Accepted Manuscript

Title: Mechanical performance and thermal stability of glass

fiber reinforced silica aerogel composites based on
co-precursor method by freeze drying

Authors: Ting Zhou, Xudong Cheng, Yuelei Pan, Congcong

Li, Lunlun Gong, Heping Zhang

PII: S0169-4332(17)33734-0
DOI: https://doi.org/10.1016/j.apsusc.2017.12.146
Reference: APSUSC 38016

To appear in: APSUSC

Received date: 26-9-2017

Revised date: 12-12-2017
Accepted date: 18-12-2017

Please cite this article as: Zhou T, Cheng X, Pan Y, Li C, Gong L, Zhang H, Mechanical
performance and thermal stability of glass fiber reinforced silica aerogel composites
based on co-precursor method by freeze drying, Applied Surface Science (2010),
https://doi.org/10.1016/j.apsusc.2017.12.146

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
Mechanical performance and thermal stability of glass fiber reinforced silica
aerogel composites based on co-precursor method by freeze drying

Ting Zhou, Xudong Cheng, Yuelei Pan, Congcong Li, Lunlun Gong, Heping
Zhang

T
State Key Laboratory of Fire Science, University of Science and Technology of China,

IP
Hefei, Anhui 230027, PR China

R
 Corresponding author.
E-mail address: zhanghp@ustc.edu.cn, chengxd@ustc.edu.cn

SC
Graphical abstract

U
N
A
M
ED
E PT
CC
A
Highlights
· Glass-fiber reinforced aerogel composites showed remarkable mechanical strength
and flexibility compared with pure aerogel powders.
· The hybrid aerogel showed superhydrophobicity, great thermal stability and low
thermal conductivity.
· The MTMS/water glass hybrid aerogels were prepared via freeze drying without
further surface modification.

T
· The molar ratio of MTMS/water glass could significantly influence the properties

IP
of composite.

R
SC
Abstract

U
In order to maintain the integrity, glass fiber (GF) reinforced silica aerogel
N
composites were synthesized using methltrimethoxysilane (MTMS) and water glass
A
co-precursor by freeze drying method. The composites were characterized by
M

scanning electron microscopy, Brunauer-Emmett-Teller analysis, uniaxial

compressive test, three-point bending test, thermal conductivity analysis, contact
ED

angle test, TG-DSC analysis. It was found that the molar ratio of MTMS/water glass
could significantly affect the properties of composites. The bulk density and thermal
PT

conductivity first decreased and then increased with the increasing molar ratio. The
composites showed remarkable mechanical strength and flexibility compared with
E

pure silica aerogel. Moreover, when the molar ratio is 1.8, the composites showed
CC

high specific surface area (870.9 m2/g), high contact angle (150°), great thermal
stability (560 °C) and low thermal conductivity (0.0248 W/m·K). These outstanding
A

properties indicate that GF/aerogels have broad prospects in the field of thermal
insulation.

Keywords

GF/aerogel composites; Co-precursor; Freeze drying; Mechanical properties; Thermal

stability

1. Introduction

Silica aerogels are nanostructured materials with fascinating characteristics, such

as extremely low density (0.03-0.20 g/cm3), high specific surface area (>1000 m2/g),
low thermal conductivity (0.005-0.021 W/m·K), which have drawn substantial

T
attention in thermal insulation, aerospace application, catalytic supports, etc [1, 2].

IP
Pan et al. obtained hybrid aerogels based on MTMS/water glass with low thermal

R
conductivity and high thermal stability [3]. But the low strength, fragility and

SC
brittleness of the aerogel restrict the practical application. Lots of researches have
been made to improve the mechanical properties using fibers as supporting skeletons.

U
Inorganic and organic fibers, including mineral [4], ceramic [5, 6], aramid [7] and
glass fibers [8, 9], can decrease the bulk size of aerogel and improve the compressive
N
strength. Glass fiber, a kind of noncombustible fiber, possess high compressive
A
fracture strength, which is suited for fragile aerogels as the reinforcement. Chang et al.
M

synthesized flexible aerogel-glass fiber composites by ambient drying with improved

mechanical properties [10].
ED

Another critical factor, which limits the aerogels’ application, is the surface
modification process with arduous solvent exchanges and hazardous organic solvent.
PT

