Chemical Engineering Journal 382 (2020) 122880

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Chemical Engineering Journal

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Synthesis and textural evolution of mesoporous Si3N4 aerogel with high T

specific surface area and excellent thermal insulation property via the urea
assisted sol-gel technique
⁎
Jie Dinga,b, Xiaodong Wua,b, , Xiaodong Shena,b, Sheng Cuia,b, Ya Zhonga,b, Chen Ana, Yi Cuia,
Xiangbao Chenc
a
College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, China
b
Jiangsu Collaborative Innovation Center for Advanced Inorganic Function Composites, Nanjing Tech University, Nanjing 210009, China
c
Beijing Institute of Aeronautic Materials, Beijing 100095, China

H I GH L IG H T S

• Mesoporous Si N aerogel is firstly synthesized via the urea assisted sol-gel technique.
3 4

• SiSi NN aerogel
3 4 possesses a tremendously large BET specific surface area.
• Formation
3 aerogel has an excellent thermal insulation property.
4

• mechanism of Si N aerogel is revealed.

3 4

A R T I C LE I N FO A B S T R A C T

Keywords: Si3N4 aerogel, which is one of the most promising materials for application as high-temperature thermal in-
Sol-gel sulation, is synthesized by the urea-assisted sol-gel technique, followed by the supercritical drying, carboniza-
Si3N4 aerogel tion, carbothermal reduction and carbon combustion processes. The effects of heat treatment temperatures on
Porosity the physicochemical and textural evolution of mesoporous Si3N4 aerogel are investigated. Si3N4 aerogel is
Heat treatment
formed when the heat treatment temperature increases to 1500 °C, whereas it transforms into SiC phase with a
Nanoparticles
further higher temperature of 1600 °C. The SEM analysis confirms the existence of Si3N4 nanoparticles, and the
particle size of Si3N4 nanoparticles is around 20–40 nm, with pore size around 20–40 nm. The XPS measurement
reveals that Si3N4 aerogel is composed of 74.4% Si3N4 phase, with lower content of 25.6% SiO2. Si3N4 aerogel
possesses a large BET specific surface area of 519.6 m2/g, which results from the mesoporous pores left after
carbon combustion. This value is much larger than that of the conventional Si3N4 porous ceramics and Si3N4
nano materials ever reported. The BJH adsorption average pore diameter of Si3N4 aerogel is around 11.8 nm,
with a large pore volume of 3.5 cm3/g. Si3N4 oxidation with forming amorphous SiO2 layer on the surface is
observed by the TG measurement. Moreover, the resulting Si3N4 aerogel shows low bulk density of 0.075 g/cm3,
as well as low thermal conductivity of 0.045 W/(m·K) at room temperature. The mechanism of Si3N4 formation is
based on the VS growth between C, SiO2 and N2. The structures evolution and formation mechanism of Si3N4
aerogel are also investigated in this study.

1. Introduction for used in many high-temperature applications, such as structural

Si3N4 is one of the most promising advanced ceramic materials,
which possesses unique properties such as low density, high-tempera-
ture stability, high thermal shock, high mechanical strength and good
resistance to oxidation and corrosion, making them especially suitable
components of gas turbines, reciprocating engine parts, filters, catalyst
supports, and cutting tools [1–3]. Porous Si3N4 ceramics have been
attracting great interest for various applications due to its excellent
properties. Many methods including sintering with fugitive substance,
hydrothermal process [4], pore forming method [5], foam-gelcasting

⁎
Corresponding author at: College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, China.
E-mail address: wuxiaodong@njtech.edu.cn (X. Wu).

