Composites Part B 230 (2022) 109496

Contents lists available at ScienceDirect

Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Highly elastic and fatigue resistant wood/silica composite aerogel operated

at extremely low temperature
Mingyuan Yan a, Yangyang Fu a, Yuelei Pan a, *, Xudong Cheng a, Lunlun Gong a, Yong Zhou a,
Hoda Ahmed b, Heping Zhang a, **
a
State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui, 230027, PR China
b
Materials Engineering Department, McGill University, Montréal, Québec, H3A 0G4, Canada

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

Keywords: Advanced aerogel materials have great potential for applications in areas such as thermal insulation. However,
Wood/silica aerogels the creation of a low-temperature resistant elastic aerogel remains a considerable challenge. Herein, we
Thermal insulation materials demonstrate an organic and inorganic hybrid strategy to develop a wood-based composite aerogel (wood/silica
Low temperature resistance
aerogels) by freeze drying. The silica nanoparticles are in situ grafted onto the wood nanofibers through the sol-
Elasticity
gel method. The obtained wood/silica aerogels exhibit excellent hydrophobic (127◦ ), flame-retardant (LOI =
Fatigue resistance
44%), and thermal insulation performances (0.032 W m− 1 K− 1). More notably, wood/silica aerogels demon­
strated elasticity and flexibility, performing torsion and elastic recovery even in liquid nitrogen (− 196 ◦ C). The
successful synthesis of wood/silica aerogel provides a new idea for designing flexible thermal insulation mate­
rials with low temperature resistance.

1. Introduction
Traditional silica aerogels are brittle, which limits its thermal insu­
lation application [1–3]. In order to overcome the brittleness of aerogels,
many elastic aerogels have been developed and studied, such as polymer
aerogels, graphene aerogels, cellulose aerogels, wood aerogels, etc
[4–11]. Among them, wood aerogels have been widely studied due to its
good biocompatibility, high source abundance and low cost [12–14].
After simple delignification, wood aerogels could possess excellent
elasticity (a strain of 60%) and superior thermal insulation [13].
Nevertheless, the poor fatigue resistance and flammability of wood
aerogels limit its development and application.
To improve the elasticity and fatigue resistance of wood aerogels,
prior efforts primarily focused on the composite of wood aerogels and
polymers, including polyvinyl alcohol and polydimethylsiloxane [15,
16]. Cai et al. prepared wood composite aerogels reinforced with poly­
vinyl alcohol [15]. The prepared aerogels showed excellent fatigue
resistance with a height retention rate of 100% after 200 cycles under
30% strain. But the aerogels were still flammable, which greatly limited
its practical application. To improve the flame-retardancy of wood
aerogels, many studies have been carried out by incorporating organic
and inorganic flame retardants [17–21]. For example, Kong et al.
improved the flame-retardancy of wood composites by introducing
furfuryl alcohol resin [17]. But a large number of organic reagents could
cause environmental and health hazards. In contrast, inorganic flame
retardants are more environmentally friendly [21]. Many inorganic
flame retardants, including calcium carbonate, montmorillonite clay,
titanium dioxide, and boron nitride, have been used to improve the
flame-retardancy of wood aerogels [22,23]. However, these inorganic
flame retardants are often introduced through physical recombination,
and their poor compatibility with wood aerogels will lead to a decline of
elasticity and fatigue resistance of wood aerogels. Therefore, it is still a
great challenge to prepare wood aerogels with good elasticity, fatigue
resistance as well as excellent flame-retardancy.
Herein, an organic and inorganic hybrid approach was adopted to
prepare wood/silica aerogels with excellent elasticity, fatigue resistance
and flame-retardant properties. The honeycomb-like cellular structure
endowed wood/silica aerogels with excellent flexibility and elasticity.
And the height retention of wood/silica aerogels could remain at 92.8%
after 300 cycles of fatigue test at ε = 40%, showing fatigue resistance.
Moreover, with the introduction of inorganic particles, wood aerogels
showed excellent flame-retardant performances with a limit oxygen

* Corresponding author.;
** Corresponding author.
E-mail addresses: panyl@ustc.edu.cn (Y. Pan), zhanghp@ustc.edu.cn (H. Zhang).