Co-precursor could be a good choice without further surface modification. Rao et al.
prepared MTMS/ TMOS aerogel with thermal stability of 277 °C and thermal
E

conductivity of 0.069 W/m·K [11]. Nadargi et al. prepared TEOS based aerogel using
CC

trimethylmethoxysilane (TMMS), dimethyldimethoxysilane (DMMS) and

methyltrimethoxysilane (MTMS) as co-precursor, respectively, with low thermal
A

stability (300 °C) and high thermal conductivity (0.065 W/m·K) [12]. From the above,
although the co-precursor aerogels were successfully obtained by co-precursor
method, the aerogels prepared using this way all presented poorer thermal stability
and higher thermal conductivity than that of pure MTMS aerogels or pure TEOS
aerogels. Lots of efforts have been done to improve the thermal insulation properties
by researchers. In the present work, the thermal stability of aerogels is improved
based co-precursor method with organic and inorganic silicon source hybridization.
It is known that supercritical drying is the earliest method used to prepare silica
aerogel [13]. However, it is difficult for large-scale commercialization requiring
intensive energy, high-cost facility and high pressure. Thus, ambient pressure drying
has aroused widespread concern [14, 15]. But it involves repetitive solvent exchange
and surface modification before drying to obtain hydrophobic aerogel. These toxic

T
solvents are harmful to environment and human. Freeze drying is another promising

IP
method which is based on sublimation of excess solvent. Ren et al. found an easy way

R
to prepare monolithic inorganic oxide aerogels under vacuum conditions [16]. Sanosh

SC
et al. successfully synthesized silica cryogel-glass fiber blankets by vacuum freeze
drying [17]. In this study, we employed freeze drying method to reduce capillary

U
pressure and obtain versatile glass fiber reinforced silica aerogel composites.
N
2. Experimental
A
M

2.1 Materials and preparation

ED

Glass fibers (diameter of 8-15 µm) used as reinforcement were purchased from
Sinopharm Chemical Reagent Co., Ltd. (China). The precursors were water glass
(Qingdao Dongyue Sodium Silicate Co., Ltd., China) and MTMS (Aladdin). Other
PT

chemicals including Tert-butyl alcohol, hydrochloric acid and ammonia were also
purchased from SCRC. 0.1 mol/L HCl (aq) and 0.5 mol/L NH4OH (aq) were prepared
E

and used as acid and base catalysts in the sol-gel process, respectively. All agents
CC

were chemical pure grade.

The experimental procedure for the preparation is illustrated in Fig. 1. Firstly, the
A

precursors of MTMS and water glass were hydrolyzed separately. The MTMS and
solvent was stirred for 30 min to ensure sufficient hydrolysis under acidic condition.
The molar ratio of MTMS: Tert-butyl alcohol: H2O: HCl was fixed at 1:2.97:15.8:5.7
×10-3. Water glass was diluted with deionized water passing through amberlite ion
exchanged resin to replace the Na+ with H+ ion. The molar ratio of MTMS/water glass
was defined as X, and the values of X are 1.8, 1.3, 1, 0.6 and 0, respectively. MTMS
and water glass sol mixed together and added NH4OH solution to adjust the pH to 6.
Secondly, the resulting alcosol was quickly poured into a rectangular polyethylene
plastic mold with the dimensions of 87 mm×57 mm×20 mm and the glass fiber was
completely immersed in the alcosol. Then the condensation occurred and the gel
generally formed in 30 min. The GF/aerogels aged with Tert-butyl alcohol for 3 days
to strengthen the skeleton. At last, the GF/aerogels were placed in the laboratory

T
freeze dryer for 8 h at a low temperature of -80 °C and then were dried for about 48h

IP
at vacuum pressure. Finally, the glass fiber-reinforced silica aerogels were obtained.

R
SC
U
N
A
M
ED
E PT
CC

Fig. 1. Experimental illustration of the preparation of glass fiber-reinforced aerogels

A

2.2 Methods of characterization

The density of the GF/aerogel was calculated based on its weight to volume ratio.
The microstructure of the composite was studied by field emission scanning electron
microscope (SEM, SIRION200, FEI). The specific surface areas and pore size
distributions (PSD) were estimated by Brunauer-Emmett-Teller (BET) analysis and
Barrett-Joyner-Halenda (BJH) method (Tristar II 3020M，Micromeritics Instrument
Corporation, USA), respectively.
Uniaxial compression test and three-point bending test were performed using
Electronic dynamic and static fatigue testing machine (E3000K8953, Instron). The
size for uniaxial compression test is 25 mm×25 mm×12 mm. The rectangular
samples with the dimension of 85 mm×15 mm×12 mm were prepared for

T
three-point bending test. The test was shown in Fig. 2 and the loading rate was set as

IP
2 mm/min. The flexural modulus is calculated from Eqs. (1) - (3).

