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A novel high-entropy (Sm0.2Eu0.2Tb0.2Dy0.2Lu0.2)2Zr2O7 ceramic aerogel

with ultralow thermal conductivity

Article in Ceramics International · July 2021

DOI: 10.1016/j.ceramint.2021.07.170

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 Ceramics International 47 (2021) 29960–29968

Contents lists available at ScienceDirect

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

A novel high-entropy (Sm0.2Eu0.2Tb0.2Dy0.2Lu0.2)2Zr2O7 ceramic aerogel

with ultralow thermal conductivity
Debao Liu, Yiguang Wang, Feifei Zhou, Baosheng Xu *, Bowen Lv **
Institute of Advanced Structure Technology, Beijing Institute of Technology, Beijing, 100081, PR China

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

Keywords: Here, we report a novel high-entropy rare earth zirconate (HE-REZ) (Sm0.2Eu0.2Tb0.2Dy0.2Lu0.2)2Zr2O7 ceramic
High-entropy ceramics aerogel prepared through a sol-gel template method and high-temperature calcination followed by 3-D-structure
Aerogel reconstruction. The structural evolution and crystallisation behaviour of the prepared aerogel were characterised
Rare earth zirconates
through scanning electron microscopy, X-ray diffraction and transmission electron microscopy. The results
Thermal conductivity
indicated that the as-prepared HE-REZ ceramic aerogels had a typical nanoporous structure. The HE-REZ ceramic
aerogels thermally treated at 900 ◦ C presented an ultralow room temperature thermal conductivity of 0.031 W/
(m⋅K), high specific surface areas of 443.26 m2/g and a relatively high strength of 12.95 MPa. The effects of
different calcination temperatures on the microstructure of the samples were also investigated. Therefore, the
excellent insulation performance of these unique HE-REZ ceramic aerogels indicate that they can be used as high-
temperature insulators for hypersonic vehicles in the future.

1. Introduction insulation material, which has a wide applications in aerospace, chem­

With the rapid development of aerospace industries, demands on
hypersonic vehicle thermal protection systems with an enhanced per­
formance have increased and intrigued great research interest. As is
known to us, the hypersonic vehicles will face extremely harsh aero­
dynamic heating environment when serviced at high speed in hyper­
sonic regimes and their surface temperature can reach up to 1300 ◦ C or
higher values [1,2]. Therefore, in order to make sure the safe operation
of the internal components of hypersonic vehicle systems, a new type of
lightweight thermal protection material that can withstand higher
operation temperatures should be developed [3].
Aerogel is a new type of nanoporous material with a controllable
structure. The porosity and specific surface areas of aerogels can reach
up to 80.0%–99.8% and 800–1000 m2/g, respectively. The typical pore
size and solid-state network structure unit size are 1–100 and 1–20 nm,
respectively [4,5]. Aerogel performs ultralow solid and gaseous heat
conduction because of its 3-D nanoporous network structure. Its total
thermal conductivity under normal temperature and pressure is as low
as 0.01 W/(m⋅K). Consequently, aerogel has been considered an excel­
lent material with the lowest thermal conductivity and density amongst
solid materials [6,7]. The aerogel is a kind of light and efficient
ical industry, metallurgy and energy-saving building fields.
One of the advanced insulating materials of single oxide aerogels is
SiO2 aerogel which obtains a very low thermal conductivity (≤0.015 W/
(m⋅K)) at ambient temperature and pressure. However, its structure is
unstable as the working temperature increases up to 650 ◦ C [8–10]. In
addition, traditional methods of SiO2 aerogel preparation require high
temperature and pressure which greatly limit the commercial applica­
tions of SiO2 aerogel. The hydrophilicity of SiO2 aerogel is prone to
cause the collapse of its 3-D nanoporous network structure. SiO2 aerogel
easily cracks during the drying process, thereby reducing the thermal
insulation performance of SiO2 aerogel. Hence, other composite aerogel
with more thermal stable properties has been explored. For example,
Guo et al. [11] produced ZrO2–SiO2 composite aerogel with a high
specific area (up to 172 m2/g) and large pore volume (0.97 m3/g). Wu
et al. [12] synthesised an Al2O3–SiO2 composite aerogel with ultra-low
thermal conductivity (0.023 W/(m⋅K)) and a specific surface area of 166
m2/g. Zhang et al. [13] reported a high-strength ZrO2–SiO2 composite
aerogel prepared with a newly modified method and obtained a good
compressive strength property. However, the pore structures of these
reported aerogels easily collapse and shrink when used at high tem­
perature (≥1000 ◦ C). Therefore, a new kind of aerogel with structural

