Ceramics International 48 (2022) 16290–16299

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Improvement of thermal insulation and compressive performance of

Al2O3–SiO2 aerogel by doping carbon nanotubes
Daiping Jiang a, Jin Qin a, Xiangfa Zhou b, Qiaoli Li a, Danqing Yi a, Bin Wang a, *
a
School of Materials Science and Engineering, Central South University, Changsha, Hunan, 410083, PR China
b
School of Biotechnology and Environmental Engineering, Changsha University, Changsha, Hunan, 410083, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Carbon nanotubes (CNTs) have attracted significant attention from researchers due to their high specific strength
Composites and good extinction properties. In this study, Al2O3–SiO2 aerogel composites doped with 0–1.0 wt% CNTs were
Thermal conductivity prepared by sol-gel and supercritical drying technologies, and the effects of CNT content on their microstructure,
Al2O3
mechanical properties, heat insulation properties, and theoretical thermal conductivity were examined. With an
SiO2
CNTs
increase in the CNT amount, the specific surface area and pore diameter of the aerogel composites decreased,
while their compressive properties were enhanced. The obtained results revealed that the 1.0 wt% CNT-doped
Al2O3–SiO2 aerogel composite exhibited the best comprehensive properties, while its thermal conductivity of
0.178 W/mK at 1000 ◦ C was 15% lower than that of pure aerogel. In addition, the theoretical thermal con­
ductivities of all samples were calculated in the temperature range of 25–1000 ◦ C. This study explained that the
addition of CNTs can significantly improve the comprehensive properties of Al2O3–SiO2 aerogel composites.

1. Introduction embedded on aerogel composites as a thermal barrier. Wang et al. [15]

Aerogels prepared by sol-gel technology possess unique network
structures and nanopores, which endow them with advantageous
properties, including high porosity, low density, and low thermal con­
ductivity [1–4]. Owing to the high heat resistance of alumina oxide
aerogel and excellent heat insulation characteristics of silica aerogel [5],
Al2O3–SiO2 composite aerogel exhibits superior characteristics and can
be potentially utilised in aviation, aerospace, and industrial applications
as a high-temperature thermal insulation material [6–9]. However, the
high infrared transparency of alumina-based aerogels increases the
infrared radiation intensity at elevated temperatures, which produces a
negative effect on their thermal insulation performance [10,11].
Therefore, the development of aerogels with advanced thermal insu­
lation characteristics would be highly beneficial for various research
fields.
Numerous studies focusing on the preparation of aerogels with low
thermal conductivity have been conducted over the past several de­
cades. One of the commonly used methods for improving the thermal
insulation performance of aerogel composites involves the addition of
fibres or opacifiers to an aerogel matrix. For example, ZrO2 fibre felt
[12], Al2O3 particles [13] and aluminum borate whisker [14] have been
proposed a method for fabricating TiO2 opacifier/fibre/alumina-based
aerogel ternary composites with sub-micrometre TiO2 opacifier parti­
cles uniformly dispersed in fibre reinforcements. The obtained
high-temperature thermal conductivity was as low as 0.168 W/mK at
1000 ◦ C. In addition, the introduction of carbon black [16] and carbides
[17] into the composite structure enhanced its absorption and reflection
capabilities in the infrared region, which significantly reduced the
infrared transmittance of the composite and improved its heat insulation
performance [18]. To date, a large number of relevant studies have
focused on the modification of aerogels by large-size materials, and little
attention has been paid to the influence of carbon nanomaterials on their
thermal insulation performance.
Nano-sized carbon materials match the nanoporous structure of
aerogels and can be uniformly dispersed in their pores to augment the
matrix strength and enhance the thermal insulation performance of the
composite [19]. It has been shown previously that the addition of a small
amount of one-dimensional or two-dimensional carbon materials may
considerably reduce the total thermal conductivity of the material [20,
21]. For example, Liu et al. [22] effectively enhanced the thermal
insulation performance of composites at room temperature by intro­
ducing graphene oxide (GO) into a silica aerogel network. As an ideal

* Corresponding author. School of Material Science and Engineering, Central South University, Changsha, 410083, PR China.
E-mail address: wangbin325@263.net (B. Wang).

