.
temperature increased to 1200 °C. From the above results it can be concluded that the shrinkage char-
The volume shrinkage of the aerogels followed a trend similar to that acteristics of the silica aerogels except the SA-1 sample composed of
of the density. The volume shrinkage of silica aerogels increased obvi- small particles had no particularly obvious difference at high tempera-
ously with the increase of temperature, especially the SA-1 sample ture. In addition, SA-2 sample had larger specific surface area and

Fig. 4. Bulk density of silica aerogels after 0.5 h (a) and 2.0 h (b) heat treatment at different temperature; volume shrinkage of silica aerogels after 0.5 h (c) and 2.0 h (d) heat treatment at
different temperature.
6 H. Cai et al. / Materials and Design 191 (2020) 108640

Fig. 5. SEM images of SA-2 sample before (a) and after (b–i) heat treatment.

lower thermal conductivity among the three samples consisted of big (Fig. 5 b and c) were almost no difference, and the aerogel maintained
particles, therefore SA-2 sample consisted of 20.31 ± 1.21 nm particles the structure of single particle connected to each other, which indicated
have excellent comprehensive properties with high temperature resis- that the silica aerogel prepared by monodispersed silica sol had good
tance and low thermal conductivity. temperature resistance during this temperature range. At 1000 °C, the
morphology and structure of the aerogel began to change. After holding
3.2. Structural evolution at high temperature the temperature at 1000 °C for 0.5 h (Fig. 5 d), the aerogel structure
changed a little with some particles beginning to fuse together, but
Fig. 5 showed the morphology and structure of SA-2 sample before there was no significant change in the pore structure; after holding for
and after heat treatment observed by high resolution SEM. Compared 2 h (Fig. 5 e), the silica aerogel particles fused together partially and
with the untreated sample as shown in Fig. 5 (a), the morphology and the number of pores decreased obviously. When the temperature was
structure after holding the temperature at 800 and 900 °C for 2 h raised to 1100 °C, the morphology and structure of the aerogel changed

Fig. 6. Nitrogen sorption isotherms (a) and size distribution (b) of SA-2 sample after different temperature heat treatments.
 H. Cai et al. / Materials and Design 191 (2020) 108640 7

Table 3
The physical properties of SA-2 sample before and after heat treatment.

Sample Specific surface area (m2/g) Average pore diameter (nm) Most probable aperture (nm) Volume shrinkage (%)

SA-2 286.63 25.41 34.33 0

SA-2(800 °C, 2 h) 280.56 24.06 34.33 3.41 ± 1.21
SA-2(900 °C, 2 h) 271.35 24.53 34.33 12.41 ± 2.01
SA-2(1000 °C, 2 h) 222.08 19.97 25.25 35.14 ± 4.93
SA-2(1100 °C, 2 h) 114.89 13.06 17.20 83.82 ± 5.08
SA-2(1200 °C, 0.5 h) 6.39 10.23 17.20 89.86 ± 5.67

more obviously and rapidly. After holding the temperature at 1100 °C aerogel particles were fused further, the pores especially the macropore
for 0.5 h (Fig. 5 f), there are obvious clusters and fusion between parti- were seriously collapse and the number and the size of pores decreased
cles, and the number and the size of pores decreased simultaneously. obviously. After maintaining heating for 2 h, the aerogel particles almost
With prolonged heating (1 h at 1100 °C), as shown in Fig. 5 g, the silica completely fused together and nanoporous structure was almost

Fig. 7. Bulk density (a) and volume shrinkage (b) of SA-2 sample after different durations of heat treatment; (c) Nitrogen sorption isotherms, BET specific surface area (inset) and (d) pore
size distribution of SA-2 sample after different durations of heat treatment at 1000 °C; (e) Nitrogen sorption isotherms, BET specific surface area (inset) and (f) pore size distribution of SA-
2 sample after different durations of heat treatment at 1100 °C.
8 H. Cai et al. / Materials and Design 191 (2020) 108640