R
3PL
f 

SC
2bd 2 （1）

6 Dd
f 
L2
U （2）
N
 f 2  f 1
Ef 
 f 2  f1
A
（3）
In which, σf is the flexural stress, in MPa; εf is the flexural strain in outer surface;
M

Ef is the flexural modulus, in MPa; P is the load, in N; L is the support span, set as 60
ED

mm; D is the maximum deflection of the center of the specimen, in mm; b and d are
the width and thickness of the specimen, in mm, respectively.
TG-DSC (SDT Q600, TA) was employed to test the thermal stability operating in
PT

oxygen atmospheres with a heating rate of 10 °C/min from room temperature to

800 °C. The hydrophobicity of the samples was measured with contact angle
E

instrument (SL200K, USA). The information of chemical bonds was given by Fourier
CC

transform infrared spectroscopy (Nicolet 8700, TFS, USA). Thermal conductivity (λ)
was determined by thermal conductivity measurement (TC 3000E, Xiaxi technology,
A

China).
 T
R IP
SC
Fig. 2. Photograph of the three-point bending test.

U
N
3. Results and discussion
A
3.1 Reaction process
M

The fibers act as supporting skeleton, which are just a physical combination with
ED

silica aerogels [18]. The main chemical reactions are the hydrolysis and condensation
of MTMS and water glass. As can be seen from Eqs. (4) and (5), the hydroxyl groups
PT

presented on the surface of precursors after sufficient hydrolysis. Hydrolyzed MTMS

still remained one non-hydrolysable –CH3 group. Then the hydrolyzed MTMS reacted
E

with the hydrolyzed water glass and the –CH3 groups can successfully adhere to the
CC

surface of the aerogel. The formation of the gel skeleton is described in Eq. (6). The
introduction of MTMS is equal to the conventional surface modification so that the
A

network is strong enough to reduce volume shrinkage.

 T
R IP
SC
U
N
A
M

3.2 Structure analysis

ED

Fig. 3 gives the microstructures of different samples. Fig. 3(a) shows silica
aerogel matrix adhered to the glass fibers tightly. The diameter of a singer glass fiber
PT

is approximately 17 µm. Fig. 3(b)-(f) show the SEM photographs of samples G1 to

G5 which is the magnification of aerogel matrix on the glass fiber. The aerogel is
E

consisted of nanoparticles and it reveals that the introduction of glass fiber does not
CC

influence the three-dimensional nanoporous structure of the aerogel. With the

decrease of MTMS/water-glass molar ratio, the size of the pores is smaller and the
A

distribution of nanoparticles is more uniform. Seen from the Fig. 3(a) and (b), the
large pores and aggregated clusters are formed with high X value.
 T
R IP
Fig. 3. Glass fiber surface covered with aerogel (a), aerogel nanoparticles on the fiber
surface prepared with: X=1.8 (b), X=1.3 (c), X=1 (d), X=0.6 (e), X=0 (f).

SC
3.3 Pore size distribution

U
Table 1 lists a summary of pore structure including specific surface area, pore
N
volume and average pore size. It is obvious that the pore volume and average pore
A
size decrease with the increase of MTMS in aerogels. But the trend of specific surface
M

area is a little different. The specific surface area reaches the maximum value of 870.9
m2/g when X=1. But the sample G5 prepared by pure water glass without any MTMS
ED

has minimum surface area of 487.2 m2/g compared with other samples. This is
because the capillary pressure will occur when the solvent is removed through
PT

sublimation. The capillary differential pressure can give rise to structure collapse and
be calculated according to the following equation:
E

2 cos 
P
CC

r （7）

In which, P is capillary pressure, in Pa; σ is surface tension of the solvent, in N;