https://doi.org/10.1016/j.cej.2019.122880
Received 7 June 2019; Received in revised form 27 August 2019; Accepted 18 September 2019
Available online 18 September 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
J. Ding, et al.
technique [6], freeze-thaw technique [7], microwave-nitridation
method [8], and carbothermal reduction technique [9] have been
proposed to fabricate Si3N4 porous ceramics. However, Si3N4 porous
ceramics prepared by these methods possess mainly macropores with
diameters over tens of micrometers. The mechanical strength of Si3N4
porous ceramic is well improved due to its specific microstructure,
while the thermal insulation property is not good enough due to the
high bulk thermal conductivity of Si3N4 particles [8]. Therefore, the
application of Si3N4 porous materials in thermal insulation filed has
been limited.
Aerogels are porous materials, with low bulk density, high specific
surface area, high porosity and low thermal conductivity, which are
prepared by using air to replace liquid solvent within the wet gel. Their
unique properties make them of immense importance in various ap-
plications, such as thermal insulations, catalyst barriers, energy storage,
piezoelectrics, and sensors [10–18]. During the recent years, many re-
searchers have paid attention to making Si3N4 aerogel based nano
materials via different methods, within which the carbothermal re-
duction method is frequently used due to its low cost and high quality
of the products [19]. Carbothermal reduction needs the reaction be-
tween carbon and silica nanoparticles, therefore, many researchers
have paid attention to the preparation of resorcinol-formaldehyde (RF)
aerogels or the N-doped carbon aerogels. Mirzaeian [20] et al. pre-
sented a novel N-doped RF based carbon aerogel with controlled ni-
trogen content by varying the molar ratio of resorcinol/melamine
during the synthesis of the aerogel precursors. The N-doped carbon
aerogel showed an increase trend in pore volume and BET specific
surface area after doping with nitrogen element and the aerogel showed
excellent capacitive performance of cell as a result of improved por-
osity/active sites of the electrode. Ahamad [21] et al. developed a novel
porous magnetic N-doped carbon aerogel derived from sugarcane ba-
gasse cellulose. The aerogel showed an excellent adsorption property on
bisphenol-A from aqueous solution. The maximum removal rate can be
98–99% with condition at pH 7, temperature 343 K, and initial bi-
sphenol-A concentration of 100 ppm. The aerogel could be a high-effi-
cient adsorbent for environmental pollutant. Shanmugamet [22] al.
presented a new N-doped carbon aerogel using hydrothermal treatment
of cotton and ovalbumin as a carbon and nitrogen source, which can be
of potential use in the field of electrocatalysis for hydrogen production
and catalytic reduction of organic toxic pollutant. Nagy [23] et al.
showed a novel N-doped carbon aerogel which was derived from the
graphene oxide containing resorcinol-formaldehyde-melamine polymer
aerogel. The reduced graphene oxide and nitrogen functionalities sy-
nergistically promoted the electrochemical behavior of carbon aerogel.
The dominant reduction pathway changed from the slow 2e− to the
more efficient 4e− route. Up to now, some methods have been proposed
for fabrication of Si3N4 based nanoporous materials. Su [2] et al. de-
veloped a method of fabricating siloxane xerogel prepared from me-
thyltrimethoxysilane and dimethyldimethoxysilaneas as silica source.
The graphite substrate was then used for depositing α-Si3N4 nanobelt
aerogel at elevated temperatures under flowing nitrogen. Wang [19]
et al. proposed α-Si3N4 nanofibers and nanobelts prepared from me-
soporous silica-carbon nanocomposites via the carbothermal reduction
process. Polyethylene oxide-polypropylene oxide-polyethylene was
used as carbon source, while tetraethoxysilane is adopted as silica
source. Liu [24] presented a Fe(NO3)3-assisted large scale synthesis
method for fabricating three-dimensional Si3N4 nanobelt using quartz
and graphite as raw materials followed by carbothermal reduction
process.
Having known that catechol/formaldehyde/SiO2 (CF/SiO2) organic-
inorganic aerogel can be pyrolyzed into Carbon/SiO2 aerogel in similar
manner as the RF/SiO2 aerogel, calcination of N-doped Carbon/SiO2
aerogel under flowing nitrogen might lead to a Si3N4 nanomaterial with
high porosity and large specific surface area. This approach also pro-
vides a benefit of controlling different factors that influence the struc-
ture of the resulting aerogel. Therefore, this technique is considered as a
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Chemical Engineering Journal 382 (2020) 122880
simple method for fabricating porous Si3N4 aerogel without a special
equipment and complicated procedures. In this work, we developed a
novel one-step method to fabricate the Si3N4 aerogel with low bulk
density, high specific surface area and excellent thermal insulation
property. Urea containing nitrogen source is firstly mixed with the CF
sol before gelation, which promotes the formation of Si3N4 aerogel
afterwards. Aminopropyltriethoxysilane (APTES) is then adopted in this
mixture, which can be used as silica source, as well as gelation agent. N-
doped CF/SiO2 aerogel is formed after aging, solvent exchange and
supercritical drying processes, after which pyrolysis is performed on the
aerogel for fabricating N-doped Carbon/SiO2 aerogel. The Si3N4 aerogel
is ultimately obtained via carbothermal reduction under flowing ni-