https://doi.org/10.1016/j.ceramint.2022.02.178
Received 30 November 2021; Received in revised form 8 February 2022; Accepted 16 February 2022
Available online 25 February 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
D. Jiang et al.
nanofiller, carbon nanotubes (CNTs) can be utilised to improve the
comprehensive performance of host materials due to their high specific
strength and extinction coefficient. Mahesh et al. [23] prepared
multi-walled CNT-doped SiO2 aerogel composites and found that CNT
addition decreased the thermal conductivity of the aerogel. In addition,
Patil’s team has done a great deal of research on aerogel composites
from the aspect of molecular dynamics simulation, such as establishing a
whole atom model of aerogel [24], studying the mechanical behavior of
aerogel composites under tensile and compression tests [25] and the
thermal conductivity of SiO2 aerogel composites was calculated [26].
However, very few studies on the effects of CNTs on the comprehensive
properties of binary composite aerogels have been conducted.
In this work, CNTs were uniformly dispersed in an Al2O3–SiO2 so­
lution by a rapid gel method and ultrasonic treatment, and CNT/
Al2O3–SiO2 aerogel composites were prepared by supercritical drying
technology. The effects of CNT content (0–1.0 wt%) on the micro­
structure, compressive properties, thermal insulation properties, and
theoretical thermal conductivity of the obtained Al2O3–SiO2 aerogel
composites were investigated for the first time, and their heat transfer
mechanism was discussed.
2. Experimental
2.1. Materials
CNTs used as a reinforcement were purchased from Beijing Deke
Daojin Science and Technology Co., Ltd. (their morphology is shown in
Fig. 1). The original CNTs had a large aspect ratio (length: 10–30 μm,
diameter >50 nm) and smooth surface nanotube-like structure with
some curvature. Aluminium chloride hexahydrate (AlCl3⋅6H2O,>97%)
and tetraethylorthosilicate (TEOS) used as aluminium and silicon pre­
cursors, respectively, were supplied by Hunan Ronglan Intelligent
Technology Co., Ltd. Nitric acid (HNO3) catalyst was supplied by Tianjin
Kemiou Chemical Co., China. 1, 2-epoxypropane (PO) was supplied by
Sinopharm Chemical Reagent Co., LTD.A mixture of ethanol (EtOH>
99%) and distilled water (H2O) was used as the solvent.
2.2. Preparation of CNT/Al2O3–SiO2 gel
The synthesis process of CNT/Al2O3–SiO2 is described in Fig. 2. First,
CNT/Al2O3–SiO2 sols were prepared in the following three steps. In step
1, alumina sol and silica sol were obtained by stirring the AlCl3⋅6H2O:
EtOH:H2O and TEOS:H2O:EtOH:HNO3 mixtures with molar ratios of
Fig. 1. Microscopic scanning morphology of CNTs.
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1:4:12:0.001 and 1:16:4, respectively, at 25 ◦ C. After 2 h of prehy­
drolysis, the SiO2 sol was added dropwise to the Al2O3 sol at an Al:Si
molar ratio of 2:1 and stirred for 10 h to obtain a homogeneous
Al2O3–SiO2 sol.
In step 2, 1, 2-epoxypropane gelation promoter was added to the
mixed sol at a volume ratio of 1:8 to accelerate the condensation process.
At the same time, a small amount of CNTs was added to the solution. To
ensure the homogenous dispersion of CNTs without aggregation, the
mixed solution was stirred for 10 min and ultrasonicated at 100W power
for 20 min. Subsequently, the solution was poured into a glass beaker
and kept sealed until the sol was converted into a CNT/Al2O3–SiO2
alcohol gel.
In step 3, the network skeleton structure was further enhanced. For
this purpose, the composite gel was aged at 25 ◦ C for 48 h in an EtOH
solution containing 20 vol% TEOS and then in pure EtOH for 48 h.
Finally, Al2O3–SiO2 aerogel composites were obtained by supercritical
drying using EtOH as the drying agent. The samples were denoted AS/
CNT-X, where X represented various CNT mass fractions.
2.3. Characterizations
The bulk density of AS/CNT-X composites is obtained by the ratio of
mass to the volume, where the volume is gained by measuring the
diameter and height of the samples with vernier caliper. The porosity is
defined by the formula: ∅ = (1 − ρa /ρbulk )⋅100%.Scanning electron
microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) was
used to morphologies and elemental analysis of the samples (TDCLS-
4800, Japan). Fourier transform infrared spectroscopy (FT–IR,
TENSOR27, Germany) was performed to analyse surface compositions
of the prepared samples. A surface area and pore size analyser (Micro­
meritics ASAP2020, USA) was used to record N2 adsorption – desorption
isotherms. Surface areas, pore volumes, and pore sizes were determined
by the Brunauer–Emmett–Teller and Barrett–Joyner–Halenda methods.
X-ray diffraction (XRD, D/Max-2550 VB, Japan) was performed to
determine the crystalline phases of the studied samples, while their
thermal properties were investigated by differential scanning calorim­
etry (DSC) and thermogravimetry (TG) in the temperature range from 30
to 1200 ◦ C at a heating rate of 20 ◦ C/min in flowing air using a thermal
analyser (NetzschSta449C, Germany). A hot disk thermal analyser
(TPS2500S, China) was used to measure the thermal conductivities of
the samples between 25 and 1000 ◦ C, while a dynamic mechanical
analyser (DMA8000, USA) was utilised to determine their compressive
strengths.
2.4. Theoretical calculation of thermal conductivity
In this study, it is assumed that the influence of temperature on the
structural deformation of Al2O3–SiO2 aerogel composites is negligible.
Because the pores of CNT/Al2O3–SiO2 aerogel composites are between 2
and 50 nm, convection can be ignored, so heat is transmitted in the
composites through conduction and radiation [27].The total thermal
conductivity ktotal of CNTs doped aerogel composites can be expressed as
the sum of radiation thermal conductivity and kr conduction thermal
conductivity kc based on the diffusion approximation. Where the radi­
ative thermal conductivity, kr, can be given as [15,28,29]:
16n2t σT 3
Kr = (1)
βt
Where σ is the Stefan–Boltzmann constant,5.67 × 10− 8Wm− 2K− 4; and
βtotal is the mean extinction coefficient of the composite, βt is the
extinction coefficient of composite material, which is calculated by
Lambert-Beer equation. T is absolute temperature of aerogel composites;
nt is the effective refractive index of the composite based on volume
averaging of the CNTs and aerogel refractive indices:
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Fig. 2. Preparation process of Al2O3–SiO2 aerogel composites doped carbon nanotubes.