θ is the contact angle and r is the meniscus of radius. Generally, solvent exchange
A

and surface modification can reduce the capillary pressure. The samples G5 without
any surface modification will have great shrinkage during freeze drying process [19].
Table 1 Pore parameters of different samples
Molar ratio of BET surface Pore volume Average pore
MTMS/water glass area(m2/g) (cm3/g) size(nm)
 G1 1.8 669.8 3.186 13.710
G2 1.3 740.9 3.091 13.369
G3 1 870.9 1.803 9.125
G4 0.6 852.4 1.549 8.186
G5 0 487.2 2.097 7.553

The N2 adsorption-desorption isotherms curves of all five samples in Fig. 4

exhibit a typical type IV, which generally presents in the mesoporous materials. The

T
same hysteresis loops of type H3 for five samples indicate the probable presence of

IP
silt-shaped pores [20]. The results of the pore size distribution (PSD), measured by
BJH method, are shown in Fig. 5. It is known that most of the pore diameter

R
distributed between 20-40 nm for all five samples. But the highest dV/dlog (D) pore

SC
volume for G1 and G2 are only 0.91 and 1.28 cm3/g, respectively. It is obviously
lower than those of G3-G5, which indicates more mesopores exist in aerogel with low
molar ratios. U
N
A
M
ED
E PT
CC
A

Fig. 4. N2 adsorption-desorption isotherms of five GF/aerogels prepared with various

molar ratio.
 T
R IP
SC
U
Fig. 5. Pore size distributions of five GF/aerogels prepared with various molar ratio.
N
3.4 Mechanical properties
A

Fig. 6 shows the photograph of typical uniaxial compression test of the

M

GF/aerogels. Fig. 6(a) is the initial stage of the test and the compression machine
could not contact the GF/aerogel tightly because of the unsmooth surface of the
ED

specimen. With higher molar ratio of MTMS/water glass, the composites exhibited
high deformability and recovered their original shape without breaking when the
PT

stress released.
E
CC
A
 T
R IP
SC
Fig. 6. Uniaxial compression test of the GF/aerogels.

U
From Fig. 7, it can be seen that the stress-strain curve of the GF/aerogels could
N
be divided into four different stages: the contact stage, the linear stage, the yielding
A
stage and the densification stage [21]. The contact stage with low strains from 0 to 10%
M

is caused by the uneven surface of the specimen. At the linear stage, the strain ranges
from 10 to 20% and the slope of the curve remains unchanged. The nanopores of
ED

silica aerogel act as the main bearing part while the fibers are only responsible for the
integrity of the GF/aerogel [18]. At the yielding stage, the stress increases rapidly and
PT

fibers would be contributed to the main bearing part which is different from the pure
aerogels. At the densification stage, the slope of curve rises significantly which is
E

mainly due to the collapse of aerogel and gradual densification of the porous
CC

structure.
A
 T
R IP
SC
Fig. 7. A typical uniaxial compression stress-strain curve of sample G2 at 25 °C.

U
The stress-strain curves of the five composites with various molar ratio are
shown in Fig. 8. All curves could be divided into four parts. The curves showed better
N
linearity when the strain is from 15% to 20%. Table 2 listed the summaries of the
A
stress at the strains of 15%, 20% and elastic modulus. Elastic modulus is used to
M

measure the degree of elastic deformation of the material. With the increasing value,
the stress deformation of the material is increasing, which indicates a great rigidity of
ED

the material [21]. As shown in Table 2, the σ15%, σ20% and compressive elastic
modulus increase with increasing molar ratio in which the composites show great
PT

elasticity at X=1.8 and 1.3. Glass giber as a whole acted as supporting skeleton and
retained the integrality of aerogel matrix. The volume and mass were keeping
E

constant in this study, so the difference of elastic modulus was caused by difference of
CC

MTMS. It is indicated that the elasticity of material is better with more MTMS.
A
 T
R IP
SC
Fig. 8. Uniaxial compressive curve of five composites with various molar ratio: (G1)
X=1.8; (G2) X=1.3; (G3) X=1; (G4) X=0.6; (G5) X=0.
Table 2 U
N
Analytical data of compressive curve of GF/aerogels
A
Molar ratio (X) σ15% (kPa) σ20% (kPa) Elastic modulus (kPa)
M