trogen and carbon combustion under air atmosphere. The effect of heat
treatment temperatures on the physicochemical properties of the re-
sulting aerogels is investigated and the detailed preparation procedures,
characteristics of the products and the mechanism of Si3N4 aerogel
formation are also proposed.
2. Experimental procedures
2.1. Synthesis
Catechol (C), formaldehyde (F), anhydrous alcohol (EtOH), 3-ami-
nopropyltriethoxysilane (APTES), and urea were used as raw materials.
C was first dissolved in EtOH solvent, followed by the addition of F with
a molar ratio of C:F:EtOH = 1:2:22. Urea was then added into the
mixed solution, stirring for 5 min with the specific molar ratio of
urea:C = 0.83:1. APTES was then dropped wise into the solution with
the molar ratio of APTES:C fixed at 0.77:1. The reaction mixture was
further stirred for 10 min at room temperature, after which it was
transferred into steel molds, and it was allowed to gel at room tem-
perature within 30 min. The wet gel was aged at 50 °C for 1 d.
Subsequently, the resultant wet gel was washed with ethanol to remove
the water, organic solvent and impurities inside the pores. The wet gel
was dried with CO2 supercritical drying, thus to afford the as-dried N-
doped CF/SiO2 composite aerogel. The as-dried aerogel is carbonized at
800 °C for 3 h under flowing nitrogen with a flowing rate of 100 mL/
min, thus to form the N-doped Carbon/SiO2 aerogel. Carbothermal
reduction processes with different heat treatment temperatures at
1300 °C, 1400 °C, 1500 °C and 1600 °C for 5 h with a flow rate of ap-
proximately 100 mL/min under flowing nitrogen were performed on
the N-doped Carbon/SiO2 aerogel. The carbon combustion at 600 °C for
3 h under air atmosphere was then carried out for getting rid out of
residual carbon nanoparticles within the composite aerogel, thus to
obtain the Si3N4 aerogel with high specific surface area and excellent
thermal insulation property.
2.2. Characterizations
The X-ray diffraction (XRD) patterns were recorded using a X'Pert
PRO MPD, a diffractometer with CuKα1 radiation (λ = 0.15406 nm).
The X-ray tube was operated at 40 kV and 40 mA. Thermal gravimetric
(TG) and differential scanning calorimetry analysis (DSC) were per-
formed by NETZSCH STA449C Thermogravimetric analyzer under a
specific flowing rate of 30 mL/min with a heating rate of 10 °C/min.
Scanning electron microscopy (SEM) was conducted using a Nova
NanoSEM 450 field emission scanning electron microscope.
Photographs and EDS spectra of the aerogels were taken with a trans-
mission electron microscope (TEM) using JEOL JEM-2100 (UHR) op-
erating at the acceleration voltage of 200 kV. Surface areas, pore vo-
lume and pore distribution were measured by using a V-Sorb 2800P
surface area and pore distribution analyzer. Vacuum degassing was
done prior to BET analysis. The pretreatment condition is 300 °C with
the dwelling time of 6 h. The bulk densities of the samples with dif-
ferent heat treatment temperatures are calculated with a cylindrical
shape by measuring mass, diameter and height. Each measurement was
J. Ding, et al.
Fig. 1. XRD patterns of the aerogel materials heat treated at different tem-
peratures under flowing nitrogen.
carried out for three times. The thermal insulation property was carried
out by an infrared imaging device, detecting the transient temperature
change on the cold face with a constant temperature of the hot face. The
room temperature thermal conductivity of the aerogel is investigated by
the measuring apparatus (TPS2500, Hot Disk, Sweden) using a transient
plane heat source method at 25 °C. The size of the sample is
40 mm × 40 mm × 10 mm, and the type of the probe is kapton (C5501)
with its radius at 6.403 mm. The probe is also acted as the heat source
and two pieces of the Si3N4 aerogels are placed below and above the
testing sensor to ensure good thermal contact. The high temperature
thermal conductivities are carryout out by the hot-plate method, with
the sample size of 300 mm × 300 mm × 10 mm. The XPS spectra of the
aerogel composites were obtained on the 250XI X-ray photoelectron
spectroscopy. The FTIR spectra of the aerogel samples are characterized
on the Nicolet IS 10 FT-IR using a resolution of 4 cm−1 and 32 scans.
3. Results and discussion
Fig. 1 shows the typical XRD patterns of the samples heat treated at
Fig. 2. Photographs of the (a) aerogel materials heat treated at different temperatures under flowing nitrogen and (b) Si3N4 aerogel after further carbon combustion
at 600 °C for 3 h under air atmosphere.
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Chemical Engineering Journal 382 (2020) 122880
different temperatures under flowing nitrogen to detect the formation
route of Si3N4 aerogel. There are no obvious diffraction peaks for the as-
dried N-doped CF/SiO2 aerogel, while there is a broad and weak peak at
ca. 20°, which corresponds to the amorphous silica caused by the silica
clusters within the composite aerogel. After carbonization at 800 °C for
3 h, the N-doped CF/SiO2 aerogel is converted into N-doped Carbon/
SiO2 aerogel, with a peak shift from 20° to 23°, which originates from
the carbon nanoparticles formation with the release of CO, H2 and CH4
gas, et al. The N-doped Carbon/SiO2 aerogel is then heat treated under
flowing air to confirm the Carbon/SiO2 mass ratio in the sample, which
is vital for further formation of Si3N4 aerogel via carbothermal reduc-
tion process. The C/SiO2 mass ratio is thus determined at 1.53 as cal-
culated by the carbon mass and silica mass, respectively. It is noted that