https://doi.org/10.1016/j.compositesb.2021.109496
Received 16 August 2021; Received in revised form 11 November 2021; Accepted 19 November 2021
Available online 20 November 2021
M. Yan et al.
Fig. 1. (a) Schematic illustration of the fabrication of wood/silica aerogels. (b) The mechanical properties of wood/silica aerogels. (c) Elastic recover of wood/silica
aerogels in liquid nitrogen.
index of 44%. More remarkably, thanks to the low coefficient of linear
expansion, wood/silica aerogels maintained excellent mechanical
properties and can perform compression and recovery actions under
extreme conditions, even in liquid nitrogen (− 196 ◦ C). Wood/silica
aerogels with excellent mechanical properties and fatigue resistance
were expected to be applied in the field of thermal insulation in extreme
environments, such as pipelines for transporting liquid nitrogen and
liquefied natural gas.
2. Experimental section
2.1. Materials
Balsa wood as raw materials, was purchased in Taobao. Sodium
chlorite (NaClO2, 80%), acetic acid, methyltrimethoxysilane (MTMS,
98%), Cetyl trimethyl ammonium bromide (CTAB), Hydrochloric acid
(HCl) and Ammonium hydroxide (NH3•H2O) were purchased from
Shanghai Aladdin Biochemical Technology Co., Ltd., all analytical pure.
Oil was purchased from Local shops.
2.2. Preparation of wood aerogels
Wood aerogels were prepared from balsa wood by delignification. In
a typical procedure, the wood sample was treated with 2% sodium
chlorite aqueous solution at 85 ◦ C and buffered with acetic acid for 8h at
a pH of 4.5. This step was repeated until the wood sample turns white.
After delignification, the sample was then carefully washed in deionized
water at 90 ◦ C for 5 h to remove any remaining chemicals. Then, the
sample was frozen with a freeze-dryer at − 40 ◦ C for 12 h. Finally, the
sample was freeze-dried in a freeze-dryer for 48 h at a pressure below 20
Pa.
2.3. Preparation of wood/silica aerogels
In a typical procedure, 0.5 mL of hydrochloric acid (0.1 mol L− 1),
0.02 g of CTAB, 10 mL of deionized water, and 10 mL of MTMS were
mixed in a beaker. After stirring vigorously at room temperature for 20
2
Composites Part B 230 (2022) 109496
min, 10 mL of NH3•H2O (0.5 mol L− 1) was added to the beaker. After
stirring for 2min, the wood aerogel was completely impregnated with
the above solution until gel was formed to obtain wood/silica gel. Then,
wood/silica gel was freeze-dried for 36 h. And finally, the sample was
heated in 100 ◦ C for 2 h to obtain wood/silica aerogels.
2.4. Characterization
The morphology of the samples was observed by Scanning Electron
Microscope (SEM) (SU8220). The contact angles of the samples were
obtained by Theta contact angle tester (SL200K). The anisotropic ther­
mal conductivity of samples was measured using Hot Disk TPS2500S.
Fourier transform infrared spectroscopy (FTIR) (Nicolet 8700) and X-ray
photoelectron spectroscopy (XPS) (ESCALAB 250Xi) were utilized to
analyze the synthesis of the samples. And X-ray diffraction (XRD) (TTR-
III) and Raman spectroscopy (LabRamHR) were performed to analyze
the residues of the samples after combustion. TG-DSC (SDT Q600) was
performed to analyze thermal stability with a heating rate of 10 ◦ C
min− 1.
Mechanics performance tests were conducted with the Universal
Testing Machine (Instron E3000K8953). In the cyclic test, the loading
rate was set to 60 mm/min, and the sample size in the mechanical test
was set as 20 mm × 20 mm × 20 mm. Dynamic thermomechanical
analysis (DMA) was used to viscoelastic properties of samples. The
thermal insulation performances of the samples were studied by the
infrared thermal imager (FLIR A655sc). And the distance between the
thermal imager and the front side of the samples was set to 30 cm. The
thermal hazards of samples were studied by a micro combustion calo­
rimetry (MCC) (Fire Testing Technology, UK). According to the ISO
4589–1:1996 standard method, the limit oxygen index (LOI) tests were
performed at room temperature by using an HC-2CZ oxygen index meter
5801A. The size of samples was 100 mm × 10 mm × 10 mm. The cone
calorimeter (FTT, UK) were performed to explore the flame-retardant
performances of the samples. According to ASTM D 3801, UL-94 verti­
cal tests were carried out by using a vertical burning tester (5402,
Suzhou Vouch Testing Technology Co.,Ltd). The size of samples was
125 mm × 13 mm × 3.2 mm. Thermomechanical analysis (TMA) (Q400)
M. Yan et al.
Fig. 2. Photograph and SEM of natural wood (a), wood aerogels (b) and (c) wood/silica aerogels. (d) XPS spectrum of the samples and C1s, Si 2p spectrum of wood/
silica aerogels.
was used to analyze mechanical properties of the samples at low tem­
peratures. The phase transition temperatures at low temperatures were
obtained by DSC (Q2000) with a heating rate of 10 ◦ C min− 1.
3. Results and discussion
3.1. Fabrication of wood/silica aerogels
Here, we demonstrated a hybrid strategy to prepare wood/silica
aerogels by the in-situ assembly of silica particles onto wood aerogels
(Fig. 1). Balsa wood with low density was used as the raw material to
fabricate the wood/silica aerogels. As shown in Fig. 2a, the natural wood
presented a closed honeycomb-like cellular structure on the cross-
section, while the parallel cell lumina could be observed on the longi­
tudinal section. After delignification, the color of the prepared wood
aerogels changed from the original light brown to white, corresponding
to the removal of brown lignin. The characteristic lignin peaks at 1596,
1505, and 1461 cm− 1 (aromatic skeletal vibrations) in FT-IR spectra
disappeared after delignification, which confirmed the removal of lignin
(Fig. S1) [12]. The chemical composition analysis also showed that
compared to natural wood, the lignin content of wood aerogels
decreased from 11.02% to 0.30%, which indicated that the lignin was
almost completely removed after delignification (Fig. S2). As shown in
3
Composites Part B 230 (2022) 109496
Fig. 2b, the honeycomb-like cellular structure on the cross-section of the
wood aerogels became open to facilitate the next step of silica intro­
duction. Meanwhile, the cell walls became thinner after delignification,
and the longitudinal cell lumina almost completely disappeared. Silica
particles were grafted onto the cell walls of wood/silica aerogels.
(Fig. 2c). The FT-IR spectra further revealed the interfacial interaction
between silica particles and wood aerogels. For the case of silica aerogels
made of MTMS, the characteristic peak of Si–OH was located at 920
cm− 1, while the characteristic peak of Si–OH of wood/silica aerogels
moved to 901 cm− 1, corresponding to a red shift [24–26]. The red shift
usually indicates a decrease in bond energy, indicating that Si–OH
formed hydrogen bonds with the hydroxyl groups on the surface of the
wood aerogel [24,25]. The FTIR results confirmed that the silica parti­
cles were successfully grafted onto the wood aerogel in situ (Fig. S3)
[27–30]. As shown in Fig. 2c, the honeycomb-like cellular structure of
wood/silica aerogels was still visible on the cross-section, and a layer of
tightly bonded silica particles was distributed on the longitudinal cell
wall. Owing to the specific structure and inorganic silica particles, the
prepared wood/silica aerogels exhibited excellent properties such as
machinability and large angle bending (Fig. 1b).
To further prove the successful graft of silica particles, XRD and XPS
were used. The XRD pattern of wood/silica aerogels was the system
superposition of diffraction peaks of pure silica and wood aerogels
M. Yan et al.
Fig. 3. (a) Photographs of water and oil droplets on the wood aerogel and wood/silica aerogels. (b) Water contact angles of natural wood, wood aerogels and wood/
silica aerogels. (c) Dynamic water repelling of wood/silica aerogels. (d) Oil absorption of wood/silica aerogels. (e) Hydrophobic properties of wood/silica aerogels
being heated by alcohol lamp flame for 1 min.
(Fig. S4) [31]. In addition, The full spectrum of the XPS showed that C
and O elements were the dominant components of wood aerogels, while
the two additional peaks of Si 2s and Si 2p in spectra of wood/silica
aerogels indicated the successful introduction of Si into wood/silica
[32]. The C 1s spectra of wood/silica aerogels was fitted with three
peaks at 284.8, 286.3, and 287.7 eV, respectively (Fig. 2d). It was worth
noting that the peak at 284.8 eV corresponded to C–Si introduced by
MTMS [27]. The Si 2p Spectra was fitted with Si–O Peak at 102.6 eV and
Si–C peak at 103.3 eV [33]. In summary, XRD and XPS spectra showed
that the aerogel had been cross− linked with the silica nanoparticles
successfully in the preparation process.
3.2. Hydrophobic properties
Hydrophobic properties can reduce water absorption, which is
conducive to maintenance of materials. However, due to the amphi­
philicity of wood, untreated pure wood aerogels can both absorb water
and kerosene oil (Fig. 3a). The dynamic water absorption process also
confirmed the hydrophilicity of pure wood aerogels (Fig. S5). With the
in-situ introduction of MTMS, the hydrophobic structure was skillfully
introduced, which made wood/silica aerogels had excellent hydropho­
bic and oil-wet properties with a higher water contact angle of 127◦
(Fig. 3b). To further investigate its hydrophobic properties, the process
of dynamic water repulsion was recorded. Fig. 3c presented wood/silica
aerogels’ ability to bounce off falling water droplets, indicating excellent
hydrophobic performance. Furthermore, wood/silica aerogels can also
be used as a promising absorbent material for oil cleaning and the
separation of water and oil. As shown in Fig. 3d, when a block of wood/
silica aerogels was placed in the oil/water mixture, it selectively
absorbed the red oil completely. After the oil adsorption was completed,
wood/silica aerogels still floated on the water surface for easy collection
and further processing. After adsorption of oil, wood/silica aerogels still
maintained good mechanical properties, which could complete the
mechanical behaviors of squeezing and release, showing the potential of
reuse. In addition, the hydrophobic properties of the wood/silica
4
Composites Part B 230 (2022) 109496
aerogels in the high temperature environment for a short time were
explored (Fig. 3e). After being heated by alcohol lamp flame for 1 min,
wood/silica aerogels retained excellent hydrophobic properties with a
water contact angle of more than 120◦ . Moreover, the heated wood/
silica aerogels can float on the surface of the water and formed a film of
water underwater, indicating that a short period of high temperature did
not damage the hydrophobic performance of wood/silica aerogels. The
strong hydrophobic properties are beneficial for the self-cleaning and
long-term use under extreme conditions.
3.3. Mechanical properties
Excellent mechanical properties are essential for the transportation,
installation, and use of thermal insulation materials [10]. To explore the
elasticity and fatigue resistance of wood aerogels and wood/silica aer­
ogels, universal testing machine was performed. As a comparison, the
aerogel obtained by combining natural wood and silica is not elastic and
cannot be used as an elastic thermal insulation material (Fig. S6). While
wood aerogels and wood/silica aerogels exhibited elasticity and fatigue
resistance. The wood aerogels could withstand the maximum stress of
59.2 kPa and perform elastic recovery at a strain (ε) of 40% (Fig. 4a). In
the test of 50 loading-unloading cycles, the stress changed periodically
with time and showed no obvious attenuation (Fig. S7). Moreover, after
50 cycles of loading-unloading test, the height retention rate of wood
aerogels could still reach 93.8% (Fig. 4b). Compared to wood aerogels,
the elasticity of wood/silica aerogels with silica particles was well pre­
served, and wood/silica aerogels could also complete an elastic defor­
mation of 40%. Notably, wood/silica aerogels can withstand a
maximum stress of 200.4 kPa at ε = 40%, which was 3.4 times of that for
wood aerogels (Fig. 4c), indicating that the mechanical strength of
wood/silica aerogels was greatly improved. In order to analyze the fa­
tigue resistance of wood/silica aerogels, a test of 300 loading-unloading
cycles at ε = 40% was carried out (Video S1). During the cyclic process,
the stress changed periodically with time, and the data was highly
repeatable, indicating that wood/silica aerogels with no obvious
M. Yan et al. Composites Part B 230 (2022) 109496

