Journal of the European Ceramic Society 41 (2021) 5495–5504

Contents lists available at ScienceDirect

Journal of the European Ceramic Society

journal homepage: www.elsevier.com/locate/jeurceramsoc

Preparation of broadband transparent Si3N4-SiO2 ceramics by digital light

processing (DLP) 3D printing technology
Rufei Chen a, b, Wenyan Duan a, *, Gong Wang a, *, Bingshan Liu a, Yantong Zhao a, b, Shan Li a
a
Key Laboratory of Space Manufacturing Technology (SMT), Technology and Engineering Centre of Space Utilization, Chinese Academy of Sciences, Beijing 100094, PR
China
b
University of Chinese Academy of Sciences, Beijing 100049, PR China

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

Keywords: Wave-transmitting materials are a kind of multi-functional materials that protect the normal operation of
Broadband transparent material communication and guidance systems of spacecraft in harsh environments. In this paper, we fabricate a
Si3N4-SiO2 broadband microwave transparent Si3N4-SiO2 composite ceramic with excellent performance through digital
3D printing
light processing (DLP) 3D printing technology. The influences of sintering temperature on the weight increase
Photocuring
rate, density, dimensional shrinkage, phase composition, microstructure, bending strength and dielectric prop­
erties of Si3N4-SiO2 ceramic were all systematically studied. The strength of Si3N4-SiO2 ceramic sintered at 1350
℃ was 77 ± 5 MPa. The relative permittivity of the ceramic is within the range of less than 4, and the loss
tangent can be below 0.003. The 3D printed Si3N4-SiO2 ceramic material exhibited excellent wave-transparent
performance.

1. Introduction
Wave-transmitting materials are an important part of missiles,
aircraft radomes and antenna window panels. Nitride ceramics (Si3N4,
BN, SiBN, etc.) have excellent thermal stability, thermal shock resis­
tance, low dielectric constants and low dielectric loss. They still have
good thermophysical properties and stability of dielectric properties in a
wide temperature range. Si3N4 has high mechanical strength and
excellent rain corrosion resistance [1–4]. However, the relative dielec­
tric constant of Si3N4 ceramics is relatively high (ε = 7.9, tanδ = 0.0080,
10 GHz, 25 ℃), resulting in a small tolerance on the thickness of the
radome. This brings many difficulties in processing [5–7]. There are two
main methods to reduce the dielectric properties of silicon nitride ce­
ramics: (1) preparation of porous silicon nitride ceramics and (2) syn­
thesis of Si2N2O composite materials [8–13]. However, it is difficult to
prepare a porous structure and the mechanical strength of the product is
also low [14–16]. So preparation of Si2N2O composite materials is the
selected choice.
The traditional ceramic molding process requires complex molds. It
is difficult to manufacture complicated components, which massively
increases fabricating costs and production times [17,18]. Additive
manufacturing (AM) technology provides a more efficient way to
produce ceramic parts which can shorten the production cycle [19,20].
Digital light processing (DLP) 3D printing technology is a relatively
mature AM technology, which can project and integrate the entire layer
during printing, so the printing speed is faster and the molding accuracy
is higher. DLP takes ceramic slurry as the raw materials in the manu­
facture of ceramic products. The ceramic slurry is prepared by mixing
ceramic powder, photosensitive resin, initiator and so on. The ceramic
particles are bonded into ceramic bodies with complex shapes after
exposure to a specific wavelength ultraviolet light for a few seconds
[21–24].
The refractive index difference between the Si3N4 powder and the
resin is large, so the main problem is that the curing depth of the slurry is
too low for fabricating Si3N4 ceramic via DLP 3D printing [25]. Up until
now, some works have been focused on improving the curing depth of
pure Si3N4 ceramic slurry. For example, the amorphous SiO2 layer was
attached onto the surface of Si3N4 powder by surface oxidation. Another
process is by adding other oxides to the Si3N4 ceramic slurry, such as
Al2O3, which can increase its curing depth. However, very few works
have been reported on sintered Si3N4 ceramics successfully [26,27].
In this work, we are trying to get a 3D printed Si3N4-SiO2 ceramic,
which exhibits excellent mechanical properties and electromagnetic
properties. Ceramic slurry with 50 % solid content was prepared and

* Corresponding authors at: Key Laboratory of Space Manufacturing Technology (SMT), Chinese Academy of Sciences, Beijing, 100094, PR China.
E-mail addresses: duanwenyan03@yeah.net (W. Duan), wanggong@csu.ac.cn (G. Wang).