there is no obvious change for the carbothermal reduction temperatures
ranging from 1200 °C to 1400 °C, however, after heat treatment tem-
perature at 1500 °C for 5 h, the XRD analysis result reveals that the α-
Si3N4 (PDF No. 76–1410) is formed in the aerogel. Peaks at 20.56°,
22.81°, 26.45°, 30.89°, 34.42°, 35.20°, 41.84°, and 43.29° can be as-
signed to the (1 0 1), (1 1 0), (2 0 0), (2 0 1), (1 0 2), (2 1 0), (2 0 2) and
(3 0 1) planes of α-Si3N4 phase. With a further heat treatment at 1600 °C
for 5 h, SiC (PDF No. 89-2226) phase begins to dominate within the
aerogel, which is suggested to be the result from reaction (1) [25,26]. It
is noted that there can be two reaction routes for SiC formation as listed
in reaction (2) and reaction (3) [27,28], where SiO is obtained by re-
action of SiO2 and carbon nanoparticles. The production of Si3N4 and
SiC are competitive process during the carbothermal reduction process
since Si3N4 is mainly formed in the sample after 1500 °C heat treatment
while there is only SiC is detected after further heat treatment at
1600 °C. The carbothermal reduction temperature is therefore de-
termined at 1500 °C for 5 h based on the XRD results. The mechanism of
Si3N4 formation will be discussed afterwards.
SiO2 (s) + 3C(S) → SiC(s) + 2CO(g) (1)
SiO(g) + 2C(s) → SiC(s) + CO(g) (2)
SiO(g) + 3CO(g) → SiC(s) + 2CO2 (g) (3)
Fig. 2 presents the photographs of the aerogel materials during heat
treatment processes. As seen in the figure, the as-dried N-doped CF/
SiO2 is crack-free with an opalescent color, while the other samples
after heat treatment at 800 °C, 1300 °C, 1400 °C, and 1500 °C under
J. Ding, et al.
Fig.3. FTIR spectra of aerogel materials heat treated at different temperatures
under flowing nitrogen.
flowing nitrogen present black color due to carbon nanoparticles inside.
However, after further carbon combustion at 600 °C for 3 h under
flowing air, the black carbon nanoparticles disappear after oxidation.
The bulk densities of the samples in Fig. 2(a) are 0.11 g/cm3, 0.14 g/
cm3, 0.12 g/cm3, 0.11 g/cm3 and 0.10 g/cm3, respectively, while the
bulk density of Si3N4 aerogel in Fig. 2(b) is 0.075 g/cm3. After carbo-
nization at 800 °C for 3 h, the N-doped Carbon/SiO2 aerogel exhibits a
linear shrinkage in diameter of 27.7% combined with a mass loss of
47.4%. After further carbothermal reduction process with temperatures
at 1300 °C, 1400 °C and 1500 °C, the composite aerogels exhibit further
mass losses of 20%, 28% and 42% as compared with the 800 °C heat
treated sample, respectively. It is observed that in the sample after
1500 °C heat treatment, a light-green color layer is shown in the surface
of the sample, indicating that little amount of SiC phase is formed on
Fig. 4. SEM images of the aerogel materials heat treated at different temperatures (a) as-dried, (b) 800 °C, and (c) 1500 °C under flowing nitrogen, and (d) after
further carbon combustion at 600 °C for 3 h under flowing air.
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Chemical Engineering Journal 382 (2020) 122880
the surface of Si3N4 aerogel.
Fig. 3 shows the FTIR spectra of aerogel materials heat treated at
different temperatures under flowing nitrogen. The most distinct peak
at 3396 cm−1 is commonly assigned to the stretching vibration of O–H
bonds [3,29]. The band at 1648 cm−1 for the as-dried N-doped CF/SiO2
aerogel is caused by the aliphatic tertiary amides, which originates from
the incorporation of APTES. These small and weak bands at 2937 cm−1,
2875 cm−1, 1363 cm−1 and 694 cm−1 are assigned to the C–H bond,
which indicates that carbonaceous residuals are lined to this N-doped
CF/SiO2 aerogel. Furthermore, the band at 1041 cm−1 is corresponding
to the vibration of –CH2OH group in the typical CF aerogel. It is ob-
viously that the FTIR features corresponding to N-doped CF/SiO2
aerogel disappear after carbonization at 800 °C for 3 h. The contribution
of water is confirmed by the absorption band at 1654 cm−1 [30]. The
band at 1116 cm−1 belongs to the antisymmetric stretching vibration
and the band at 763 cm−1 can be assigned to the asymmetry stretching
vibration of Si–O–Si, and they shift to a smaller value after carbon
formation during carbonization [26], which confirms the presence of
silica in all composites. The signal with a wavenumber of 465 cm−1 can
be indexed to the deformation vibration of Si–O–Si group [25]. Almost
no change are observed between the sample with heat temperatures at
800 °C, 1300 °C and 1400 °C, except the further pyrolysis of organic
groups within composite aerogel. It is found that the peak at 763 cm−1
becomes weaker, and almost disappears when the heat treatment
temperature increases to 1400 °C, indicating the carbothermal reduc-
tion process which consumes silica amount. It is indicated that after
carbonization at 800 °C for 3 h, the organic groups mainly disappear,
and the composite aerogel is recognized to form the porous structure,
which is essential for further formation of Si3N4 nanoparticles. It is
noted that after heat treatment at 1500 °C for 5 h under flowing ni-
trogen, the bands at 950 cm−1 corresponding to amorphous Si3N4 begin
to show in the composite aerogel [31], which keeps consistent with the
XRD results aforementioned. The FTIR result also confirms the forma-
tion of SiC on the surface of Si3N4 aerogel after heat treatment tem-
peratures at 1500 °C, since adsorption band corresponding to Si-C
bonding, e. g. at 818 cm−1 is observed.
J. Ding, et al. Chemical Engineering Journal 382 (2020) 122880