disappeared. When the temperature rose further to 1200 °C, the aerogel
particles completely fused together and the pore structure almost
completely disappeared in a short time (within 0.5 h).
Fig. 6 (a) showed the nitrogen sorption isotherms at different heat
treatment temperatures. It can be seen that silica aerogel samples
after heat treatment at different temperature still exhibited a mesopo-
rous structure according to the classification of the International
Union of Pure and Applied Chemistry [62]. Fig. 6 (b) showed the distri-
bution of the silica aerogel diameter pore size at different heat treat-
ment temperatures. After holding the temperature at 800 and 900 °C
for 2 h, the aerogel samples similar pore size distributions to the un-
treated samples and the specific surface area had no obvious decrease
as shown in Table 3. After holding the temperature at 1000 °C for 2 h,
the aerogels maintained a wide pore size distribution but the pore vol-
ume decreased, and the most probable diameter changed from
34.33 nm to 25.25 nm, in addition, the specific surface area reduced
from 286.63 to 222.08 m2/g. After holding the temperature at 1100 °C
for 2 h, the pore volume decreased obviously, the pore size distribution
became more concentrated with the macropore almost disappeared,
and the specific surface area reduced from 286.63 to 114.89 m2/g. Fig. 8. TG-DSC curves of original SA-2 sample from 25 to 1200 °C.
When the sample was heated to 1200 °C, the pore structure can hardly
be measured, which indicated that the pore structure completely disap-
peared, and the silica aerogels were in a dense state. It can be seen that 3.3. Thermal and chemical characteristics
the aerogel samples had high structural stability after 2 h heat treat-
ment when the temperature at 800 and 900 °C; the aerogel structure Fig. 8 showed the TG-DSC of original SA-2 sample (untreated after
changed obviously but can maintain part of the pore structure after ethanol supercritical drying) in air. There was an obvious weightless-
heating for a long time at 1000 and 1100 °C; and the porous structure ness processes occurred before 500 °C. Also, exothermic phenomena ap-
of aerogel disappeared in a very short period of time and silica aerogels peared in the DSC curve. The weight loss was caused by the removal of
cannot be used at this temperature at 1200 °C. Therefore, in order to fur- unreacted organic groups, thus the exothermic peak is caused by the ox-
ther determine the high temperature stability of aerogels after different idative decomposition of organic remnants in the sample. The residual
time heat treatment, the properties of aerogels at 1000 and 1100 °C organic groups on the surface of silica aerogels will oxidize and eventu-
were systematically studied. ally form Si–OH. For temperatures beyond 500 °C, the sample undergoes
It can be seen from Fig. 7 (a) and (b) that the density and volume continuous loss of weight, but there was no obvious endothermic peak
shrinkage of SA-2 sample increased slowly with the prolongation of or exothermic peak on the DSC curve beyond 500 °C. This phenomenon
heating time at 1000 °C. After 0.5 h heating at 1000 °C, the volume may be caused by the polycondensation of Si–OH on the surface and in-
shrinkage of aerogel was 18.11 ± 4.98%, and the volume shrinkage side of the silica particles. With the increase in temperature, the Si–OH
of aerogel was only about 35% after 2 h heat treatment. The aerogel bonds continuously condensed and eventually formed Si–O–Si bonds.
maintained mesoporous structure (Fig. 7 (c)) and had a wide pore Therefore, the weight of the sample was continuously reduced at tem-
size distribution (Fig. 7 (d)) all the heating time, and the specific sur- peratures between 600 °C and 1200 °C.
face area decreased slowly with the pore volume and the most prob- The XRD pattern of silica aerogel before and after rapid heating
able pore diameter gradually decrease in the heating process at was presented in Fig. 9. A single broad peak appeared at approxi-
1000 °C. The above results indicated that the aerogel sample can mately 2θ = 23° and was present before and after heating, which
maintain a relatively stable structure and show a good temperature was a typical characteristic for amorphous silica. It can be concluded
resistance at 1000 °C.
When the temperature rose to 1100 °C, as shown in Fig. 7
(a) and (b), the density and volume shrinkage of SA-2 sample in-
creased rapidly with the prolongation of heating time. After 0.5 h
heating at 1100 °C, the volume shrinkage of aerogel exceeded 40%,
and the volume shrinkage increased rapidly and finally exceeded
80% with the aerogel density closed to compact density. Fig. 7
(e) presents the nitrogen sorption isotherms and BET specific sur-
face area of silica aerogel at different heat treatment times at
1100 °C. It can be seen that for longer heating time, the silica
aerogel maintained a mesoporous structure, and the specific surface
area rapidly decreased. In Fig. 6 (f), the distribution of the silica
aerogel pore diameter for different heat treatment times at
1100 °C is shown. After 0.5 h heating, the pore volume decreased
rapidly with the most probable pore diameter being 29.45 nm.
When the heat treatment was extended to 1 h, the pore volume es-
pecially the macropore volume decreased obviously, and the pore
size distribution was narrower with 20.06 nm being the most prob-
able pore diameter. After 2 h heating, the pore volume further de-
creased with the volume of the macropores completely
disappeared. The above results indicated that the aerogel sample
cannot maintain a relatively stable structure and aerogels can only
be used during a short period at 1100 °C. Fig. 9. XRD patterns of SA-2 sample at different heat temperature.
 H. Cai et al. / Materials and Design 191 (2020) 108640 9