* Corresponding author.
** Corresponding author.
E-mail address: xubsh@bit.edu.cn (B. Xu).

https://doi.org/10.1016/j.ceramint.2021.07.170
Received 3 July 2021; Received in revised form 16 July 2021; Accepted 17 July 2021
Available online 18 July 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 D. Liu et al.
Fig. 1. The schematic diagram of the formation of metal ions doped RF aerogel and its transformation to HE-REZ ceramic aerogel powders.
stability at a working temperature of above 1000 ◦ C should be prepared.
High-entropy ceramics (HECs) are single-phase solid solution such as
carbides [14], oxides [15], borides [16], and other systems. These sys­
tems were demonstrated to have many excellent properties, including
low thermal conductivity colossal dielectric constants, super ionic con­
ductivity and enhanced mechanical properties, which open up new
possibilities to improve the performance of established ceramic systems.
Resently, researchers have found that the high-entropy rare earth zirc­
onate ceramics (HE-REZs) have been widely explored because of their
super mechanical properties, excellent high-temperature stability,
improved chemical stability, oxidation resistance, lower thermal con­
ductivity and other excellent characteristics, which showed potential
applications in high-temperature insulation environments [17–19].
Zhang et al. [20] prepared (La0.2Nd0.2Sm0.2Eu0.2Gd0.2)2Zr2O7
HE-REZ powders through a ball milling method combining a
high-temperature solid-phase reaction method. Obviously, the
as-prepared coatings demonstrated improved durability during thermal
cycling test at 1100 ◦ C in air, and its lifetime was 53 times, compared to
the lifetime with 10 times for the LZ system. However, the solid-phase
reaction process required a very high sintering temperature. Wang
et al. [21] fabricated (Sm0.2Eu0.2Tb0.2Dy0.2Lu0.2)2Zr2O7 HE-REZ pow­
ders which exhibited ultralow thermal conductivity (0.75 W/(m⋅K)) at
high temperature. Zhang et al. [22] synthesised pyrochlore HE-REZ
powders using as coating materials for thermal barriers and the ther­
mal conductivity was below 1 W/(m⋅K) in the temperature range of
300–1200 ◦ C. However, the average grain sizes are in a micrometer scale
(4.0 μm). Zhou et al. [23] produced (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2Zr2O7
high-entropy ceramic with low thermal conductivity (0.76 W/(m⋅K)) at
room temperature, which also exhibits slow grain growth rate.
Based on the previous study [24], the final microstructure and me­
chanical properties strongly depend on the particle size. Small grain size
generally result in fine grain size and enhanced mechanical properties.
When the size of HE-REZs decreased to a nanometer level, the increasing
grain boundaries between particles will enhance the phonon scattering
effect and reduce the thermal conductivity [25,26]. Compared with rare
earth oxides, the decomposition of rare earth nitrates and the rear­
rangement of atoms occur simultaneously at high temperature. Conse­
quently, the required activation energy will reduce and reactions can be
easily carried out. However, the HE-REZs prepared with currently
available technologies have many problems such as high preparation
temperature and pressure, tedious process, large material size and poor
mechanical properties, etc. The combination can form a new type of
material with potential applications in the field of high-temperature
insulation. However, rare earth materials for the preparation of
HE-REZ ceramic aerogels are usually nitrates or chlorides and the
formed structure is prone to collapse; as such, the development of
HE-REZ ceramic aerogel materials is limited.
In this study, we aim to synthesize the HE-REZ ((Sm0.2Eu0.2Tb0.2
Dy0.2Lu0.2)2Zr2O7) nanopowders with special 3-D porous structures.
Therefore, a novel HE-REZ ceramic aerogel with good thermal insu­
lation property was prepared and characterised through the sol-gel
template method and high-temperature calcination followed by 3-D-
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Ceramics International 47 (2021) 29960–29968
structure reconstruction. Since the highly difference of ion radius can
enhance the high mixing configuration and lattice distortion. The
criteria for selecting the five rare earth elements are based on the dif­
ference of ion radius and types of crystal structure. The HE-REZ ceramic
with defective fluorite structures have plenty of oxygen vacancies and
the disordered distribution of rare earth elements will increase the
configuration entropy, causing lattice distortion, which would affect
both the mechanical and thermophysical properties [21]. The particle
size of the material prepared by this method is very small (30–50 nm).
The micro-structural, thermal and mechanical properties of HE-REZ