1.8 47.26 78.97 634.2

1.3 50.87 87.44 731.4
ED

1 85.28 154.93 1393.0

0.6 141.23 250.54 2186.2
0 128.88 288.10 3184.4
PT

Fig. 9 (a) shows the flexural strain-stress curves of the GF/aerogels obtained by
three-point bending test. It can be seen that the flexural stress continues to increase
E

with the increasing flexural strain. The tested specimen was only bent without
CC

material failure because glass fiber connected tightly layer by layer. Flexural modulus
(Ef) is to characterize the stiffness of the material, that is, the ability of the material to
A

resist deformation. The Ef first increases steadily and then increases rapidly as the
molar ratio increases in Fig. 9 (b). With the molar ratio increasing, the composites
become stiffer and the flexibility of the composites decreases with the flexural
modulus rising. The mass of glass fibers in five samples is the same. Therefore, the
change in molar ratio is the key factor affecting the elasticity of the material.
 T
IP
Fig. 9. Flexural stress-strain curves (a) and flexural modulus (b) of the five
composites with various molar ratios in three-bending bending test.

R
SC
3.5 FTIR analysis and hydrophobicity

U
The FTIR spectrum given in Fig. 10 indicates the information of chemical bonds.
The strong adsorption peaks around 1100 cm-1 and 800 cm-1 are caused by the
N
symmetric and asymmetric stretching vibrations of Si-O-Si bonds, respectively [11].
A
For five samples, the vibrations at 3435 cm-1 and 1631 cm-1 are due to residual –OH
M

groups or the adsorbed water [22].

The presence of Si-CH3 groups is derived from MTMS by vibrational bands at
ED

1275 cm-1 and 917 cm-1, and the intensity decreases as the molar ratio of
MTMS/water glass decreases. This indicates that the amount of Si-CH3 functionalities
PT

declines with the decrease in MTMS [23]. Particularly, the bonds of Si-CH3 groups
disappear when X=0. Furthermore, the faint peak at 960 cm-1 is attributed to the
E

stretching vibrations of ≡Si-OH group for samples G4 and G5 [24]. The samples
CC

possess unreacted Si–OH from orthosilicate with lower molar ratio of MTMS/water
glass. From above, it explains why the GF/aerogels show decreased contact angle and
A

demonstrates that samples G4 and G5 show hydrophilicity. The images of contact

angles are presented in Fig. 11.
 T
R IP
SC
Fig. 10. FTIR spectrum of five samples (G1-G5).
Fig. 11 shows the water contact angles of GF/aerogels with different molar ratio

U
of MTMS/water-glass. Fig. 11(a) shows a water droplet on the top surface of aerogel
blanket and the hydrophobicity is further quantified by contact angle. It is known
N
from G1 to G5 that the increasing MTMS/water-glass molar ratio results in an
A
increase of contact angle, and the contact angle of 150° for G1 indicates
M

superhydrophobic properties. It is consistent with the FTIR spectra analysis that the
surface chemical groups (≡Si-CH3) from MTMS successfully replaced the hydroxyl
ED

groups. On the contrary, the samples of G3-G5 are hydrophilic which is caused by the
remained ≡Si-OH groups and G5 is completely hydrophilic with no surface chemical
PT

group [25].
E
CC
A

Fig. 11. A water droplet on the surface of GF/aerogel (a), photograph of the contact
angle test for the G1-G5 aerogel samples.
3.6 Thermal properties

Fig. 12 shows that the bulk density of the GF/aerogels first decreases and then
grows up when X decreases from 1.8 to 0. The thermal conductivity shows the same
trend with the density. At a MTMS/water glass molar ratio of 1, the aerogel shows
low density 0.174 g/cm3 and low thermal conductivity 0.0213 W/m·K.

T
R IP
SC
U
N
A
M
ED

Fig. 12. Bulk density and thermal conductivity of GF/aerogels with the increasing X.
Fig. 13 presents the TG-DSC analysis in air atmosphere of two samples with
PT

different molar ratio 1.8 and 0, respectively. The process in Fig. 13(a) can be divided
into three stages. The specimen first loses weight at a low temperature which is lower
E

than 200 °C because of the evaporation of residual solvent and absorbed water [26].
CC

The second stage is the condensation of ≡Si-OH groups. There is a dramatic

exothermic peak at the third stage which is considered to be the oxidation of Si-CH3
A

groups. One of the key points to measure the thermal stability is the initial
temperature of the exothermic reaction. The thermal stability temperature is about
560 °C and the hydrophobicity turns into the hydrophilicity with the decomposition of
–CH3 groups when exceeding 560 °C.
It can be seen from Fig. 13(b) that only two stages in TG curve when the molar
ratio is 0. There is no exothermic peak because no –CH3 group exists in aerogel
without any surface modification. The first weight loss stage is 15.97% between
30 °C and 230 °C which is larger than that in Fig. 13(a). It is caused by the
dehydration of hydroxyl groups on the surface of aerogel.