nt = nc f + na (1 − f ) (2) { ( )
16n2t σ T 3 πa21 a22 ( ) π a21 1 − a22
Ktotal = + + 1 − a21 − [α + ln(1 − α)]
Where f is the mass fraction of the CNTs in the composite and the 3βt 4(1 − α) 2α2
refractive index (na) of the aerogel is about 1.04. ( )[ ]} (5)
π 1 1 1 − αa1 a2
Thermal conductive includes gas and solid conduction, also their + √ ̅̅̅̅̅̅̅̅̅̅̅̅̅ − a1 In − (1 − a2 ) × Kg
α 1 − a22 αa1 1 − αa1
coupling effect. The gas thermal conductivity in nanoporous aerogels is
expressed as [30]:
Where a is the contact diameter between nanoparticles (nm); d is the
60.22 × 105 PT − 0.5 ∅ diameter of the nanoparticle (nm); D is the pore size formed by nano­
Kg = (3)
0.25ρSa ∅− 1 + 4.01 × 109 PT − 1 particles (nm);a2 is the contact parameter between aerogel nano­
Kg
particles,0.8; a1 = Dd α = 1 − Ks ;
Where kg is the gas thermal conductivity (Wm− 1K− 1), p is the pressure
(Pa), and T is the temperature (K). Sa is the specific surface area of
3. Results and discussion
nanoporous aerogels (m2/kg), it can be determined by the nitrogen
adsorption and desorption measurement. ∅ is the porosity, In the pre­
3.1. Morphology and structure of the CNT/Al2O3–SiO2 composites
sent paper, we determine the porosity by∅ = 1 − ρa /ρbulk . ρa is the
density of the pure aerogels and it has different values for different
Fig. 3 shows the macroscopic and microscopic structures of the
samples which can be obtained by measuring its mass and volume; ρbulk
Al2O3–SiO2 aerogel composites with different CNT contents obtained
is the bulk density of theAl2O3–SiO2 aerogel, 3970 kg/m3.
after supercritical drying. As shown in Fig. 3(a–c), both pure aerogel and
The Solid phase conduction thermal conductivity of the Al2O3–SiO2
the CNT-containing aerogel composites exhibit good surface morphol­
aerogel composites [31,32]:
ogies without visible cracks. When the CNT amount was increased from
Ksι 0.5 to 1.0 wt%, the aerogel composites surface became smoother. Ac­
Ks = ρνι (4)
ρs νs cording to Fig. 3(a1), the AS/CNT-0 aerogel sample has a highly porous
network skeleton. The contents of the main elements in the pure
Where ρ is the apparent density of Al2O3–SiO2aerogel (kg/m3), and its Al2O3–SiO2 aerogel were determined by energy-dispersive X-ray spec­
value can be measured experimentally. ρs is the skeletal density (kg/m3). troscopy (EDS). Fig. 3(a1 (inset)) shows the presence of Al, Si, and O
νι is the apparent density of Al2O3–SiO2 aerogel corresponding sound elements in the composite structure. The mass fraction of Al (35.74 wt%)
velocity (m/s); νs is the Al2O3–SiO2 aerogel skeleton density corre­ is larger than that of Si (17.84 wt%), while the calculated Al-to-Si molar
sponding to the speed of sound (m/s); Kιs is the thermal conductivity of ratio is equal to 2:1. Fig. 3(b1) and (c1) denote the microstructures of the
the base material (W/(m⋅K)). aerogel composites containing 0.5 wt% and 1.0 wt% CNTs, respectively.
However, the effective thermalconduction of aerogels is not a simple Both samples exhibit unique embedded network structures including
superposition of gas phase heat conduction and solid phase heat con­ homogeneously distributed CNTs with different orientations. After the
duction. In this paper, a simplified cubic array structure model is used to CNT content increased from 0% to 1.0 wt%, the composite porosity
evaluate the gas-solid coupled thermal conductivity of aerogels. gradually decreased.
Assuming that aerogel particles are regularly spherical and heat flow is Fig. 4 displays the SEM and EDS images of the AS/CNT-1.0 com­
steady heat transfer in one-dimensional direction from the bottom to the posite. As shown in Fig. 4(b) and (c), CNTs serve as the skeleton of the
top of the unit. According to the above formula, the total thermal con­ composite material with an apparent tubular structure covered by
ductivitycan be obtained formula (5): Al2O3–SiO2 aerogel particles. The surface scanning energy spectra of the