https://doi.org/10.1016/j.jeurceramsoc.2021.04.045
Received 23 January 2021; Received in revised form 13 April 2021; Accepted 23 April 2021
Available online 27 April 2021
0955-2219/© 2021 Published by Elsevier Ltd.
R. Chen et al.
Si3N4-resin composites were formed by DLP 3D printing technology for
the first time. Then, Si3N4-resin composites were debinded and sintered
at different temperatures, which can introduced SiO2 to get Si2N2O.
Finally, the microstructure, physical properties and dielectric properties
of printed ceramic materials were also studied and discussed. In this
study, both simple-shaped Si3N4-SiO2 ceramic testing bars and complex-
shaped Si3N4-SiO2 ceramic porous structures were prepared by using the
above-mentioned processing methods.
2. Experimental procedure
2.1. Materials
Silicon nitride ceramic paste in this research was made up of 90 wt%
Si3N4 and 10 wt% yttria-alumina (Y2O3-Al2O3). The yttria-alumina
system is the most widely used sintering aid system, which promotes
the liquid phase sintering of Si3N4 to achieve the densification of ce­
ramics. The particle size distribution of original Si3N4 powder is shown
in Fig. 1. The particle size, D50 of raw Si3N4 powder is 3.452 μm. The
SEM micrograph of raw Si3N4 powder is shown in Fig. 2. The dispersant
was a copolymer with acidic groups. The trimethylolpropane triacrylate
(TMPTA) was supplied by Zhongshan Qianyou Chemical Material Co.,
Ltd. TMPTA is an ultraviolet curable acrylate resin with high photo­
polymerization activity and high printing accuracy, which is very suit­
able for DLP printing of materials. The photoinitiator, Irgacure 819, was
purchased from Aladdin.
2.2. Fabrication
Before digital light processing 3D printing, a high solid loading and
highly dispersed Si3N4 slurry should be obtained. Micron-sized Si3N4
particles, TMPTA resin monomers, Y2O3-Al2O3 sintering additives and
dispersants (5 wt% relative to the total powder mass) were weighted and
ball milled for 5 h in a planetary mill. Photoinitiator (1 wt% relative to
the total resin weight) was added to the slurry, and ball milled for 1 h.
Finally, a uniformly dispersed Si3N4 slurry with a solid content of 50 vol
% was obtained. Si3N4 ceramic bodies were fabricated by using the
above-mentioned processing methods. Detailed fabrication procedure is
presented in Fig. 3.
(1) First, a CAD model was designed in the computer and imported
into the digital light processing 3D printer (Quickdemos Intelli­
gent Manuf Acturing High-tech Co., Ltd, China). Then, according
to the light curing ability of the paste, we adjusted the exposure
time and light intensity. The photosensitive groups were cross-
linked to produce a polymer network under ultraviolet light.
Three-dimensional parts were obtained layer by layer in a similar
way.
Fig. 1. Particle size distribution of raw Si3N4 powder.
5496
Journal of the European Ceramic Society 41 (2021) 5495–5504
Fig. 2. SEM micrograph of raw Si3N4 powder.
(2) After printing, the ceramic green body was put in a muffle furnace
(LT, Nabertherm, Germany) for sintering to remove the photo­
sensitive resin. The debinding process of green bodies is shown in
Fig. 4 (a). The printed green bodies were first heated at a constant
rate of 0.5 ℃/min from room temperature to 600 ℃, then heated
up to 800 ℃ with 1.5 ℃/min heating rate and then held at 800 ℃
for 1 h.
(3) Finally, Si3N4-SiO2 ceramic was sintered in an O2 atmosphere by
using a tube-furnace (GSL-1700X, HF-Kejing, China). The sin­
tering process of green bodies is shown in Fig. 4 (b). The con­
version process of the polymer to ceramic is carried out in the
tube furnace with an oxygen atmosphere. In order to explore the
influence of temperature on the microstructure and properties of
ceramics, the green bodies were sintered at different tempera­
tures with the same heating rate and cooling rate. The samples
were designated as S-1250, S-1300, S-1350, and S-1400, respec­
tively, corresponding to the sintering temperature of 1250 ℃,
1300 ℃, 1350 ℃, and 1400 ℃. Fig. 5 presents the images of Si3N4
ceramic cuboid structure and the pyrolyzed body. There were no
cracks observed on the ceramic surface.
2.3. Characterizations
The density and porosity of Si3N4-SiO2 ceramics were measured by
Archimedes method. The porosity test were performed on the mercury
porosimeter (AutoPore V9600, USA). Fourier transform infrared spec­
troscopy (FTIR) measurements were performed on a Bruker Tensor-27
spectrometer at room temperature. The fracture surfaces of the prin­
ted samples were observed by using a scanning electron microscope
R. Chen et al.
Fig. 3. Flow diagram of Si3N4-SiO2 ceramic.
Fig. 4. Debinding and sintering of green bodies: (a) debinding, (b)sintering (For interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article).
(SEM, Hitachi S-8020) with an accelerating voltage of 5 kV, and trans­
mission electron microscopy (TEM, JEM-1200 F). Powder X-ray
diffraction (PXRD) measurements were performed on the Rigaku D/max
2500 powder X-ray diffractometer (Japan) with Cu-Kα radiation (λ =
1.5418 Å) in the reflection mode. The bending test in the three-point
bending configuration was carried out on the Instron 5965 universal
testing machine (INSTRON Co., Ltd, Norwood, MA, USA). Five samples
of each material were broken in bending. The real permittivity and loss
tangent of the sample with a size of 22.86 × 10.16 × 3 mm3 and 15.799
× 7.899 × 3 mm3 were measured in the frequency range of 8.2–12.4
GHz and 12.4–18 GHz on a vector network analyzer (VNA, MS4644A;
Japan).
5497
Journal of the European Ceramic Society 41 (2021) 5495–5504
3. Results and discussion
3.1. Cure depth of Si3N4 suspension
To evaluate the effect of sintering aids on the photocuring ability of
silicon nitride ceramic paste, the cure depth of Si3N4 and Si3N4-Y2O3-
Al2O3 were compared. The Cure depth of Si3N4 and Si3N4-Y2O3-Al2O3
suspension was exposed to ultraviolet light under the conditions as
shown in Fig. 6. The cure depth of each sample increased with incre­
mental increases of exposure energy. Under different light intensity, the
highest curing depth of Si3N4 slurry is 50 μm, and the lowest is 30 μm.
The highest curing depth of Si3N4-Y2O3-Al2O3 slurry is only 60 μm and
the lowest is 50 μm. It shows thus that the cure depth of the suspension
after adding Y2O3-Al2O3 is higher than the cure depth of the pure silicon
nitride slurry. Therefore, it can be proved that the addition of the Y2O3-
Al2O3 significantly enhances the photocuring ability of the Si3N4
ceramic slurry.
R. Chen et al. Journal of the European Ceramic Society 41 (2021) 5495–5504