The products obtained from different heat treatment temperatures

are characterized by the SEM technique as revealed in Fig. 4(a–d), re-
spectively. All samples exhibit porous morphology. The morphologies
of the samples at different stages are not significantly changed after
carbonization and carbothermal reduction processes. It is due to the
fact that the amount of carbon is in great excess of 1.53 (the stoichio-
metric C/SiO2 mass ratio for Si3N4 formation is 0.4) for the Si3N4 for-
mation reaction, therefore, some amount of carbon remains in the re-
sulting aerogel materials. The N-doped Carbon/SiO2 aerogel shows
similar spherical grains with relatively uniform size, as compared with
the N-doped CF/SiO2 aerogel, which is common as is reported for other
organic aerogels. Hence, the structure, morphology and the porosity of
all the samples afterwards depend on the formation of the N-doped CF/
SiO2 aerogel. The particle size of the as-dried N-doped CF/SiO2 aerogel
is around 60–80 nm, with the pore diameters at several tens of nan-
ometers, a typical mesoporous structure of aerogel material, which is
totally different from that reported by Marisa et al. [25]. Many large
pores with diameters larger than 500 nm are formed after carbonization
at 800 °C for 3 h because some of the colloidal particles decompose into
Fig. 6. A survey XPS spectrum of the aerogel materials after heat treatment at
volatile gases due to the pyrolysis of CF organic groups [32]. The N-
different temperatures.
doped Carbon/SiO2 aerogel presents porous structures of a typical
colloidal gel, which consists of carbon nanoparticles and SiO2 nano-
particles. After further heat treatment at 1500 °C for 5 h, Si3N4 nano- pores with diameters over 100 nm exist within the pore structures of the
particles are formed via the reaction between carbon, N-doped silica Si3N4 aerogel. It shows a typical structure of aerogel materials, but the
and nitrogen gas. The amount of large pores is decreased, and Si3N4 product is amorphous without ordered structure as no obvious dif-
particles are formed with some amount of carbon nanoparticles em- fraction spots are observed in the SAED results, and this is also verified
bedded in the composite aerogel. The carbon nanoparticles are there- by the SEM results. The EDX analysis shows that the sample is mainly
fore removed after further carbon combustion, as is presented in composed of C, O, Si, and N elements. The C signal appearing in the
Fig. 4(d), leaving the Si3N4 nanoparticles and small amount of silica EDX result originates from the carbon member on the copper grid for
particles in the product. This aerogel possesses a much more compact supporting samples. The mass percentage of N element is 14.8%, and it
microstructure in comparison with the former aerogel materials, and is 19.7% for Si element. The atomic ratio of N to Si is thus calculated as
the particles with smaller diameters at around 20–40 nm are well dis- 1.52, being close to the precise atomic ratio of 1.33, therefore, in-
persed in the matrix. dicating the successful synthesis of Si3N4 aerogel.
Fig. 5 shows the TEM image, SAED patterns, and EDS spectra of the Fig. 6 displays the XPS spectrum of the composite aerogel after
resulting Si3N4 aerogel product. It can be clearly seen that the aerogel different heat treatment temperatures. The resulting aerogels primarily
possesses nanoparticles with diameters at around 20–40 nm and na- have elements of O, C, Si and N. It is noted that after carbonization at
nopores with pore diameters at around 20–40 nm. Small amount of 800 °C for 3 h, the peaks corresponding to Si 2p increase, while the

Fig. 5. (a, b) TEM image, (c) SAED patterns, and (d) EDS spectra of Si3N4 aerogel.

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J. Ding, et al. Chemical Engineering Journal 382 (2020) 122880

Fig. 7. XPS Si2p and C1s spectrum of the aerogel materials heat treated at different temperatures (a, b) 800 °C/3h and (c, d) 1500 °C/5h under flowing nitrogen.