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Fig. 3. The macroscopic and microscopic structures of Al2O3–SiO2 aerogel composites with different CNTs contents after supercritical drying: (a) and (a1) AS/CNTs-
0.0 aerogel; (b) and (b1) AS/CNTs-0.5 composite; (c) and (c1) AS/CNTs-1.0 composite.

Fig. 4. SEM images(a), (b) and (c) of AS/CNTs-1.0 composites, and EDS element mapping of corresponding Al (a1), Si(a2),C (a3)and O (a4).

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AS/CNT-1.0 aerogel composite (Fig. 4(a1–a4)) confirm the skeleton Table 1

structure of Al2O3–SiO2 particles and homogeneous distribution of Al, Physical properties of CNTs/Al2O3–SiO2 aerogel composites.
Si, C, O, and other elements, indicating that CNTs in the composite are Samples Specific pore average pore Porosity Density
uniformly distributed in the composite matrix without agglomeration. In surface area volume diameter (%) (g/cm3)
a previous study, a random distribution of ceramic fibres and adhesion (m2/g) (cm3/g) (nm)
of nanoscale aerogel particles to reinforced fibres were observed [29]. In AS/ 539.186 5.855 25.1846 93.4 0.15
another work, uniformly dispersed Si3N4 particles were adhered to the CNTs-
silica network and coated with aerogel nanoparticles [33]. Finally, 0.0
AS/ 501.793 4.098 24.3254 92.1 0.18
aluminium borate whisker dispersed in Al2O3–SiO2 aerogel served as a CNTs-
skeleton and remained compatible with aerogel molecules [14]. The 0.5
reinforcement was evenly embedded into the aerogel network micro­ AS/ 446.335 3.844 23.036 89.7 0.23
structure, and the composite morphology changed after CNT addition, CNTs-
1.0
but the aerogel microstructure remained intact. It is noteworthy that
CNTs and Al2O3–SiO2 aerogel were highly compatible with each other
and that the filled aerogel retained a three-dimensional porous struc­ decreased with an increase in the doping concentration. This trend was
ture, indicating that the introduction of CNTs produced little effect on very similar to the results of the present study.
the aerogel matrix. Because the added CNTs partially fill aerogel nanopores, the original
aerogel surface becomes covered with a CNT layer [13]. Furthermore,
the dispersion of CNTs limits the ability of the adsorbed Al2O3–SiO2
3.2. Pore structure analysis of the CNT/Al2O3–SiO2 composites
nanoparticles to grow freely in space, which reduces their degrees of
freedom and randomness [37] and inhibits the formation of a large
Fig. 5 shows the pore size distributions and nitrogen adsorption and
network structure. Therefore, the addition of CNTs increases the com­
desorption isotherms of the CNT/Al2O3–SiO2 aerogel composites with
posite density and decreases the pore size and porosity.
different CNT contents. According to Fig. 5(a), the nitrogen adsorption
and desorption volumes decrease significantly with an increase in the
CNT amount from 0% to 1.0 wt%. In addition, an apparent hysteresis
loop is observed at a relative pressure of 0.64–1.0, and a short platform
appears at a relative pressure close to 1.0. The nitrogen adsorption and
desorption isotherms of the Al2O3–SiO2 aerogel composites represent
type IV curves of the IUPAC classification, and the hysteresis loops
exhibit H1-type characteristics, indicating that these composites are
mesoporous materials with cylindrical pores [34]. According to the re­
sults of previous studies, the observed similarity between the nitrogen
adsorption and desorption curves of the studied aerogel composites is
due to the large number of mesopores in the composite structure and the
occurrence of capillary condensation during the nitrogen adsorption and
desorption processes [13]. The pore size distribution curve (Fig. 5(b))
shows that the average pore size gradually decreases to below 50 nm and
that the pore size distribution becomes more uniform with increasing
CNT content from 0 to 1.0 wt%. Notably, all samples contained pores
with sizes ranging from 2 to 50 nm. The physical properties of different
CNT/Al2O3–SiO2 aerogel composites are listed in Table 1. When the CNT
amount increased from 0 to 1.0 wt%, the composite specific surface area
decreased from 539.186 to 446.335 m2/g, and their average pore size
decreased from 25.1846 to 23.036 nm. Meanwhile, the total pore vol­
ume and porosity of the composites decreased significantly, while their
density increased. Other researchers have found that by adding Y2O3
Fig. 6. X-ray diffraction analysis of CNTs/Al2O3–SiO2 aerogel composites at
nanoparticles [35] or silica nanowires [36] to a SiO2 aerogel matrix, the
room temperature.
pore volume and specific surface area of the aerogel composite gradually

Fig. 5. Nitrogen adsorption-desorption isotherms (a) and pore size distribution (b) of the CNTs/Al2O3–SiO2 composites.