ceramic aerogel were studied. This work was performed to develop a
new preparation method and materials aims to using in the field of
high-temperature thermal insulators applications.
2. Experimental procedures
2.1. Materials
Commercially available thermoplastic phenolic resin (RF; 3520f,
99.9%, Shandong Shengquan Chem Co., Ltd., China), urotropine (AR,
99.0%, Guangdong Xilong Chem Co., Ltd., China) and anhydrous
ethanol (AR, Tianjin Fuchen Chem Co., Ltd., China) were used as a
sacrifice template, a curing agent and a solvent, respectively. Sm
(NO3)3⋅6H2O, Eu(NO3)3⋅6H2O, Tb(NO3)3⋅6H2O, Dy(NO3)3⋅6H2O, Lu
(NO3)3⋅6H2O (AR, > 99.9%, Shanghai Macklin Biochemical Co., Ltd.,
China) and Zr(CH3COO)4 (Zr, 15.0%–16.0%, Shanghai Aladdin
Biochemical Co., Ltd., China) were used as raw materials.
2.2. Preparation of the samples
The fabrication of metal ion-doped RF aerogel and its transformation
to HE-REZ ceramic aerogel powders were illustrated in Fig. 1. For
example, the (Sm0.2Eu0.2Tb0.2Dy0.2Lu0.2)2Zr2O7 (5RE2Zr2O7) sample
was fabricated as follows. Firstly, 0.5 g of RF was dissolved in 15 mL of
ethanol and magnetically stirred at room temperature for 1 h to obtain a
clear phenolic solution (RF sol). Afterwards, 7.5 mL of 0.4 mmol zir­
conium acetate and 0.9 g of urotropine were added and magnetically
stirred for another 1 h. Five rare earth nitrates with an equal molar
amount (0.4 mmol) were sequentially added to the RF solution while
continuous stirring for 6 h. A homogeneous mixture solution (M/RF sol)
was then introduced to a stainless steel Teflon lined autoclave, kept at
80 ◦ C for 48 h and naturally cooled to room temperature. The obtained
wet gel (M/RF gel) was placed in ethanol for solvent exchange and
aging. Then the ethanol was replaced every 6 h for 4 times. Subse­
quently, the RF aerogel doped with rare earth and zirconium salts (M/RF
aerogel) was prepared via an ethanol supercritical drying process (SCD).
Lastly, HE-REZ ceramic aerogel powder was obtained after placing the
aerogel in a corundum crucible and calcined in a muffle furnace at
900 ◦ C-1300 ◦ C in air for 2 h (2 ◦ C/min). For comparison, Sm2Zr2O7
(RE2Zr2O7) and (Sm1/3Eu1/3Lu1/3)2Zr2O7 (3RE2Zr2O7) were also pre­
pared. To facilitate the presentation, the 5RE2Zr2O7 samples calcined at
900, 1100 and 1300 ◦ C were named samples 1, 2 and 3, respectively.
D. Liu et al.
Fig. 2. Structure schematic of pyrochlore and defective fluorite: (a) 1/8 of unit cell of pyrochlore structure; (b) defective fluorite structure.
The as-synthesised powders were manually ground with an agate
mortar with 5% PVA (AR, 99.99%, Shanghai Aladdin Biochemical Co.,
Ltd.) solution as adhesives and then dried in an oven for 4 h in air to
obtain HE-REZ ceramic aerogel bulks. Afterwards, the pelleted fine
powders were pressed into cylindrical pellets (Φ = 18 mm × 4 mm) at a
uniaxial pressure of 20 MPa for 1 min and cold isostatic pressed at 50
MPa for 2 min. They were then calcined at 600 ◦ C for 5 h to burn out the
PVA binders and at 1200 ◦ C for 2 h in air for densification.
2.3. Materials characterization
A field emission scanning electron microscope (FE-SEM, Hitachi,
SU8010, Japan) with dispersive spectrometry (EDS) was applied to
observe microstructural and elemental distributions. Transmission
electron microscopy (TEM, JEOL 2010 F, Japan) with selected-area
electron diffraction (SAED) was conducted to analyse the morpholog­
ical characteristics and crystalline structure of the obtained samples. X-
Scheme 1. (a) The thermal decomposition equation of urotropin; (b) Illustration of the coordination mechanism between metal ions and phenolic resin.
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Ceramics International 47 (2021) 29960–29968
ray diffraction (XRD) measurement was performed using a diffractom­
eter (XRD diffractometer Bruker AXS D8, Germany) with Cu Kα radia­
tion (λ = 1.54 Å) in a 2θ range of 10◦ –80◦ with a scanning rate of 10◦ /
min. Thermogravimetric analysis (TGA) and differential scanning calo­
rimetry (DSC) were performed using a thermogravimetric analyser
(NETZSCH STA 449F3, Germany). The samples were heated to 1400 ◦ C
at a rate of 5 ◦ C/min in a flowing air atmosphere. The Raman spectra of
the powder were obtained on a microscopic confocal Raman spec­
trometer (Renishaw, RM2000, UK) by using an argon ion laser with
radiation at 532 nm.
2.4. Measurements of thermal and mechanical properties
Thermal conductivity measurements were conducted at 25 ◦ C by
using a thermal conductivity instrument (DRE-III, Xiangtan Xiangyi In­
strument Co., Ltd., Xiangtan, China). The standard sample used for in­
strument calibration is SiO2 aerogel (λ = 0.028 W/(m⋅K); Φ = 50 mm).
D. Liu et al. Ceramics International 47 (2021) 29960–29968