intensity of N 1s decreases, indicating that silica clusters are formed

after carbonization, while N element is partially consumed due to the
pyrolysis process. After heat treatment at 1500 °C for 5 h, we can find
that the peaks corresponding to Si 2p decrease sharply, while the
carbon content is strongly increased due to the process of carbothermal
reduction process under flowing nitrogen. Silica is consumed while C is
left after this reaction. However, the silica content begins to increase
after further carbon combustion under flowing air, which indicates that
silica is surrounded by carbon nanoparticles after carbothermal re-
duction process, and after burning with air, silica cluster is exposed
with Si3N4 nanoparticles inside the material. Therefore, the Si3N4
aerogel is composed of Si3N4 nanoparticles and SiO2 particles as well.
To understand the fundamental issues of Si3N4 formation, XPS
technique is utilized as a tool to characterize the sample after carbo-
nization at 800 °C for 3 h and carbothermal reduction process at 1500 °C
for 5 h (Fig. 7). The signal curves are fitted by peak addition by Gaus-
sian-Lorenzian peak approximations and Shirley background reduction.
The Si 2p spectra can be consisted of three peaks: 100.3 eV, 101.4 eV
and 102.8 eV, which are identified as SiC, Si3N4 and SiO2, respectively Fig. 8. Nitrogen sorption isotherms and BJH pore size distributions of the
[33,34]. In our XPS study, only one peak at 103.16 eV corresponding to aerogel materials heat treated at different temperatures under flowing nitrogen.
Si–O bond for the 800 °C carbonized sample is observed, and there is a
small charge shift, which may result from the effect of amino propyl distributions of the different kinds of aerogel materials. The pore
group in the composite. This is also verified by the C 1s spectra, which structures data are summarized in Table. 1. According to Figs. 8 and 9,
shows that the spectra is composed of two peaks, corresponding to the all the curves exhibit type IV isotherms with distinct capillary con-
C–C bond and C–N bond, respectively. It is noted that after heat densation steps in the range of relative pressure between 0.5 and 1.0,
treatment at 1500 °C, the Si 2p spectra in our work consists of two which demonstrates the mesoporous three-dimensional network struc-
peaks. The Si-N bond at 101.4 eV occupies 74.4% and Si–O bond at ture of the aerogel composites [35,36]. The BET specific surface areas
102.8 eV occupies 25.6%, which indicates that after 1500 °C for 5 h, the of the as-dried N-doped CF/SiO2 aerogel is 279.9 m2/g, however, this
aerogel is composed of mainly Si3N4, with small content of SiO2. No value decreases to 74.5 m2/g after 800 °C for carbonization process.
track of SiC phase is observed. This further confirms the existence of SiC This is explained by the phenomenon that many large pores appear
phase on the surface of Si3N4 aerogel, which keeps consistent with the inside the aerogel matrix during volatile gases release, as is consistent
results of FTIR analysis. The C 1s spectra is composed with two C–N with the SEM results. It is noted that after heat treatments at 1400 °C
peaks at 284.85 eV and 288.83 eV, which has been similarly reported in and 1500 °C, the micropores show an abrupt increase since the ad-
previous study [33]. sorbed volumes increases sharply at the relative pressure below 0.05,
Figs. 8 and 9 present nitrogen sorption isotherms and BJH pore size which corresponds to the region of the micropore adsorption. The