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3.3. Composition and phase nature of the CNT/Al2O3–SiO2 composites
Fig. 6 shows the powder XRD patterns of the synthesised CNT/
Al2O3–SiO2 aerogel composites, which contain three diffraction bands
centred at 2θ = 25.34◦ , 49.5◦ , and 64.95◦ . The broad peak at 25.34◦
corresponds to an atypical amorphous SiO2 structure with very low
crystallinity. The other bands at 2θ = 49.5◦ and 64.95◦ represent the
boehmite phase. Moreover, the corresponding CNT peaks in the com­
posite patterns were not detected, because their main diffraction peak at
2θ = 25◦ overlapped with that of the Al2O3–SiO2 network, and the
remaining bands were not observable due to the low contents of carbon
nanomaterials (similar results were obtained in previous studies [10,
18]). Hence, the addition of CNTs did not destroy the composite phase
structure.
Fig. 7 shows the FT–IR spectra of the pristine CNTs and CNT/
Al2O3–SiO2 composite aerogels recorded between 4000 and 400 cm− 1 at
room temperature. The absorption peaks at 3446.26 and 1638.05 cm− 1
were assigned to the stretching and bending vibrations of the –OH
groups of the adsorbed water and EtOH molecules. The bands at 2973.88
and 2931.92 cm− 1 were due the stretching and bending vibrations of
–CH groups. The bands centred at 608.96 and 784.33 cm− 1 originated
from octahedral Al–O antisymmetric stretching vibrations, which were
consistent with those of Al2O3–SiO2 aerogels reported by Wu et al. [23],
Ji et al. [38], and Chen et al. [5]. The intense bands near 1054.46 and
497.76 cm− 1 were assigned to the asymmetric bond stretching vibra­
tions and bond bending vibrations of three-dimensional Si–O–Si groups,
respectively, indicating that Si–OH monomers in the sol polymerised
and formed a three-dimensional Si–O–Si network structure. The band at
900.46 cm− 1 corresponds to Al–O–Si stretching vibrations caused by the
formation of –Al–O–Si–O– species in the gel structure. Note that the
FT–IR spectra of the AS/CNT-X aerogel composites contained no new
absorption peaks, indicating that CNTs were physically embedded into
the Al2O3–SiO2 matrix without affecting the aerogel structure. However,
after CNT addition, the characteristic band of the AS/CNT-X composites
(3000–2800 cm− 1) was red-shifted due to the conjugate effect the CNT
surface, which produced more delocalised electrons, thus reducing the
transition potential of electrons and facilitating their transport [39].
3.4. Thermogravimetric (TG) and differential scanning calorimetry(DSC)
analysis of the CNT/Al2O3–SiO2 composites
The TG and DSC curves of the CNT/Al2O3–SiO2 composite aerogels
are presented in Fig. 8. Fig. 8(a) shows that the total mass loss of the
Al2O3–SiO2 aerogel increased significantly with an increase in the CNT
Fig. 7. The FT-IR curves of CNTs and CNTs/Al2O3–SiO2composite between
4000 and 400 cm− 1.
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content between room temperature and 1200 ◦ C. At temperatures below
700 ◦ C, the mass loss of the CNT/Al2O3–SiO2 composites was relatively
small, and its lowest value was observed for the AS/CNT-0.5 composite.
When the temperature exceeded 700 ◦ C and the CNT content increased
from 0 to 1.0 wt%, the composite mass loss increased significantly with
the largest value of 21.78% obtained for AS/CNT-1.0 for the following
reasons. First, the water adsorbed on the aerogel surface evaporated and
a small number of residual Si–OH and Al–OH groups formed Si–O–Si,
Al–O–Al, and Si–O–Al species [34]. Second, as the temperature