3.4. Temperature resistance mechanism

The skeleton of silica aerogels is formed by the interconnection of

secondary particles; therefore, the sintering behavior of aerogel is
mainly caused by sintering between secondary particles [66,67]. Pure
silica aerogels are amorphous materials [26], so viscous flow is the
main reason for the sintering of silica aerogels at high temperature. At
high temperature, the atoms on the aerogel particle surface will migrate
to the junction of the aerogel particles and form the sintering neck. The
sintering driving force between the interconnected particles can be
expressed by the chemical potential [21].
The chemical potential (μ1) of atoms under a circular curved surface
with a positive radius of curvature can be expressed by the following
formula:

μ 1 ¼ μ 0 þ 2Ωγ=r 1 ð3  1Þ

The chemical potential (μ2) of atoms at the sintering neck with a

negative radius of curvature can be expressed by the following formula:

μ 2 ¼ μ 0 −2Ωγ=r 2 ð3  2Þ

Fig. 10. FT-IR spectra of SA-2 sample at different heat temperature.

wherein, μ0 is the chemical potential of plane, Ω is the atomic weight, γ
is the surface free energy, r1 is the particle surface curvature, r2 is the
sintering neck curvature.
that the silica aerogels remained amorphous after heat treatment There will be a potential energy difference (Δμ) between the particle
from 800 °C to 1200 °C, and no phase transition process occurred in surface and the sintering neck:
the silica aerogel after heat treatment. The nanostructure change of
silica aerogel after heat treatment was not related to crystal Δμ ¼ 2Ωγ ð1=r 1 þ 1=r 2 Þ ð3  3Þ
transformation.
Fig. 10 showed the FT-IR spectra of the silica aerogel treated at dif- The small-sized particles possess a higher sintering driving force, as
ferent rapid heating temperatures. At room temperature, peaks from indicated in Eq. (3-3). The silica aerogels prepared by acid-base two-
the stretching and bending vibrations of the –OH group on the surface step method has pearl chain structure formed by the connection of
of the silica aerogel were detected at 3450 and 1635 cm −1. Also, small particles with each other, and it is prone to fuse between the par-
peaks caused by asymmetrical stretching, symmetrical stretching, ticles at high temperature [68–71]; in addition, for the slender skeleton,
and bending of Si–O–Si were found at 1085 cm−1, 800 cm−1 and the pores in the silica aerogels is more prone to collapse caused by skel-
465 cm−1. In addition, there were a few Si–OH stretching peaks at eton failure under sintering stress. The above is the reason for the
960 cm−1 [63–65]. With the increase of temperature, the Si–OH shrinkage and deformation of silica aerogels at high temperature.
peak gradually diminished, and eventually disappeared at 1100 °C, As indicated in Eq. (3-2), when the particle size increases, the
and the new Si–O–Si groups formed by the polycondensation reac- sintering driving force between particles will decrease obviously.
tion of connected Si–OH. Fig. 11 shows the structure change of SA-2 silica aerogels prepared

Fig. 11. Structure change of SA-2 silica aerogels prepared by mono-dispersed silica sol at high temperature.
10 H. Cai et al. / Materials and Design 191 (2020) 108640

by mono-dispersed silica sol at high temperature. The silica aerogels Acknowledgment

prepared by mono-dispersed silica sol have a large particle size with
narrow size distribution. This unique structure can effectively de- This work was supported by Natural Science Foundation of Hunan
crease sintering driving force and inhibit the viscous flow between Province of China (No. 2018JJ2469).
aerogel particles. Therefore the silica aerogels prepared by mono-
dispersed silica sol can maintain a stable structure until 900 °C. In ad-
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