6
J. Ding, et al.
Fig. 9. Nitrogen sorption isotherms and BJH pore size distribution of the re-
sulting Si3N4 aerogel.
micropore volumes are measured as 0.15 cm3/g and 0.11 cm3/g, with
the BET specific surface area of 361.7 m2/g and 324.4 m2/g, respec-
tively, which are much bigger than that of the sample after carboni-
zation at 800 °C. The top inlet of Fig. 8 shows that the most probable
diameter of the as-dried N-doped CF/SiO2 aerogel is between 2.0 nm
and 7.0 nm. It is found that after further carbon combustion, the most
probable diameter in the mesoporous range is not obviously changed.
The BET specific surface area is as large as 519.6 m2/g, which is much
higher than that of the conventional Si3N4 porous ceramics and pre-
viously reported Si3N4 nanomaterial [1,25,26,37]. In addition, the
specific surface area is lower than that of carbon aerogel [38,39] due to
the existence of large amount of micropores after pyrolysis under inert
gas. However, it is much higher than that of nanostructured BN network
[40,41] with the similar high heat treatment temperatures. The BJH
adsorption pore volume also increases to 3.5 cm3/g with a large extent
due to the carbon combustion and mesoporous voids left inside the
aerogel.
Fig. 10 shows the thermogram profiles of the aerogel samples with
the flowing rate of 30 mL/min and heating rate of 10 °C/min. The as-
dried N-doped CF/SiO2 aerogel is performed under flowing nitrogen
and the 1500 °C heat-treated composite aerogel is tested under flowing
air. It is found in Fig. 10(a) that for the as-dried N-doped CF/SiO2
aerogel, mass loss of about 40% is observed during the carbonization
process after 800 °C for 3 h, along with a wide and broad exothermic
peak during this process. The mass loss value is lower than 47.4% due
to the lack of dwelling time at the carbonization temperature at 800 °C.
The endothermic peak with the temperature at about 200 °C is attrib-
uted to the evolution of physically adsorbed water. No other obvious
exothermic or endothermic peaks are found in this process. For the
aerogel material after carbothermal reduction at 1500 °C for 5 h, the
thermogram profile can be divided into three main regions:
20 °C–120 °C, 120 °C–930 °C and 930 °C above. The first region is caused
by the removal of physically adsorbed water, while the second region
Table 1
Pore structures of the composite aerogel with different heat treatment temperatures.
Heat treatment temperatures (°C) Micropore pore volumes (cm3/ BET specific surface areas
g) (m2/g)
As-dried 0.11 279.9
800 0.030 74.5
1300 0.064 135.5
1400 0.15 361.7
1500 0.11 324.4
1500–600 0.22 519.6
7
Chemical Engineering Journal 382 (2020) 122880
originates from the carbon removal process. Therefore, after car-
bothermal reduction process at 1500 °C, the amount of carbon nano
particles remains 2.45% inside the aerogel composite, which partly
leads to the micropore volume of 0.11 cm3/g as indicated by the ni-
trogen sorption isotherms measurement. The pores between Si3N4
aerogel nanoparticles may also contribute to the large micropore vo-
lume. The mass gradually increases with further increase in tempera-
ture, which results from the Si3N4 oxidation, forming amorphous SiO2
layer on the surface. The increased amorphous silica layer can protect
the Si3N4 aerogel from further oxidation, which is also reported by
previous study [2]. Moreover, in order to evaluate the thermal insula-
tion property of the resulting Si3N4 aerogel, the room temperature and
high temperature thermal conductivities are conducted as well. The
room temperature thermal conductivity tested by the Hot disk is
0.045 W/(m·K), which is comparable to that of SiC aerogel [42] and
mullite whisker aerogel [43] previously reported. The low room tem-
perature thermal conductivity confirms the excellent thermal insulation
property of this material under room temperature. The Si3N4 aerogel is
derived from thermal treatment at 1500 °C for 5 h under flowing ni-
trogen, therefore the thermal resistance of this aerogel is no less than
1500 °C under inert atmosphere, which is much larger than the original
silica aerogel since pore collapse and volume shrinkage occurs for silica
aerogel at temperatures over 650 °C. Moreover, the high temperature
thermal conductivity is tested using the hot-plate method. The thermal
conductivities of the Si3N4 aerogel are 0.062 W/(m·K) and 0.12 W/
(m·K) at 400 °C and 800 °C, respectively, which is superior to SiC
aerogel previously published[44].
From the above mentioned analysis of the aerogel composites with
different heat treatment temperatures, the mechanism of the Si3N4
aerogel formation is revealed. The overall process can be illustrated in
Fig. 11. The CF primary particles, SiO2 primary particles and CF/SiO2
primary particles coexist in the composite gel after the hydrolysis-
condensation processes. The N-doped CF/SiO2 is thus obtained after
aging, solvent exchange and supercritical drying processes, and the N
atoms addition by urea promotes the formation of Si3N4. The amount of
N atoms decreases as is indicated in the XPS result and the CF clusters
transform into the carbon clusters after carbonization process. The SEM
analysis reveals that the sample after final carbon combustion is Si3N4
nanoparticles. Therefore, Fig. 4(d) is indeed porous Si3N4 structure, of
which the grains are formed from the carbothermal reduction process of
silica clusters dispersed within the Carbon/SiO2 composite. The APTES
used in this work is at low concentration in order to ensure the good
dispersion of silica clusters inside the N-doped Carbon/SiO2 aerogel and
limit contact between silica and surrounding carbon nanoparticles [26].
With such intimate contact between silica and carbon nanoparticles,
reaction (4) is enhanced. In order to investigate the Si3N4 aerogel
SiO2 (s) + C(s) → SiO(g) + CO(g) (4)
formation mechanism, the Gibbs free energy calculations are also
carried out. As seen in Fig. 12(a), with the decrease of SiO partial