increased, –CH3 groups oxidised on the aerogel surface (250–600 ◦ C),
inducing a continuous structural transformation from boehmite to
γ-Al2O3 (2AlO(OH) →γ-Al2O3 + H2O,300–1000 ◦ C) [6]. Finally, the
decomposition of CNTs occurred at high temperatures. Fig. 8(b) clearly
shows a strong exothermic peak at approximately 720 ◦ C, which
appeared after increasing the CNT content from 0 to 1.0 wt% with the
largest intensity achieved at 1.0 wt%.
3.5. Compression performance of the CNT/Al2O3–SiO2 composites
Fig. 9 displays the mechanical properties of the CNT/Al2O3–SiO2
aerogel composite samples. As shown in Fig. 9 (a) presents a typical non-
linear stress-strain curves, the pure aerogels can hardly support force
and get crack immediately as the stress exerts on them. The CNTs/
Al2O3–SiO2 composite aerogels present obvious fragility. It shows that
the compressive strength of the composites significantly increased with
an increase in the CNT content. Compared with the low mechanical
strength of pure aerogel materials, the CNT/Al2O3–SiO2 composite
aerogels can endure higher stresses and exhibit large compression
moduli. As the CNT content increased from 0 to 1.0 wt%, the
compressive strengths of the AS/CNT-0.5 and AS/CNT-1.0 composites
increased by 16.2% and 83.8% to 0.86 and 1.36 MPa, while their
compressive moduli increased by the factors of two and four shown in
Fig. 9 (b),respectively. The results of previous studies revealed that the
compressive strengths of 30 wt%. aluminium borate whisker-reinforced
Al2O3–SiO2 aerogel composite [14] and 5.0 wt% GO/SiO2 aerogel
composite [37] were equal to 1.02 and 1.25 MPa, respectively. There­
fore, the mechanical properties of the CNT-reinforced composites pre­
pared in this work are superior to those of similar materials fabricated by
other researchers.
3.6. Thermal conductivity of the CNT/Al2O3–SiO2 composites
The experimental thermal conductivities and temperature histo­
grams of the aerogel composites doped with different CNT contents are
presented in Fig. 10(a). It shows that the thermal conductivity of the
CNT/Al2O3–SiO2 composites gradually decreases with increasing CNT
content from 0 to 1.0 wt% at all temperatures. Moreover, no significant
differences in the thermal conductivities of the Al2O3–SiO2 composites
were observed at low temperatures. These results indicate that the
thermal conductivities of the AS/CNT-0.5 and AS/CNT-1.0 composites
were 11.2% and 14.8% lower than that of pure aerogel at room tem­
perature, respectively, while the optimal thermal conductivity of the
AS/CNT-1.0 composite was 0.0495 W/m⋅K at 25 ◦ C. When the tem­
perature increased from room temperature to 1000 ◦ C, the thermal
conductivity of the CNT/Al2O3–SiO2 aerogel composites increased
significantly (especially above 500 ◦ C). It is noteworthy that the high-
temperature thermal conductivity of the Al2O3–SiO2 aerogel compos­
ite was strongly related to the CNT content, while the Al2O3–SiO2 aer­
ogel with 1.0 wt% CNTs possessed the lowest thermal conductivity at
high temperatures. The thermal conductivity of the AS/CNT-1.0 aerogel
composite was equal to 0.1781 W/m⋅K at 1000 ◦ C, which was 6% and
15% lower than those of the AS/CNT-0.5 composite and AS/CNT-
0 aerogel, respectively. Thus, the CNT/Al2O3–SiO2 aerogel composites
exhibited better thermal insulation properties than those of pure
aerogel.
In addition, the thermal conductivities of our AS/CNT-1.0 composite
D. Jiang et al. Ceramics International 48 (2022) 16290–16299