Fig. 3. (a) SEM; (b) X-ray diffraction pattern; (c) TEM; (d) HTEM image and (e) EDS mapping of the as-prepared powders (Sample 2).

The as-prepared samples were machined into 50 mm with paralleled
upper and lower surfaces. The compressive strength of the sample with
the dimensions of 5 × 5 × 20 mm was measured using a tester (Zwick
Z050, Zwick, Germany) with a crosshead velocity of 0.5 mm min− 1. The
high-temperature insulation performance measurements of the samples
(Φ = 40 mm) were carried out with a single-side heating device, which
contained an upper part for a heating area and a lower part for a tem­
perature monitor area. During the experiment, the front surface of the
sample was exposed to the heating area, and the temperature of the back
surface was measured.
3. Results and discussion
The crystal structures of pyrochlore and defective fluorite structures
are depicted in Fig. 2. An ideal pyrochlore structure (Fig. 2a) belongs to
the space group Fd3m (Z = 8), where the five rare earth elements are
distributed randomly and equally at the 16c site, and the Zr atoms
equally and homogeneously occupy the 16d site. Oxygen occupies the
8b and 48f sites, while the oxygen vacancy occupies the 8a site [27,28].
The defective fluorite structure exhibits the space group of Fm3m (Z =
1), as shown in Fig. 2 (b) and the arrangement of the cations and the
distribution of oxygen vacancies become disordered: the five rare earth
elements and the Zr atoms are equally occupy the 4a site randomly.
However, the oxygen vacancies present randomly distributions at the 8b
site that occupies 1/8 of the whole sites, which is a typical feature of the
defective fluorite structure [29].
The coordination bonding mechanisms between metal ions and RF
were depicted in Scheme 1. In Scheme 1 (a), as temperature increases,
urotropine, served as a curing agent, can produce HCHO and the pro­
duced HCHO reacts with ortho- and para-active sites on RF. As the

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Fig. 4. The results of (a)TG-DSC curves of the Sample 2 and (b) Raman spectrum.