Fig. 4. (a) The stress-strain fatigue curves for the 50 loading-unloading cycles of the wood aerogels. (b) Maximum stress and height retention of wood aerogels in the
test. (c) The stress-strain curves of wood/silica aerogels under different strains. (d) The stress-time fatigue curves for the 300 loading-unloading cycles of the wood/
silica aerogels. (e) The stress-strain fatigue curves for the 300 loading-unloading cycles of wood/silica aerogels. (f) Maximum stress and Young’s modulus of wood/
silica aerogels in the test. (g) Height retention and energy loss coefficient of wood/silica aerogels in the test.

structural change revealed the fatigue resistance and mechanical
robustness (Fig. 4d). Similarly, the shape of the stress-strain curve
remained almost constant in 300 cycles (Fig. 4e). And when the pressure
was released to zero, the strain can still decrease to zero, indicating that
the complete elastic recovery of the wood/silica aerogels with no plastic
deformation at ε = 40% [10].
Supplementary data related to this article can be found at https://do
i.org/10.1016/j.compositesb.2021.109496.
The key parameters of the cycle test, including maximum stress,
Young’s modulus, energy loss coefficient, and height retention, were
used to quantitatively analyze the fatigue resistance of wood/silica
aerogels (Fig. 4f and g). After 300 cycles, the maximum stress could still

Fig. 5. (a) A comparison of properties between wood/silica aerogels with other similar elastomeric materials previously reported. (b) Schematic illustration of
anisotropic mechanical properties.

5
M. Yan et al. Composites Part B 230 (2022) 109496

Fig. 6. (a) Thermal conductivity of natural wood, wood aerogels and wood/silica aerogels. (b) Schematic diagram of radial and axial heat transfer mechanism of
wood/silica aerogels. (c) The plot of surface temperature of the wood/silica aerogels in axially and radially, respectively. (d) A comparison of axial and radial infrared
images at hot plate of 125 ◦ C. (e) The infrared images of wood/silica aerogels and PU foam at hot plate of 160 ◦ C.

reach 80%, showing no significant decrease in the stiffness or strength of
the wood/silica aerogels. Compared with wood aerogels, wood/silica
aerogels showed a height retention of 95.5% after 50 cycles, which was
better than that of wood aerogels. Moreover, after 300 cycles, the height
retention of wood/silica aerogels could remain at 92.8%, showing a
slight plastic deformation. It indicated that the introduction of silica
particles had improved the mechanical robustness and fatigue resistance
of wood/silica aerogels. Encouragingly, after 50 cycles of loading-
unloading tests at ε = 90%, the maximum stress of wood/silica aero­
gels can still be reach about 60%, demonstrating the good fatigue
resistance of wood aerogel under super large strain (Fig. S8). In addition,
we studied the energy loss coefficient of wood silica aerogels during the
cycles. At ε = 40%, in the first circle, the energy dissipation was divided
by the compression work, and the energy loss coefficient of 44.8% was
obtained, which could reach 37.5% even after 300 cycles. A higher
energy loss coefficient endows the material with impact resistance.
Therefore, wood/silica aerogels can be used as a potential energy
damping material [34]. And the results of DMA tests showed that the
wood/silica aerogels exhibited constant viscoelastic properties in the
frequency range of 0.1–10 Hz, indicating its structural stability (Fig. S9)
[35]. Thus, the impact resistance and mechanical robustness of
wood/silica aerogels increased significantly compared to other similar
elastomeric materials previously reported (Fig. 5a and Table S1).
Moreover, wood/silica aerogels showed significant anisotropic me­
chanical properties. When pressed in the axial direction (parallel to the
fiber bundle direction), wood/silica aerogels can withstand maximum
stress of 361.2 kPa, which was 1.8 times of the radial maximum stress at
ε = 40% (Fig. S10). This performance is mainly because the elliptical
cross-section structure of the cell lumina endow wood/silica aerogels
with the elastic deformation ability in the radial direction, while the
axial structure with high mechanical robustness can withstand higher
stress (Fig. 5b) [36].
3.4. Thermal insulation properties
TG− DSC was performed to explore the thermal stability of the