pressure and increase of reaction temperature, the delta Gibbs energy
decreases. When the SiO partial pressure is lower than 0.001 standard
atmospheric pressure (0.001 atm), this reaction occurs with the reac-
tion temperature increases to 1740 K (1467 °C). In our work, the
BJH adsorption average pore BJH adsorption Pore volumes
diameters (nm) (cm3/g)
9.4 0.73
10.5 0.32
11.3 0.22
12.7 0.75
15.0 0.36
11.8 3.50
J. Ding, et al.
Fig. 10. (a) TG/DSC curves of the as-dried N-doped CF/SiO2 aerogel under flowing nitrogen and (b) TG curve of the 1500 °C heat-treated composite aerogel under
flowing air.
reaction temperature is at 1500 °C, and the SiO partial pressure is ex-
tremely low at the very beginning, reaction (4) is therefore enhanced. It
is mentioned that the overall stoichiometric equations for the synthesis
of Si3N4 in this technique can be described as reaction (5):
3SiO2 (s) + 6C(s) + 2N2 (g) → Si3N4 (s) + 6CO(g) (5)
The delta Gibbs free energy during this reaction can be described as
Fig. 12(b). The flowing nitrogen with the flow rate at 100 mL/min is
continuous during the total process of Si3N4 aerogel fabrication. We
have guaranteed that the N2 partial pressure is slightly positive. It is
observed that when the N2 partial pressure is 5 atm, the formation
temperature of Si3N4 aerogel is at around 1760 K (1487 °C). During the
high temperature carbothermal reduction process, SiO2 reacts with C
forming SiO and CO gases, and SiO2 can also further reacts with CO to
form SiO as is seen in reaction (6). When SiO is formed, it will react
with N2 together with C, to nucleate Si3N4 nanoparticles according to
reaction (7).
SiO2 (s) + CO(s) → SiO(g) + CO2 (g) (6)
Fig. 11. Formation of N-CF/SiO2 aerogel and its transformation to Si3N4 aerogel.
8
Chemical Engineering Journal 382 (2020) 122880
3SiO(g) + 3C(s) + 2N2 (g) → Si3N4 (s) + 3CO(g) (7)
The mechanism of Si3N4 formation through reactions (6) and (7)
can also be verified by the analysis of delta Gibbs free energy of these
two reactions, as can be seen in Fig. 12(c) and Fig. 12(d). Reaction (6) is
difficult to happen since the delta Gibbs free energy is almost positive
when the SiO partial pressure is over 0.000001 atm. However, since the
carbothermal reduction is conducted under dynamic N2 atmosphere,
the intermediate products of SiO can be largely carried out by the
flowing argon, thus the partial pressure of SiO can be lower than
0.000001 atm, therefore, reaction (6) happens when the temperature
increases to 1720 K (1447 °C). This conclusion keeps consistent with the
former discussion on reaction (4). Reaction (6) provides SiO which is
necessary for the formation of Si3N4 through reaction (7). It is found
that the delta Gibbs free energy keeps almost negative when the N2
partial pressure is over 1 atm, therefore, this reaction can easily occur at
elevated temperatures. This further confirms the proposed formation
mechanism of Si3N4 aerogel.
It is reported that the Si3N4 nanowire, nanowhisker and nanobelt
J. Ding, et al.
Fig. 12. The calculated Gibbs free energy changes of different reactions at different SiO and N2 partial pressure.
will grow along a low direction based on the Si3N4 nucleus via reaction
(8) [24,45]. However, it should be noted that neither wire nor whisker
is observed in the product of this work. This can be explained by the
fact that no transition metal is introduced for the Si3N4 VLS growth
[24]. Luyjew et al. have also reported the similar phenomenon and they
attributes it to the fact that the silica particles are dispersed into very
small clusters in the carbon matrix, therefore, the generation of SiO
vapor is limited to be localized and dramatic growth of Si3N4 whisker
and nanobelt are prevented [26]. In conclusion, the formation of Si3N4
aerogel is based on the VS growth between C, SiO2 and N2.
3SiO(g) + 3CO(g) + 2N2 (g) → Si3N4 (s) + 3CO2 (g)
4. Conclusions
In summary, we have prepared Si3N4 aerogel via the urea-assisted
sol-gel technique, followed by the supercritical drying, carbonization,
carbothermal reduction and carbon combustion processes. Si3N4
aerogel can be well formed after carbothermal reduction at 1500 °C for
5 h under flowing nitrogen, with a thin SiC layer on the surface of Si3N4
aerogel. The Si3N4 aerogel transforms into SiC phase after further heat
treatment at 1600 °C. The particle size of Si3N4 nanoparticles are at
around 20–40 nm, and the pore size of the Si3N4 aerogel locates at
20–40 nm. Si3N4 aerogel is composed of 74.4% Si3N4 phase, with lower
content of 25.6% SiO2. The Si3N4 aerogel possesses an extremely large
BET specific surface area of 519.6 m2/g due to mesoporous voids left
after carbon combustion, which is much larger than that of the con-
ventional Si3N4 porous ceramics and nanomaterial. Si3N4 aerogel pos-
sesses a BJH adsorption average pore diameter at around 11.8 nm, and
a large pore volume of 3.5 cm3/g. Moreover, the resulting Si3N4 aerogel
displays low thermal conductivity of 0.045 W/(m·K) at room tempera-
ture. The mechanism of Si3N4 formation is based on the VS growth
Chemical Engineering Journal 382 (2020) 122880
between C, SiO2 and N2. These excellent properties make Si3N4 aerogel
a promising material to be used as a fireproofing material and high
temperature thermal insulator.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
(8)
This work was financially supported by the General Program of
Natural Science Fund in Colleges and Universities of Jiangsu Province
(19KJB430023), the Postgraduate Research & Practice Innovation
Program of Jiangsu Province (2019K005), National Natural Science
Foundation of China (51702156), Natural Science Foundation of
Jiangsu Province-China (BK20161003), Jiangsu Collaborative
Innovation Center for Advanced Inorganic Function Composites. Any
opinions, findings, and conclusions or recommendations expressed in
this paper are those of the authors and do not necessarily reflect the
views of these programs.
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