reaction continues, as shown in Scheme 1 (b), the rare earth ions (RE3+)
and Zr4+ can simultaneously connect to the phenolic or alcohol hydroxyl
groups on RF through coordination reactions, which stabilized the
growth of inorganic metal sources and avoided phase separation [30].
Therefore, the RF aerogel doped with metal ions can be formed.
The SEM and TEM images of the calcined HE-REZ ceramic aerogel
(5RE2Zr2O7) powders were shown in Fig. 3 (a,c). The samples have a
good microstructural integrity with a typical “pearl chain” microstruc­
ture, which presented a 3-D porous network skeleton with numerous
nanoscale particles and nanopores. The nanoscale particles were uni­
formly distribute in the whole field of vision with an average particle
size of 30–40 nm. The nanopores depicted open and close pore
structures with an average size of approximately 30–40 nm. The XRD
(5◦ /min) patterns (Fig. 3 (b)) for three samples showed that the
diffraction peaks can be indexed to (111), (200), (220), (311), (222) and
(400) planes. No characteristic reflections of impurities were detected in
the patterns, demonstrating the formation of a single-phase defective
fluorite structure. The weak peaks at approximately 15◦ , 28◦ , 45◦ and
52◦ for sample Sm2Zr2O7 and Eu2Zr2O7 can ascribed to the characteristic
superlattice diffraction peaks of pyrochlore structure. What’s more,
based on the Scherrer equation (D = Κλ/(β cos θ)), the crystallite size
was calculated to be about 22 nm.
High-resolution transmission electron microscopy (HRTEM) was
performed to further verify the information on the structure (Fig. 3 (d)).

Fig. 5. The structural evolution and corresponding phase characterization: SEM images of (a) Sample 1, (b) Sample 2, (c) Sample 3; (d) Corresponding X-ray
diffraction patterns.

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D. Liu et al.
Fig. 6. The nitrogen adsorption-desorption isotherms and corresponding pore size distributions of (a) Sample 1, (b) Sample 2, (c) Sample 3.
The observed interplanar distances of 0.26 and 0.30 nm were corre­
sponded to the (200) and (111) planes, respectively. Moreover, the
average crystallite size computed through the HRTEM was approxi­
mately 25 nm, which is approach with the crystallite size calculated
from the XRD patterns. As shown in Fig. 3 (e), the as-synthesised pow­
ders were further examined through EDS mapping to investigate the
element distribution homogeneity on the nanoscale. Since the rare earth
elements represented by different colors present same tendency or di­
rection in the whole view of EDS mappings. All the elements contained
were uniformly distributed without any segregation.
The TGA curves (Fig. 4 (a)) showed a slight weight loss (approxi­
mately 1.34%) in a wide temperature range of 50 ◦ C-1080 ◦ C, which can
be ascribed to the evaporation of absorbed and bound water in the
samples. As for the DSC curve, no significant endothermic or exothermic
peaks formed, indicating that the defective fluorite structure phase can
stabilise up to 1400 ◦ C. Moreover, the weak change between 1200 ◦ C
and 1350 ◦ C may be a result of the grain growth of the particles.
The Raman spectra of the samples were presented in Fig. 4 (b). The
pyrochlore structure usually consists of six Raman active vibration
modes as follows:
Γ (Raman) = А1g + Eg + 4F2g
For an ideal pyrochlore structure, the six vibration modes are asso­
ciated with an oxygen cation, including one mode (F2g) related to the
oxygen cation at the 8a site and five modes (A1g + Eg+3F2g) assigned to
Ceramics International 47 (2021) 29960–29968
the oxygen cation at the 48ƒ site, where Eg is derived from the O–RE–O
bending vibrations [31,32]. As for the ideal fluorite structure, only one
vibration mode (F2g) is observed in the oxygen cation at the 8c site.
Sm2Zr2O7 (RE2Zr2O7) presented four typical vibration modes in the
range of 200–800 cm− 1 without other vibration modes, indicating a
pyrochlore structure. However, 3RE2Zr2O7 performed a broad and weak
Raman peak with a defective fluorite structure and only one vibration
mode (F2g) was observed in sample 5RE2Zr2O7. This finding can be
attributed to the distribution of disordered oxygen vacancies and
disordered structures from a high-entropy effect [33,34].
Fig. 5 showed the microstructures and the corresponding XRD pat­
terns of the 5RE2Zr2O7 powders calcined at different temperatures. At
900 ◦ C (Fig. 5 (a)), the microstructure demonstrated a 3-D porous
network skeleton with numerous nanoscale particles and nanopores,
and the average sizes of particles and pores were 40 and 30 nm,
respectively. When the calcination temperature reached 1100 ◦ C (Fig. 5
(b)), the particles enlarged, and the size of the pores decreased. Never­
theless, the particles and pores still have a nanoscale size of 45 and 20
nm, respectively. As the calcination temperature increased to 1300 ◦ C
(Fig. 5 (c)), the particles grow further, and many of them (about
300–450 nm) seemed closely combined. However, the pores still remain
(1)
even though most of the holes disappear. Overall, the aerogel shrinks,
and the interconnected assembly forms a relatively dense structure. The
corresponding XRD patterns of the 5RE2Zr2O7 powders calcined at
different temperatures were shown in Fig. 5 (d). Obviously, the three
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Fig. 7. Photograph (a) and microstructure of the representative sample of 5RE2Zr2O7 ceramic aerogel bulks with different magnification (b), (c).