6
M. Yan et al.
Fig. 7. (a) A simple combustion test with the ethanol lamp. (b) HRR curves of the natural wood, wood aerogel and wood/silica aerogels measured by cone calo­
rimeter. (c) THR curves measured by cone calorimeter. (d) Photographs of natural wood, wood aerogel and wood/silica aerogels in the cone calorimeter tests. (e) CO
production rate curves of natural wood, wood aerogel and wood/silica aerogels. (f) TTI of natural wood, wood aerogels and wood/silica aerogels. (g) LOI of natural
wood, wood aerogels and wood/silica aerogels.
samples. In the natural wood case, the main decomposition stage with a
weight loss rate of 57% was related to oxidative pyrolysis of wood
(Fig. S11). After delignification，the main peak of DTG curve for the
wood aerogels was still sharp with a peak rate of 1.32% ◦ C− 1 (Fig. S12).
For the case of wood/silica aerogels, with the introduction of inorganic
silica, the residual weight of wood/silica aerogels was as high as 37%.
The exothermic peak in the main pyrolysis stage of wood/silica aerogels
decreased from 24.7 W g− 1 of the natural wood to 12.4 W g− 1, corre­
sponding to a 50% reduction (Fig. S13). The DTG analysis indicated that
the thermal stability of wood/silica aerogels was significantly improved.
At the same time, the transient plane source method was performed
to measure the axial and radial thermal conductivity of the samples. It
was worth noting that all samples exhibited anisotropic thermal con­
ductivity with higher axial and lower radial thermal conductivity
(Fig. 6a). In the case of natural wood, the axial thermal conductivity was
2.2 times of the radial thermal conductivity. Since wood aerogels
retained an anisotropic pore structure after delignification, it also
exhibited anisotropic thermal conductivity. At the same time, because of
the low density of wood aerogels, the thermal conductivity of wood
aerogel was significantly reduced, and the axial thermal conductivity
reduced from 0.11 W m− 1 K− 1 of natural wood to 0.068 W m− 1 K− 1,
corresponding to a decrease of 38.2%. Compared with wood aerogel, the
thermal conductivity of wood/silica aerogels was slightly decreased.
The decrease of thermal conductivity of wood/silica aerogels is mainly
because the micro-nano network structure composed of silica particles
limits heat transfer (Fig. S14) [37]. And wood/silica aerogels still
showed anisotropic thermal conductivity with an axial thermal con­
ductivity of 0.066 W m− 1 K− 1and a radial thermal conductivity of 0.032
W m− 1 K− 1. The anisotropic thermal conductivity is mainly due to the
anisotropic structure. Axially, because the pores extend in one direction,
gas molecules can bump into each other relatively freely (Fig. 6b). The
resulting heat transfer of gas phase is unrestricted, which increases the
7
Composites Part B 230 (2022) 109496
heat conduction. At the same time, heat transfers along with the solid
skeleton in one direction, where the path is relatively short. As a result,
the heat conduction of solid phase increases [37]. Thus, thermal insu­
lation performance in the radial direction was better than that in the
axial direction.
Anisotropic thermal insulation performance can effectively avoid
heat penetration caused by local high temperature, so the anisotropic
heat insulation performance is the pursuit of advanced heat insulation
materials [21]. To characterize the anisotropic thermal insulation per­
formance of wood/silica aerogels more directly, when the samples were
heated on a hot plate, a thermal infrared imager was used to observe the
temperature distribution of the samples (20 mm × 20 mm × 20 mm).
When the temperature of the hot plate was set to 125 ◦ C, the sample of
wood/silica aerogels was placed on the hot plate axially and radially,
respectively, and the distance between the imager and the front side of
the sample was set to 30 cm. During the heating process, the tempera­
ture at the top surface of the sample was recorded by the infrared
thermal imager and plotted in Fig. 6c. As shown in Fig. 6c, the surface
temperature of axially placed wood/silica aerogels rose rapidly, and the
top surface temperature remained around 45 ◦ C after stabilization. As a
comparison, the top surface temperature of radially placed wood/silica
aerogels rose more slowly, and the surface temperature remained about
40 ◦ C after stabilization, which was lower than that in the axial direction
(Fig. 6d). When the heating time was extended to 35 min, the temper­
ature of the upper surface of the radially placed sample did not rise
sharply, indicating its excellent thermal insulation performances
(Figs. S15 and 16). The results showed that the radial thermal insulation
performance of wood/silica aerogels was better than that of the axial
one, indicating the anisotropic thermal insulation performances of
wood/silica aerogels.
To further demonstrate the excellent thermal insulation perfor­
mances of wood/silica aerogels, as a typical commercial insulation
M. Yan et al.
Fig. 8. (a) SEM of the char residues of wood/silica aerogels after cone calorimeter test and partial enlarged SEM. (b) The corresponding the elemental mapping
images of (a). (c) Schematic diagram of flame-retardant mechanism of wood/silica aerogels.
material, PU foam was used for comparison (Fig. 6e). PU foam (20 mm
× 20 mm × 20 mm) and wood/silica aerogels (20 mm × 20 mm × 20
mm) were placed on the hot place at 160 ◦ C. For the same heating time,
wood/silica aerogels exhibited a lower top surface temperature and
larger low temperature areas (purple region). When the sample tem­
perature remained stable, the temperature at the top surface of PU foam
was 55 ◦ C, while that of wood/silica aerogels was only 46 ◦ C, which was
16% lower than that of PU foam. In addition, it is worth mentioning that
under 80% humidity environment, wood/silica aerogels still exhibit
excellent thermal insulation performance, which is mainly due to the
excellent hydrophobicity (Fig. S17). In summary, the infrared images
results showed that wood/silica aerogels exhibited excellent thermal
insulation performance, which could meet the actual insulation
requirements.
3.5. Flame-retardant properties
Superior flame-retardant performances are a vital prerequisite for
the practical application of wood-based thermal insulation materials
[38]. Through the simple combustion test with an ethanol lamp, it can
be intuitively found that wood/silica aerogels showed excellent
flame-retardant performances and self-extinguishing ability compared
with natural wood (Fig. 7a). In order to systematically analyze the
flame-retardant property of materials, micro combustion calorimetry
MCC, LOI, and cone calorimeter were used.
The inherent flammability of the samples was further assessed by
MCC. The heat release rate (HRR) curves and the total heat release
(THR) of natural wood, wood aerogels, wood/silica aerogels and natural
wood/silica aerogels were drawn in Fig. S18. Furthermore, some
important parameters, including peak heat release rate (PHRR) and total
heat release rate (THR) were summarized in Table S2. The natural wood
exhibited a sharp curve and the PHRR (170.21 W g− 1) and THR (17.55
kJ g− 1) far exceeded that of wood/silica aerogels. After chemical
treatment, the PHRR and THR of the wood aerogels further increased,