T
R IP
SC
Fig. 13. The TG-DSC curves of two different GF/aerogels prepared with: (a) X=1.8;
(b) X=0.

4. Conclusions U
N
A
Glass-fiber (GF) reinforced silica aerogel composites based on MTMS/water glass
M

were synthesized by freeze drying. The microstructure, thermal stability,

hydrophobicity and mechanical properties of the GF/aerogels with different molar
ED

ratio of MTMS to water glass (1.8-0) were systematically measured and analyzed.
The density and thermal conductivity first decreases and then grow up with the
PT

increase of molar ratio. When the molar ratio is 1.8, the obtained composites have
outstanding performance with high specific surface area (870.9 m2/g), high contact
E

angle (150°), great thermal stability (560 °C) and low thermal conductivity (0.0248
CC

W/m∙K). The microstructure analysis presents the interfacial adhesion with the glass
fiber and aerogel matrix. The silica aerogel composites show remarkable mechanical
A

strength and flexibility, which could endure large compressive and flexural strain
without structural destroyed. These outstanding characteristics indicate that the
obtained GF/aerogels by freeze drying based on organic/inorganic co-precursor have
significantly improved mechanical properties and thermal insulation performance.
Acknowledgment

The work was supported by Anhui Programs for Science and Technology
Development (No. 1604a0902175) and Fundamental Research Funds for the Central
Universities (Grant No. WK2320000032).

References

T
[1] P.C. Thapliyal, K. Singh, Aerogels as Promising Thermal Insulating Materials: An

IP
Overview, Journal of Materials, (2014) 127049 (127010 pp.)-127049 (127010 pp.).

R
[2] F. Shi, L. Wang, J. Liu, Synthesis and characterization of silica aerogels by a novel

SC
fast ambient pressure drying process, Materials Letters, 60 (2006) 3718-3722.
[3] Y. Pan, S. He, L. Gong, X. Cheng, C. Li, Z. Li, Z. Liu, H. Zhang, Low

U
thermal-conductivity and high thermal stable silica aerogel based on
N
MTMS/Water-glass co-precursor prepared by freeze drying, Materials & Design, 113
A
(2017) 246-253.
[4] S.K. Rajanna, M. Vinjamur, M. Mukhopadhyay, Mechanism for formation of
M

Hollow and Granular Silica Aerogel Microspheres from rice husk ash for drug
ED

delivery, Journal of Non-Crystalline Solids, 429 (2015) 226-231.

[5] D. Shi, Y. Sun, J. Feng, X. Yang, S. Han, C. Mi, Y. Jiang, H. Qi, Experimental
investigation on high temperature anisotropic compression properties of
PT

ceramic-fiber-reinforced SiO2 aerogel, Materials Science and Engineering

a-Structural Materials Properties Microstructure and Processing, 585 (2013) 25-31.
E

[6] A. Karout, P. Buisson, A. Perrard, A.C. Pierre, Shaping and mechanical

CC

reinforcement of silica aerogel biocatalysts with ceramic fiber felts, Journal of

Sol-Gel Science and Technology, 36 (2005) 163-171.
A

[7] Z. Li, L. Gong, X. Cheng, S. He, C. Li, H. Zhang, Flexible silica aerogel
composites strengthened with aramid fibers and their thermal behavior, Materials &
Design, 99 (2016) 349-355.
[8] J.-J. Zhao, Y.-Y. Duan, X.-D. Wang, B.-X. Wang, An analytical model for
combined radiative and conductive heat transfer in fiber-loaded silica aerogels,
Journal of Non-Crystalline Solids, 358 (2012) 1303-1312.
[9] Y. Liao, H. Wu, Y. Ding, S. Yin, M. Wang, A. Cao, Engineering thermal and
mechanical properties of flexible fiber-reinforced aerogel composites, Journal of
Sol-Gel Science and Technology, 63 (2012) 445-456.
[10] C.-Y. Kim, J.-K. Lee, B.-I. Kim, Synthesis and pore analysis of aerogel-glass
fiber composites by ambient drying method, Colloid Surface A, 313 (2008) 179-182.
[11] A.V. Rao, M.M. Kulkarni, D.P. Amalnerkar, T. Seth, Surface chemical

T
modification of silica aerogels using various alkyl-alkoxy/chloro silanes, Applied

IP
Surface Science, 206 (2003) 262-270.