Fig. 8. Comparison of (a) room temperature thermal conductivity and (b) compressive strength of the samples calcined at different temperature.

samples presented a single-phase defective fluorite structure without

Table 1
other phases. However, the diffraction peak positions slightly shifted
Thermal conductivity (λ) comparison of porous HECs.
toward a lower diffraction angle as the calcined temperatures increase.
This strange phenomenon can be explained with the following theory. Materials λ (W/(m⋅K)) Reference
As the calcination temperature increases, the lattice constant (inter­ (Hf1/3Ta1/3Nb1/3)C 0.089 [36]
planar spacing) will increase with the expanding of crystal structure foam 0.057 [37]
Y2SiO5 0.050 [38]
[28]. Therefore, according to the Bragg crystal diffraction equation
γ-(Y0.8Ho0.2)2Si2O7 0.077 [39]
(Equation (2)), the diffraction angle will decrease (toward a lower SiC–SiO2 0.066 [40]
angle) and the diffraction peak position shifts to the left: 5RE2Zr2O7 0.031 This work

nλ
2d sin θ = nλ→2θ = arc sin (2)
d
Table 2
where 2θ, d, n and λ are the diffraction angle, interplanar spacing of the Thermal conductivity (λ) comparison of aerogels.
crystal, reflection series and wavelength of the X-ray, respectively. Materials λ (W/(m⋅K)) Reference
Fig. 6 showed the N2 adsorption–desorption isotherms and Barrett-
Al2O3–ZrO2 0.032 [41]
Joyner-Halenda (BJH) pore size distribution analysis of the 5RE2Zr2O7
Al2O3–SiO2 0.023 [12]
powders calcined at different temperatures. The results demonstrated PVDF 0.036 [42]
that all the samples appear to be a typical type IV adsorption isotherm ZrO2–SiO2 0.031 [13]
with an H3-type hysteresis loop in accordance with the IUPAC classifi­ SiO2 0.023 [43]
cation. Hence, they showed the characteristic of a mesoporous structures 5RE2Zr2O7 0.031 This work

[35]. The BET specific surface areas were calculated to be 443.26,

280.15 and 80.37 m2/g for samples 1, 2 and 3, respectively. In addition,
the pore size distribution curves calculated by a Bar­
rett–Joyner–Halenda (BJH) method were shown in the corresponding
inset images. Obviously, the samples exhibited mesopore and macropore
size regions (2–48 nm) with a small average pore width and a high pore
volume. The BET specific surface area of the samples decreased because
the grains further grow. Simultaneous, the pore size of the samples
decreased as the calcination temperature increases.
Fig. 7 (a) showed the photograph of the 5RE2Zr2O7 ceramic aerogel
bulks reconstructed under a uniaxial pressure of 50 MPa, which shows
an intact overall structure. Fig. 7 (b) showed the surface morphology
with low magnification which demonstrated a uniform, regular and
dense morphology. The magnified surface morphology (Fig. 7 (c))
showed that the sample still performs a 3-D porous network skeleton
without any structural destruction.
The room temperature thermal conductivity of the samples were
shown in Fig. 8 (a). Clearly, the sample 5RE2Zr2O7 calcined at 900 ◦ C
performed the lowest thermal conductivity of 0.031 W/(m⋅K) among all
the samples. This was mainly attributed to the unique 3-D