and their inherent thermal hazards had not been solved. Moreover, the
8
Composites Part B 230 (2022) 109496
introduction of inorganic silica reduced the PHHR and THR of wood/
silica aerogels by 67% and 25%, respectively, compared with natural
wood. As a comparison, the PHHR of the aerogel obtained by combining
natural wood with silica was 150.0 g− 1, which showed poor flame-
retardant properties. This is mainly because that untreated natural
wood still has a lot of combustible substances. Therefore, it is necessary
to delignify wood. Similarly, the above comparisons confirmed that
wood/silica aerogels showed excellent flame-retardant properties.
To further study the flame-retardant performances of the samples
(100 mm × 100 mm × 10 mm) in a real fire [39–41], these samples were
studied by cone calorimeter. The heat flux was set at 35 kW m− 2 to
simulate a real fire. During the early stages, the HRR of natural wood
sharply peaked at 126 kW m− 2 under heat flux (Fig. 7b). A protective
barrier formed with the charred lignin was produced on the surface,
resulting in a short period of HRR decline. Eventually, the barrier broke
down, and another exothermic peak appeared. After the removal of
lignin, wood aerogels showed different combustion behavior. Without
the lignin barrier protection, the HRR of wood aerogels steeply reached
the maximum value of 149 kW m− 2, which was higher than that of
natural wood. With the introduction of silica, the HRR growth curve of
wood/silica aerogels slowed down significantly with the peak HRR of
106 kW m− 2. In addition, time to peak heat release rate (TTpHRR) of
wood/silica aerogels was 79 s later than that of natural wood. Compared
with natural wood, the THR of wood/silica aerogels dropped from 20
MJ m− 2 to 18 MJ m− 2,corresponding to a 10% reduction (Fig. 7c). In
addition, it can be seen from the test process that wood aerogels burned
the most furiously (Video S2), while wood/silica aerogels burned
slowly, accompanied by a weak flame (Fig. 7d and Video S3). And
remarkably, wood/silica aerogels maintained the structural integrity
after the cone calorimeter test.
Supplementary data related to this article can be found at https://do
i.org/10.1016/j.compositesb.2021.109496.
The toxicity of smoke is also an important parameter to evaluate
flame-retardant performances. In a real fire, the toxic smoke such as CO
produced by the burning of materials will have a significant adverse
M. Yan et al.
Fig. 9. (a) Photographs of the elasticity of wood/silica aerogels at room temperature. (b) The elasticity of wood/silica aerogels after treated with acid treatment and
thermal aging. (c) The elastic recovery of wood/silica aerogels in liquid nitrogen. (d) A comparison of flexibility between wood/silica aerogels and EPE foam after
rapid cooling.
impact on the personnel escape, so it is critical to reduce the toxicity of
the burning materials. As shown in Fig. 7e, the introduction of MTMS
significantly reduced the peak CO production rate of wood/silica aero­
gels. Compared to wood aerogels, the peak CO production rate of wood/
silica aerogels significantly dropped from 2.3 × 10− 3 g s− 1 to 1.5 × 10− 3
g s− 1, corresponding to a 35% reduction. In brief, the silica barrier
blocks heat flux and combustible volatiles, thus reducing combustion
kinetics; simultaneously, the silica barrier is proven to have a porous
structure (Figs. S19 and 20), which can effectively absorb toxic smoke,
thus avoiding the release of smoke into the environment. As a result, the
CO production rate of wood/silica aerogels decreased.
The time to ignition (TTI) (Fig. 7f) of materials is also an essential
part of the flame-retardant performances [21]. In a real fire, a longer
time to ignition is beneficial to slow down the spread of fire and provide
more time for fire rescue. At the heat flux of 35 kW m− 2, the TTI of
natural wood was only 17 s, while the TTI of wood/silica aerogels was
85 s, which was 5 times of that of natural wood. The TTI of wood/silica
aerogels was longer than most flame-retardant woods reported
(Table S3), which showed excellent flame-retardant performances [19,
42–44]. The longer TTI of wood/silica aerogels benefited from the
compact encapsulation of silica inorganic particles. Specifically, the
silica barrier on the surface of cellulose isolated heat and oxygen, which
made the inner cellulose thermal decomposition slow at a lower tem­
perature. Moreover, the pyrolysis products were also blocked inside,
resulting in a significant delay in TTI. Compared with natural wood, the
LOI values of wood/silica aerogels increased from 21% to 44% (Fig. 7g).
In addition, compared to no rating of natural wood, wood/silica aerogels
successfully acquired a UL-94 V-1 rating, showing improved
flame-retardant properties (Table S2 and Fig. S21). Based on the above
analysis, wood/silica aerogels showed good flame-retardant properties.
In order to explore the influence of silicon content on the compre­
hensive performance of wood/silica aerogels, wood/silica aerogels with
different silicon content were prepared by adjusting ratio of MTMS:H2O.
Tests such as TGA, MCC, and cyclic loading-unloading tests are per­
formed to analyze the properties (Figs. S22–26 and Table S4). The re­
sults show that the silicon content has a great impact on the performance
of wood/silica aerogels. In general, when the silicon content is too high,
elasticity and fatigue resistance of the wood/silica aerogels rapidly
decrease. And too low silicon content leads to poor thermal stability and
poor flame-retardant properties of the wood/silica aerogels. As a result,
in a series of wood/silica aerogels with different silicon content, wood/
silica aerogels with silicon content of 14.9% show excellent overall
performance.
9
Composites Part B 230 (2022) 109496
To explore the flame-retardant mechanism of wood/silica aerogels,
the char after combustion was analyzed. As shown in Fig. 8, compared to
wood/silica aerogels before combustion, a dense barrier composed of
many particles was observed. The corresponding the elemental mapping
images showed that the barrier was almost composed of Si and O ele­
ments (Fig. S27). Therefore, it can be inferred that this barrier was a
silica barrier. XPS for the char residues of wood/silica aerogels
confirmed the existence of a large number of Si–O bonds (Fig. S28). And
The XRD pattern of the char residues of wood/silica aerogels showed a
broad peaks at 23◦ , corresponding to the amorphous silica (Fig. S29)
[45]. Therefore, both XPS and XRD results confirm the existence of silica
barrier. Like most inorganic flame retardants, this barrier can effectively
block the transport of heat and oxygen into the inner part of the
wood/silica aerogels, slowing down the pyrolysis and ignition of
wood/silica aerogels [21]. As a result, The TTI of wood/silica aerogels is
greatly extended to 85 s. In addition, the silica barrier significantly re­
duces the pyrolysis rate of wood aerogels (Fig. 7b), which reduces the
combustible volatile products of wood aerogels. The decrease in CO
production rate in cone calorimeter test confirmed this. While the py­
rolysis products are reduced, the carbon production of wood aerogel is
also greatly increased. Compared to wood aerogels, the char residue of