R
[12] D.Y. Nadargi, R.R. Kalesh, A.V. Rao, Rapid reduction in gelation time and

SC
impregnation of hydrophobic property in the tetraethoxysilane (TEOS) based silica
aerogels using NH4F catalyzed single step sol–gel process, Journal of Alloys and
Compounds, 480 (2009) 689-695.
U
N
[13] A.V. Rao, R.R. Kalesh, Comparative studies of the physical and hydrophobic
A
properties of TEOS based silica aerogels using different co-precursors, Science and
Technology of Advanced Materials, 4 (2003) 509-515.
M

[14] J.L. Gurav, A.V. Rao, D.Y. Nadargi, H.-H. Park, Ambient pressure dried
ED

TEOS-based silica aerogels: good absorbents of organic liquids, Journal of Materials

Science, 45 (2009) 503-510.
[15] J.L. Gurav, A.V. Rao, U.K.H. Bangi, Hydrophobic and low density silica aerogels
PT

dried at ambient pressure using TEOS precursor, Journal of Alloys and Compounds,
471 (2009) 296-302.
E

[16] L. Ren, S. Cui, F. Cao, Q. Guo, An easy way to prepare monolithic inorganic
CC

oxide aerogels freeze-drying, Angew Chem Int Ed Engl, 53 (2014) 10147-10149.

[17] S.K. Padmanabhan, E. Ul Haq, A. Licciulli, Synthesis of silica cryogel-glass
A

fiber blanket by vacuum drying, Ceramics International, 42 (2016) 7216-7222.

[18] Z. Li, X. Cheng, S. He, X. Shi, L. Gong, H. Zhang, Aramid fibers reinforced
silica aerogel composites with low thermal conductivity and improved mechanical
performance, Composites Part A: Applied Science and Manufacturing, 84 (2016)
316-325.
[19] J. He, X.L. Li, D. Su, H.M. Ji, X.J. Wang, Ultra-low thermal conductivity and
high strength of aerogels/fibrous ceramic composites, J Eur Ceram Soc, 36 (2016)
1487-1493.
[20] F. Rojas, I. Kornhauser, C. Felipe, J.M. Esparza, S. Cordero, A. Domínguez, J.L.
Riccardo, Capillary condensation in heterogeneous mesoporous networks consisting
of variable connectivity and pore-size correlation, Physical Chemistry Chemical
Physics, 4 (2002) 2346-2355.

T
[21] X. Yang, Y. Sun, D. Shi, J. Liu, Experimental investigation on mechanical

IP
properties of a fiber-reinforced silica aerogel composite, Materials Science and

R
Engineering: A, 528 (2011) 4830-4836.

SC
[22] S.A. Mahadik, F. Pedraza, V.G. Parale, H.-H. Park, Organically modified silica
aerogel with different functional silylating agents and effect on their physico-chemical

U
properties, Journal of Non-Crystalline Solids, 453 (2016) 164-171.
N
[23] H. Yu, X. Liang, J. Wang, M. Wang, S. Yang, Preparation and characterization of
A
hydrophobic silica aerogel sphere products by co-precursor method, Solid State Sci,
48 (2015) 155-162.
M

[24] S. Zong, W. Wei, Z. Jiang, Z. Yan, J. Zhu, J. Xie, Characterization and

ED

comparison of uniform hydrophilic/hydrophobic transparent silica aerogel beads:

skeleton strength and surface modification, RSC Adv., 5 (2015) 55579-55587.
[25] C.C. Li, X.D. Cheng, Z. Li, Y.L. Pan, Y.J. Huang, L.L. Gong, Mechanical,
PT

thermal and flammability properties of glass fiber film/silica aerogel composites,

Journal of Non-Crystalline Solids, 457 (2017) 52-59.
E

[26] H. Liu, W. Sha, A.T. Cooper, M. Fan, Preparation and characterization of a novel
CC

silica aerogel as adsorbent for toxic organic compounds, Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 347 (2009) 38-44.
A