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D. Liu et al.
Fig. 9. The back surface temperature testing for (a) photograph of equipment and (b) curves of the samples calcined at 900 ◦ C (the loading temperature is 1200 ◦ C).
interconnected porous structures, and the ceramics grains were not
continuous that can block the heat conducting pathways. Further, the
thermal conductivity increased as the calcination temperature increases.
The thermal conductivity comparison of porous HECs and aerogels are
outlined in Table 1 and Table 2, respectively. In accordance with the
results of Fig. 5, the growth of nanocrystals increased the particle size
and decreased the porosity with the increasing of calcination
temperature.
It has been proven that the pores play an vital role on the overall
thermal conductivity of the porous ceramics [44]. Based on the “Effec­
tive Medium Percolation Theory” (EMPT) [45], the effective thermal
conductivity can be calculated as follows:
1 {[ ] [ ]2
λeff = λp (3υp − 1) + λs (3υs − 1) + ( λp (3υp − 1) + λs (3υs − 1) + 8λp λs
4
(3)
where λs and λp are the thermal conductivity for the solid matrix and the
pores, respectively; υs and υp are the corresponding volume fractions; λeff
is the effective thermal conductivity. From equation (3), we can
conclude that the high porosity can greatly reduce the effective thermal
conductivity. What’s more, the thermal conductivity decreases with the
increasing of rare earth atomic species in zirconates. It has proven that
the more rare earth element added, the more disordered the defective
fluorite structure will be [46,47]. The intense complex crystal structure
and the increasing compositional disorder result in mass difference,
charge disorder and chemical bonding vibration; consequently, the
phonon scattering effect enhances, and therefore the thermal conduc­
tivity decreases [15].
The mechanical properties of porous ceramics were significantly
affected by the microstructure, porosity, pore structure, and morphology
of the grains. The relationship of the sintering temperature and
compressive strength of the as-prepared samples were depicted in Fig. 8
(b). It can be clearly seen that the compressive strength parameters of all
the testing samples increased with the increasing of calcined tempera­
ture. According to Griffith theory [48], pores are the main source of
cracks in porous ceramics. Pores not only decrease the load area, but also
weaken the load capability because the stress concentrates on the sur­
rounding region of pores. Combining with the results of Fig. 5, the in­
crease of compressive strength parameters can be ascribed to the
decrease in the porosity of the samples. Therefore, the interconnected
particles and growth grain will significantly enhance the interaction
force between the particles [49]. Besides, the compressive strength pa­
rameters were slight increase with the increasing number of rare earth
element due to the high-entropy effect.
The back surface temperature testing was conducted to evaluate the
high-temperature insulation performance of the samples by using the
single-side heating device (Fig. 9 (a)) containing an upper part for a
Ceramics International 47 (2021) 29960–29968
heating area and a lower part for a temperature-monitoring area. In
Fig. 9 (b), the back surface temperatures of the samples increased as the
high temperature loading time increased until 250 s. As the high tem­
perature loading time was extended, the back surface temperatures of
5RE2Zr2O7, 3RE2Zr2O7 and Sm2Zr2O7 remained steady at approximately
232 ◦ C, 248 ◦ C and 270 ◦ C, respectively. The results indicated that the
samples performed an ideal high-temperature insulation performance.
Combining the results of Fig. 8a, 5RE2Zr2O7 presented a superior heat-
shielding performance because of the 3-D porous network skeleton
and the high-entropy effect, which significantly blocked the heat flow
transfer into materials.
4. Conclusions
)1/2 }
In this study, a novel HE-REZ ceramic aerogel was successfully
fabricated through a sol-gel template method and high-temperature
calcination followed by 3D-structure reconstruction. The as-prepared
HE-REZ ceramic aerogels exhibited an ultra-low room-temperature
thermal conductivity of 0.029–0.043 W/(m⋅K) and a relatively high
specific surface area of 80.37–443.26 m2/g. The effects of different
calcination temperatures on the microstructure and thermal stability of
the as-prepared samples were investigated. Moreover, the as-prepared
samples presented an ideal high-temperature insulation performance.
Thus, a new way was proposed for the efficient fabrication of HE-REZ
ceramic aerogel that could be used in the fields of high-temperature
insulators for hypersonic vehicles.
Declaration of competing interest
We declare that we have no financial and personal relationships with
other people or organizations that can inappropriately influence our
work, there is no professional or other personal interest of any nature or
kind in any product, service and company that could be construed as
influencing the position presented in,or the review of,the manuscript
entitled.
Acknowledgements
This work is supported by the Beijing Institute of Technology
Research Fund Program for Young Scholars, National Science and
Technology Major Project (2017-VI-0020-0093) and National Natural
Science Foundation of China (Nos.12090031 and 11602125).
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