wood/silica aerogels increased from 0.25% to 57.02% (Table S5). The
high char residue of wood/silica aerogels during combustion promotes
the formation of a protective char layer [46]. In Fig. 8, the carbon layer
can be observed. To further analyze the carbon layer, Raman spectra was
performed. As shown in Figs. S30 and D band (at about 1360 cm− 1) and
G band (at about 1600 cm− 1) were observed [47,48]. Compared to char
of natural wood, the D band to G band strength ratio of wood/silica
aerogels dropped from 5.45 to 1.41, indicating that wood/silica aerogels
produced a denser and non-defective graphitized carbon layer.
Based on the above analysis, the flame-retardant mechanism of
wood/silica aerogels is proposed (Fig. 8b). On the one hand, the silica
barrier can effectively isolate oxygen and heat, which delays and re­
duces the pyrolysis of wood aerogel. On the other hand, the silica barrier
promotes the formation of a dense carbon layer, which prevents further
pyrolysis and combustion inside the wood/silica aerogels. Therefore,
under the synergistic effect of the silica barrier and the carbon layer, the
thermal insulation performance of wood/silica aerogels is significantly
improved.
3.6. Low temperature resistance
The mechanical properties of traditional insulation materials will be
M. Yan et al.
Fig. 10. The TMA tests of wood aerogels and wood/silica aerogels.
poor or even fail in extreme environments such as ultra-low tempera­
tures [49–51]. To solve this problem, elastic inorganic silica nano­
particles were in situ grafted onto the wood nanofibers. At room
temperature, wood/silica aerogels showed excellent elasticity with a
maximum elastic deformation of 50% (Fig. 9a). To simulate high-heat,
high-corrosive environments, wood/silica aerogels underwent acid
treatment and thermal aging. After treatments, wood/silica aerogels
could still perform the mechanical actions of compression and elastic
recovery, showing the application potential under environments of high
heat and high corrosion (Fig. 9b). More importantly, with the intro­
duction of the inorganic silica nanoparticles in situ, wood/silica aerogels
also exhibited flexibility and elasticity with elastic deformation of 45%
at ultra-low temperatures, even in liquid nitrogen (− 196 ◦ C), demon­
strating excellent low temperature resistance (Fig. 9c). In liquid nitro­
gen, wood/silica aerogels could still be twisted after rapid cooling. As a
comparison, as a flexible insulation material at room temperature, EPE
foam was easily broken after rapid freezing in liquid nitrogen, indicating
its brittleness at ultralow temperatures (Fig. 9d).
In order to further explore the mechanical properties of wood/silica
aerogels at extremely low temperatures, DMA was performed (Fig. S31).
We evaluated storage modulus, loss modulus, and loss factor of the
wood/silica aerogels in the temperature of − 70 ◦ C and − 140 ◦ C at an
oscillatory strain of 3%. The results showed that whether it was − 140 ◦ C
or − 70 ◦ C, the storage modulus of the material was an order of magni­
tude larger than the loss modulus in the frequency range of 0.1–10 Hz,
showing the excellent elasticity of wood/silica aerogels at extremely low
temperatures [35]. In addition, it was worth noting that in the
5000-cycle DMA test, the storage modulus and loss modulus showed a
small change after 1000 cycles, showing the fatigue resistance at
extremely low temperatures [35]. As a result, the DMA test results
revealed that wood/silica aerogels showed excellent elasticity and fa­
tigue resistance properties at extremely low temperatures. Therefore,
the wood/silica was suitable for use at extremely low temperatures.
To investigate the mechanism of wood/silica aerogels’ flexibility at
low temperatures, TMA was used to analyze the linear expansion coef­
ficient and characteristic temperature of the samples (Fig. 10 and
Fig. S32). When the temperature increased from − 150 ◦ C to 100 ◦ C at a
rate of 5 ◦ C min− 1, wood/silica aerogels, natural wood, and wood aer­
ogels all underwent expansion and contraction processes. But it was
worth noting that at low temperature (from − 100 ◦ C to 0 ◦ C), the
average coefficient of expansion (α) of wood aerogel was 221 × 10− 6
K− 1, and after the introduction of inorganic silica particles, the average
coefficient of expansion of the wood/silica aerogels reduced to 88 ×
10− 6 K− 1, which was 60% lower than that of wood aerogel. Meanwhile,
the softening temperature Tf of wood/silica aerogels was − 20.89 ◦ C,
which was 46.19 ◦ C lower than that of wood aerogels. The lower coef­
ficient of thermal expansion enables the internal microstructure of the
material to remain stable in the face of low temperatures, thus reducing
local stress. And the lower softening temperature can ensure that the
material remains elastic at low temperatures. The results of DSC showed
that wood aerogels underwent phase transformation around 0 ◦ C, which
10
Composites Part B 230 (2022) 109496
could be related to the freezing point of a small amount of water inside
the material. While, wood/silica aerogels produced a phase transition
around − 93 ◦ C (Fig. S33) [52]. The low phase transition temperature
endows the material with certain frost resistance. The low-temperature
resistance and low temperature flexibility ensure that wood/silica aer­
ogels can be used for thermal insulation at extremely low temperatures.
4. Conclusions
In summary, we prepared organic-inorganic hybrid wood/silica
aerogels via freeze drying. Owing to the inorganic silica component,
wood/silica aerogels showed excellent flame-retardant performance
with LOI of 44%. In addition, the unique directional structure gives
wood/silica aerogels excellent thermal insulation performances. And at
ε = 40%, the height retention of wood/silica aerogels could remain at
92.8% after 300 cycles, showing fatigue resistance. More encouragingly,
wood/silica aerogels could perform elastic recovery with a deformation
of 45% even at extremely low temperatures (− 196 ◦ C). We believe that
wood/silica aerogels with excellent performances will be potential for
the thermal insulation applications in ultra-low temperatures.
CRediT authorship contribution statement
Mingyuan Yan: conceptualization, data curation, formal analysis,
investigation, methodology, writing – original draft. Yangyang Fu: data
curation, formal analysis. Xudong Cheng: validation, methodology,
supervision. Yong Zhou: Data curation, validation. Lunlun Gong:
methodology. Yuelei Pan: writing – review & editing, funding acqui­
sition, supervision. Hoda Ahmed: Data curation, validation. Heping
Zhang: writing – review & editing, funding acquisition, supervision.
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.
Acknowledgements
This work was supported by Natural Science Foundation of Anhui
Province (No. 2108085J28), Major Science and Technology Projects of
Anhui Province (No. 202103a05020011), China Postdoctoral Science
Foundation (No. 2020M682047and 2021T140637), Youth Innovation
Promotion Association CAS (No. CX2320007001) and USTC Research
Funds of the Double First-Class Initiative (No. YD2320002002).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.compositesb.2021.109496.
M. Yan et al. Composites Part B 230 (2022) 109496