Fig. 5. DLP printing of the ceramic cuboid (a) CAD model, (b) pyrolyzed body.

15.7 % and 1.76 g/cm3 respectively. The size of shrinkage as a per­

centage also reached its maximum: the X axis shrinkage rate of the
sample was 3.8 %, the Y axis was 2.9 % and the Z axis was 0.64 %. The
reason for the weight gain of ceramics was the reaction between Si3N4
and O2 during the sintering process. This is shown in reaction (1) [28,
29]:
Si3 N4(s) + 3O2 (g)→3SiO2 (s) + 2N2 (g) (1)

The specific values of porosity are shown in the Table 3. The open
porosity is measured by Archimedes drainage method. The open
porosity of sample S-1350 is the smallest. It shows that ceramics are the
densest at this temperature.
As the sintering temperature increases, the pore diameter decreases,
which means that the ceramic becomes densified. For ceramics sintered
at 1350 ◦ C, shows pores with pore diameter less than 100 nm (Fig.7) and
the open porosity rate is 18.27 %. This value is also consistent with the
value calculated by the Archimedes drainage method.

Fig. 6. Curing depth of suspensions with Si3N4 and Si3N4-Y2O3-Al2O3.

3.2. Physical properties of Si3N4-SiO2 ceramics
The weight loss rate after degreasing, weight gain rate, linear
shrinkage rate, material density and open porosity of the printed Si3N4-
SiO2 ceramics pyrolyzed at different temperatures were measured are
shown in Table 1. There was no change in the size of the ceramics during
the debinding process. For the sample pyrolyzed at 1250 ℃, the weight
gain rate and the linear shrinkage (x/y/z) were about 6.4 % and 3.2/
2.2/1.3 %, respectively. With the increase in sintering temperature
(1350 ℃), the weight gain rate and density all increased by going up to
3.3. Microstructure
The chemical structures of acrylate monomer, ceramic paste before
and after UV curing and sintered at different temperatures were char­
acterized by FTIR. As shown in Fig. 8 (a), in the spectrum of the blending
before curing, the peaks at 2963, 2870, 1722 cm− 1 can be attributed to
the acrylate groups, indicating that photoactive moieties have been
introduced into the blend system. After curing, the peaks of acrylic
groups became weaker, indicating a photopolymerization reaction

Table 1
Physical properties of Si3N4-SiO2 ceramics as a function of sintering
temperature.
Sample Temperature Weight loss Weight Linear Density
(℃) rate after gain rate shrinkage (g/cm3)
degreasing after (％)
(％) sintering
(％)

S-1250 1250 29.5 6.4 3.2/2.2/ 1.60

1.3
S-1300 1300 29.5 9.0 2.0/1.6/ 1.56
0.32
S-1350 1350 29.5 15.7 3.8/2.9/ 1.76
0.64
S-1400 1400 29.5 15.1 3.6/2.5/ 1.72
1.6
Fig. 7. Pore size distribution curves of Si3N4-SiO2 ceramics.