Fig. 8. Thermogravimetric (TG) (a) and differential scanning calorimetry (DSC) curves (b) of the CNTs/Al2O3–SiO2 aerogel composites.

Fig. 9. Compressive stress-strain curves and mechanical properties of CNTs/Al2O3–SiO2 aerogels composites at room temperature.

Fig. 10. Experimental thermal conductivity curves of aerogel composites at different temperatures (a); Comparison of thermal conductivity of AS/CNT-1.0 com­
posite material with other thermal insulation materials at different temperatures (b).

are compared to those of the reported aerogels, including mullite fibres/

ZrO2–SiO2 aerogel [40], Y2SiO5 ceramics/SiO2 aerogel [41], zirco­
nia/porous mullite/Al2O3–SiO2 aerogel [42],and unidirectional alumina
aerogel [43],as shown in Fig. 10(b). There is no report describing the Table 2
thermal conductivities of above aerogels at temperatures above 25 ◦ C. Parameters of theoretical thermal conductivity calculation model.
At temperatures below 1000 ◦ C, the AS/CNT-1.0 composite exhibits Sample α nt βt ρ(Kg/m3) S (m2/Kg) D (nm)
much lower thermal conductivities than those of the reported porous
AS/CNTs-0 0.927 1.04 40 150 539186 25.1
carbon-bonded carbon fiber/SiO2–Al2O3 [44] and TiO2/mullite AS/CNTs-0.5 0.945 1.18 52 180 501793 24.3
fibre/aluminium–silicon aerogel [15]. AS/CNTs-1.0 0.963 1.33 65 210 446335 23