References [27] Jiang S, Zhang ML, Li MM, Liu L, Liu LF, Yu JY. Cellulose nanofibril (CNF) based
aerogels prepared by a facile process and the investigation of thermal insulation
performance. Cellulose 2020;27(11):6217–33.
[1] Zhou T, Cheng X, Pan Y, Li C, Gong L, Zhang H. Mechanical performance and
[28] Mahadik SA, Pedraza F, Parale VG, Park H-H. Organically modified silica aerogel
thermal stability of glass fiber reinforced silica aerogel composites based on co-
with different functional silylating agents and effect on their physico-chemical
precursor method by freeze drying. Appl Surf Sci 2018;437:321–8.
properties. J Non-Cryst Solids 2016;453:164–71.
[2] Li Z, Cheng X, He S, Shi X, Gong L, Zhang H. Aramid fibers reinforced silica aerogel
[29] He S, Huang YJ, Chen GN, Feng MM, Dai HM, Yuan BH, et al. Effect of heat
composites with low thermal conductivity and improved mechanical performance.
treatment on hydrophobic silica aerogel. J Hazard Mater 2019;362:294–302.
Compos Part A-appl S 2016;84:316–25.
[30] Huang DM, Guo CN, Zhang MZ, Shi L. Characteristics of nanoporous silica aerogel
[3] Pan Y, He S, Gong L, Cheng X, Li C, Li Z, et al. Low thermal-conductivity and high
under high temperature from 950 ◦ C to 1200 ◦ C. Mater Des 2017;129:82–90.
thermal stable silica aerogel based on MTMS/Water-glass co-precursor prepared by
[31] Wan CC, Lu Y, Jiao Y, Jin CD, Sun QF, Li J. Fabrication of hydrophobic, electrically
freeze drying. Mater Des 2017;113:246–53.
conductive and flame-resistant carbon aerogels by pyrolysis of regenerated
[4] Sun H, Bi H, Lin X, Cai L, Xu M. Lightweight, Anisotropic, compressible, and
cellulose aerogels. Carbohydr Polym 2015;118:115–8.
thermally-insulating wood aerogels with aligned cellulose fibers. Polymers 2020;
[32] Zhu G, Xu H, Dufresne A, Lin N. High-adsorption, self-extinguishing, thermal, and
12(1):165.
acoustic-resistance aerogels based on organic and inorganic waste valorization
[5] Zhu M, Yan X, Xu H, Xu Y, Kong L. Ultralight, compressible, and anisotropic
from cellulose nanocrystals and red mud. ACS Sustainable Chem Eng 2018;6(5):
MXene@Wood nanocomposite aerogel with excellent electromagnetic wave
7168–80.
shielding and absorbing properties at different directions. Carbon 2021;182:
[33] Zhou SK, You TT, Zhang XM, Xu F. Superhydrophobic cellulose nanofiber-
806–14.
assembled aerogels for highly efficient water-in-oil emulsions separation. ACS Appl
[6] Yang J, Xia Y, Xu P, Chen B. Super-elastic and highly hydrophobic/superoleophilic
Nano Mater 2018;1(5):2095–103.
sodium alginate/cellulose aerogel for oil/water separation. Cellulose 2018;25(6):
[34] Su L, Wang HJ, Niu M, Fan XY, Ma MB, Shi ZQ, et al. Ultralight, recoverable, and
3533–44.
high-temperature-resistant SiC nanowire aerogel. ACS Nano 2018;12(4):3103–11.
[7] Wang L, Zhang C, Wang X, Zheng Z. Preparation and properties of ultra-elastic
[35] Wang F, Dou L, Dai J, Li Y, Huang L, Si Y, et al. In situ synthesis of biomimetic silica
graphene aerogel. J Funct Polym 2018;31(5):462–7.
nanofibrous aerogels with temperature-invariant superelasticity over one million
[8] Arndt EM, Gawryla MD, Schiraldi DA. Elastic, low density epoxy/clay aerogel
compressions. Angew Chem Int Ed 2020;59(21):8285–92.
composites. J Mater Chem 2007;17(33):3525–9.
[36] Zhu J, Xiong R, Zhao F, Peng T, Hu J, Xie L, et al. Lightweight, high-strength, and
[9] Wang T, Long M-C, Zhao H-B, Liu B-W, Shi H-G, An W-L, et al. An ultralow-
anisotropic structure composite aerogel based on hydroxyapatite nanocrystal and
temperature superelastic polymer aerogel with high strength as a great thermal
chitosan with thermal insulation and flame retardant properties. ACS Sustainable
insulator under extreme conditions. J Mater Chem 2020;8(36):18698–706.
Chem Eng 2019;8(1):71–83.
[10] Chen Z, Zhuo H, Hu Y, Lai H, Liu L, Zhong L, et al. Wood-derived lightweight and
[37] Xie T, He Y. A review of heat transfer models of nanoporous silica aerogel
elastic carbon aerogel for pressure sensing and energy storage. Adv Funct Mater
insulation material. Chin Sci Bull 2015;60(2):137–63.
2020;30(17):1910292.
[38] Zhang WY, Barrio J, Gervais C, Kocjan A, Yu AP, Wang X, et al. Synthesis of carbon-
[11] Chatterjee S, Ke W-T, Liao Y-C. Elastic nanocellulose/graphene aerogel with
nitrogen-phosphorous materials with an unprecedented high amount of
excellent shape retention and oil absorption selectivity. J Taiwan Inst Chem E
phosphorous toward an efficient fire-retardant material. Angew Chem Int Ed 2018;
2020;111:261–9.
57(31):9764–9.
[12] Guan H, Cheng ZY, Wang XQ. Highly Compressible wood sponges with a spring-
[39] Wang H, Yuan J, Zhu Z, Yin X, Weng Y, Wang Z, et al. High performance epoxy
like lamellar structure as effective and reusable oil absorbents. ACS Nano 2018;12
resin composites modified with multifunctional thiophene/phosphaphenanthrene-
(10):10365–73.
based flame retardant: excellent flame retardance, strong mechanical property and
[13] Song JW, Chen CJ, Yang Z, Kuang YD, Li T, Li YJ, et al. Highly compressible,
high transparency. Compos B Eng 2021;227:109392.
anisotropic aerogel with aligned cellulose nanofibers. ACS Nano 2018;12(1):
[40] Peng X, Liu Q, Wang D, Liu C, Zhao Y, Wang R, et al. A hyperbranched structure
140–7.
formed by in-situ crosslinking of additive flame retardant endows epoxy resins
[14] Chen CJ, Kuang YD, Zhu SZ, Burgert I, Keplinger T, Gong A, et al. Structure-
with great flame retardancy improvement. Compos B Eng 2021;224:109162.
property-function relationships of natural and engineered wood. Nat Rev Mater
[41] Liu B-W, Zhao H-B, Chen L, Chen L, Wang X-L, Wang Y-Z. Eco-friendly synergistic
2020;5(9):642–66.
cross-linking flame-retardant strategy with smoke and melt-dripping suppression
[15] Cai Y, Wu Y, Yang F, Gan J, Wang Y, Zhang J. Wood sponge reinforced with
for condensation polymers. Compos B Eng 2021;211:108664.
polyvinyl alcohol for sustainable oil-water separation. ACS Omega 2021;6(19):
[42] Luo X, Shen J, Ma Y, Liu L, Meng R, Yao J. Robust, sustainable cellulose composite
12866–76.
aerogels with outstanding flame retardancy and thermal insulation. Carbohydr
[16] Wu M-B, Huang S, Liu T-Y, Wu J, Agarwal S, Greiner A, et al. Compressible carbon
Polym 2020;230:115623.
sponges from delignified wood for fast cleanup and enhanced recovery of crude oil
[43] Nabipour H, Nie SB, Wang X, Song L, Hu Y. Highly flame retardant zeolitic
spills by joule heat and photothermal effect. Adv Funct Mater 2021;31(3):
imidazole framework-8@cellulose composite aerogels as absorption materials for
2006806.
organic pollutants. Cellulose 2020;27(4):2237–51.
[17] Kong L, Guan H, Wang X. In situ polymerization of furfuryl alcohol with
[44] Wang D, Peng HY, Yu B, Zhou KQ, Pan HF, Zhang LP, et al. Biomimetic structural
ammonium dihydrogen phosphate in poplar wood for improved dimensional
cellulose nanofiber aerogels with exceptional mechanical, flame-retardant and
stability and flame retardancy. ACS Sustainable Chem Eng 2018;6(3):3349–57.
thermal-insulating properties. Chem Eng J 2020;389:124449.
[18] Chen G, Chen C, Pei Y, He S, Liu Y, Jiang B, et al. A strong, flame-retardant, and
[45] Yan M, Pan Y, Cheng X, Zhang Z, Deng Y, Lun Z, et al. “Robust–soft” anisotropic
thermally insulating wood laminate. Chem Eng J 2020;383:123109.
nanofibrillated cellulose aerogels with superior mechanical, flame-retardant, and
[19] Fu Q, Medina L, Li Y, Carosio F, Hajian A, Berglund LA. Nanostructured wood
thermal insulating properties. ACS Appl Mater Interfaces 2021;13(23):27458–70.
hybrids for fire-retardancy prepared by clay impregnation into the cell wall. ACS
[46] Yu Z-L, Yang N, Apostolopoulou-Kalkavoura V, Qin B, Ma Z-Y, Xing W-Y, et al.
Appl Mater Interfaces 2017;9(41):36154–63.
Fire-retardant and thermally insulating phenolic-silica aerogels. Angew Chem Int
[20] Guo H, Luković M, Mendoza M, Schlepütz CM, Griffa M, Xu B, et al. Bioinspired
Ed 2018;57(17):4538–42.
struvite mineralization for fire-resistant wood. ACS Appl Mater Interfaces 2019;11
[47] Li M-E, Yan Y-W, Zhao H-B, Jian R-K, Wang Y-Z. A facile and efficient flame-
(5):5427–34.
retardant and smoke-suppressant resin coating for expanded polystyrene foams.
[21] Gan W, Chen C, Wang Z, Pei Y, Ping W, Xiao S, et al. Fire-resistant structural
Compos B Eng 2020;185:107797.
material enabled by an anisotropic thermally conductive hexagonal boron nitride
[48] Rao W, Zhao P, Yu C, Zhao H-B, Wang Y-Z. High strength, low flammability, and
coating. Adv Funct Mater 2020;30:1909196.
smoke suppression for epoxy thermoset enabled by a low-loading phosphorus-
[22] Shabir Mahr M, Hübert T, Schartel B, Bahr H, Sabel M, Militz H. Fire retardancy
nitrogen-silicon compound. Compos B Eng 2021;211:108640.
effects in single and double layered sol–gel derived TiO2 and SiO2-wood
[49] Chen F, Zhou D, Wang JH, Li TZ, Zhou XH, Gan TS, et al. Rational fabrication of
composites. J Sol-gel Sci Techn 2012;64(2):452–64.
anti-freezing, non-drying tough organohydrogels by one-pot solvent displacement.
[23] Chen H, Zhang Y, Zhong T, Wu Z, Zhan X, Ye J. Thermal insulation and
Angew Chem Int Ed 2018;57(22):6568–71.
hydrophobization of wood impregnated with silica aerogel powder. J Wood Sci
[50] Liao H, Guo X, Wan P, Yu G. Conductive mxene nanocomposite organohydrogel for
2020;66(1):81.
flexible, healable, low-temperature tolerant strain sensors. Adv Funct Mater 2019;
[24] Mason TG, Seeger ZL, Nguyen ALP, Fujita K, Izgorodina EI. Predicting entropic
29(39):1904507.
effects of water mixing with ionic liquids containing anions of strong hydrogen
[51] Rong Q, Lei W, Chen L, Yin Y, Zhou J, Liu M. Anti-freezing, conductive self-healing
bonding ability: role of the cation. J Phys Chem B 2020;124(41):9182–94.
organohydrogels with stable strain-sensitivity at subzero temperatures. Angew
[25] Zhao G-J, Han K-L. Hydrogen bonding in the electronic excited state. Accounts
Chem Int Ed 2017;56(45):14159–63.
Chem Res 2012;45(3):404–13.
[52] Wang Z, Chen L, Chen Y, Liu P, Duan H, Cheng P. 3D printed ultrastretchable,
[26] Jiang S, Zhang M, Li M, Liu L, Liu L, Yu J. Cellulose nanofibril (CNF) based aerogels
hyper-antifreezing conductive hydrogel for sensitive motion and
prepared by a facile process and the investigation of thermal insulation
electrophysiological signal monitoring. Research 2020;2020:1426078.
performance. Cellulose 2020;27(11):6217–33.

11