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D. Jiang et al.
Fig. 11. Diagram of theoretical thermal conductivity and experimental thermal
conductivity of CNT/Al2O3–SiO2 aerogel composites at 25–1000 ◦ C.
3.7. Thermodynamics analysis
Using Equation (5) and the data presented in Table 2, the total
effective thermal conductivities of the aerogel composites were esti­
mated at different temperatures (Fig. 11). The theoretical effective
thermal conductivities of the AS/CNT-X composites were very close to
their experimental magnitudes, and the average difference between the
two datasets was approximately 8.5%, indicating high reliability of the
utilised model. Moreover, the aerogel composites exhibited a strong
infrared shading effect when the CNTs were dispersed. A possible reason
for the observed error is that the influence of temperature on the
structure and density of the aerogel composites was ignored in the
calculation procedure, while temperature variations also changed the
composite humidity and CNT content.
4. Mechanism analysis
In this study, CNT/aerogel composites with different mass fractions
of CNTs were prepared, and the CNT content produced significant effects
on the mechanical and heat insulation properties of the AS/CNT-X
samples. Hence, the mechanism of their enhancement by CNT addi­
tion is discussed below.
The results presented in Section 3.5 indicate that the introduction of
Fig. 12. Schematic of heat transfer in CNT/Al2O3–SiO2 aerogel composites.
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CNTs increases the compressive strength of the aerogel composites due
to the anchoring effect of CNTs on aerogel skeleton. CNTs exhibit high
strength and toughness as well as the ability to transfer and dissipate
external loads applied to composites, thereby improving their mechan­
ical properties. However, the load transfer efficiency of these materials
is strongly dependent on the dispersion state of CNTs [45]. The CNT size
is similar to that of aerogel apertures, and the addition of CNTs makes
the nanonetwork of the composite aerogel more uniform and enhances
its load-carrying characteristics. When aerogels are subjected to an
external force, many small cracks are formed instead of large cracks. The
anchoring effect of CNTs on the silica aerogel matrix prevents further
propagation of small cracks [22] by partially consuming the fracture
energy, which increases the mechanical strength.
The results presented in Section 3.6. show that the CNT addition to
the Al2O3–SiO2 matrix enhances the thermal insulation performance of
the Al2O3–SiO2 aerogel. The heat transfer processes occurring in aerogel
composites mainly consist of gas heat transfer, solid heat transfer, and
radiation heat transfer. Previously, it was found that gaseous heat
transfer [46] strongly contributed to the total thermal conductivity of
aerogels and that the radiation contribution was negligible at room
temperature [10,11] because gas heat transfer was realised by the gas
molecules bumping into each other in the aerogel structure. However,
the average free path of air molecules is 70 nm, which is larger than the
aerogel aperture; therefore, the heat transfer of gas molecules in the
aerogel is severely limited. From the results of previous studies, it was
concluded that the presence of micro-additives in aerogel composites at
high temperatures promoted the solid conduction heat transfer due to
their high thermal conductivity and also suppressed the radiation heat
transfer, owing to their ability to absorb and scatter heat radiation [47].
In this study, the excellent thermal insulation performance of the
CNT/Al2O3–SiO2 aerogel composites can be attributed to the infrared
shadowing effect of CNTs. As a carbon-based material (such as carbon
black), CNTs contribute to the suppression of radiation heat transfer [1].
According to Wien’s displacement law, the central wavelength of
infrared radiation ranges from 1.97 to 2.7 μm at temperatures between
800 and 1200 ◦ C [48], while CNTs have a high extinction coefficient in
this wavelength region.
Furthermore, as shown in Fig. 12, CNTs are uniformly distributed in
the aerogel structure, leading to scattered heat propagation, making the
heat propagation path multidirectional, and weakening the unidirec­
tional heat propagation. This phenomenon prevents the normal propa­
gation of the heat flow. The addition of inorganic nanofillers such as
CNTs into the composite matrix introduces a large number of phonon
potential barriers, reduces the phonon thermal conductivity, and sup­
pressed the solid heat transfer [49]. Owing to the special
three-dimensional network structure of the aerogel composite, the solid
D. Jiang et al.
heat transfer occur through complex and tortuous channels, thus
significantly reducing the solid heat conduction of the material. Mean­
while, from the energy perspective, the volatilisation of CNTs absorbs a
certain amount of heat. Therefore, the introduction of CNTs into aero­
gels not only blocks the infrared radiation path at high temperatures and
reduces the radiative heat transfer, but also weakens the solid heat
conduction to a certain extent, thus considerably improving the thermal
insulation performance of composite materials.
5. Conclusions
In this work, the CNT addition to Al2O3–SiO2 aerogels during the sol-
gel process was confirmed to be an effective approach to enhancing the
mechanical and heat insulation properties of aerogels. The microstruc­
ture, compressive strength, thermal insulation performance, and theo­
retical effective thermal conductivity of 0–1.0 wt% CNT-reinforced
composites were examined. The uniformly dispersed CNTs produced
positive effects on the compressive and heat insulation properties of the
composites. When the CNT content increased from 0 to 1.0 wt%, the
pore diameter and specific surface area of the composites decreased
from 25.1 to 23 nm and from 539 to 446 cm2/g, respectively, while their
density increased from 0.15 to 0.21 g/cm3. Compared with pure aerogel,
the added CNTs produce an anchoring effect on the Al2O3–SiO2 matrix,
and the compressive strengths of the AS/CNT-0.5 and AS/CNT-1.0
composites were increased by 16% and 84% to 0.86 and 1.36 MPa,
respectively. Meanwhile, the thermal conductivities of these composites
equal to 0.189 and 0.178 W/m⋅K at 1000 ◦ C were lower than that of pure
aerogel by 9.3% and 15%, respectively. A simplified cubic array struc­
ture model was used to calculate the theoretical thermal conductivities
of the composites at 25–1000 ◦ C, which were consistent with the
experimental data. Based on the results of this study, a possible thermal
insulation mechanism was proposed for the CNT/Al2O3–SiO2 compos­
ites. The introduction of CNTs improved the infrared shielding ability of
the composites and promoted the multidirectional heat transfer path.
Therefore, the low high-temperature thermal conductivities and high
strengths of the CNT/Al2O3–SiO2 composites make them promising
candidates for the ultrahigh temperature and super-thermal insulation
applications in the aerospace and energy conservation fields.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
Authors are special thankful to Dr. Qin of Central South University
for their guidance and contributions during the experiments. We would
like to thank Editage (www.editage.cn) for English language editing.
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