5498
R. Chen et al.
Fig. 8. (a)FTIR spectra of the arcylate monomer, blending before and after UV curing, (b)FTIR spectra of the ceramic after pyrolyzed at different temperatures.
between acrylic groups and ceramic paste after UV irradiation. The peak
at 1087 cm-1 can be assigned to Si-O-Si. With the increase in sintering
temperature, the peak value becomes stronger and it reaches the tallest
peak at 1350 ℃, confirming that more Si-O-Si groups are formed, as
shown in Fig. 8 (b). The absorption peak at 912 cm− 1 corresponded to a
stretching vibration of Si-N and the peak value became weaker as the
temperature rises. It meant that the content of silicon nitride in ceramic
parts becomes reduced [30].
XRD was used to investigate the crystallization behavior of the
ceramic samples, and the spectra are shown in Fig. 9. After sintered at
1250 ℃, the diffraction peak appears at 2θ = 22◦ , which was consistent
with the first characteristic peak (110) of tridymite. Broad diff ;raction
humps were observed at 2θ = 31.5◦ , 33◦ , which indicated the amor­
phous SiO2 is formed at the same time. With an increase in temperature,
the characteristic peak of Si3N4 gradually weaken, suggesting that more
Si3N4 reacts to form SiO2. Meanwhile, when the temperature rises from
1350 ◦ C to 1400 ◦ C, the crystalline peaks at 2θ of 26◦ decreased, sug­
gesting that the content of SiO2 decreased. The reason for this change is
that when the temperature rises directly to 1400 ◦ C, the surface layer of
Si3N4 is quickly oxidized to SiO2, and a dense layer is formed on the
surface, which prevents oxygen from entering the inside of the sample.
Fig. 10 shows the SEM micrographs of samples sintered at different
temperatures. By controlling the heating rate and proper sample posi­
tioning in the heat treatment, the process can eliminate cracks, which
are caused by rapid heating. The fracture surface was not uniform,
Fig. 9. XRD patterns of Si3N4-SiO2 ceramics.
5499
Journal of the European Ceramic Society 41 (2021) 5495–5504
indicating a ductile fracture. With the increase of sintering temperature,
the gap between printed layers decreased gradually, suggesting good
interlayer bonding. Sample S-1200 and S-1300 (Fig. 10a-b) show many
pores in the section. As the temperature rised, the number of cracks
decreased (Fig. 10c-d). In a higher-magnification (Fig. 10e-h), it was
found that the particle size of Si3N4 in sample S-1300 was larger than
that in S-1250, meanwhile, the number of pores decreased. With the
temperature increasing to 1350 ℃ and 1400 ℃, the samples had perfect
fracture surfaces without cracks, contributing to the excellent mechan­
ical properties.
Transmission electron microscopy (TEM) was used to investigate the
microstructure of raw Si3N4 powder and sample S-1350 (Fig. 11). Si3N4
lattice fringes were clearly observed in the TEM image (Fig. 11a). As
shown in Fig. 11(b–c), the sample S-1350 showed worm-like features,
which was characteristic of amorphous materials. At the same time,
there are lattice fringes different from the Si3N4 crystal, indicating the
formation of cristobalite. Fig. 10a shows the surface morphology of
sample S-1350. The EDX spectrum of the sample S-1350 are shown in
Fig. 12(b–c). It could be seen that the O elements appeared in the sin­
tered particles, which suggested that SiO2 amorphous layer and cristo­
balite were formed after sintering.
Fig. 13 shows a schematic oxidation reaction process of Si3N4 at high
temperature. The largest amount of SiO2 is formed at 1350 ℃. However,
with the increase in the pyrolyzed temperature (from 1350 ℃ to 1400
℃), the amount of silicon oxide decreased. This may be attributed to the
R. Chen et al. Journal of the European Ceramic Society 41 (2021) 5495–5504

Fig. 10. SEM of fracture surface of Si3N4-SiO2 ceramics sintered at different temperatures, (a and e) S-1250, (b and f) S-1300, (c and g) S-1350 and (d and h) S-1400;
(e, f, g and h) at high magnifications (a, b, c and d).

5500
R. Chen et al. Journal of the European Ceramic Society 41 (2021) 5495–5504

Fig. 11. TEM images of (a) raw Si3N4 powder and (b-c) sample S-1350.

Fig. 12. The TEM images the EDX spectrum of the Si3N4-SiO2 ceramic particles. (a) The microstructure of the Si3N4-SiO2 ceramic particles; (b-c) The EDX spectrum
of the Si3N4-SiO2 ceramic particles.

rearrangement of the Si3N4-SiO2 ceramic microstructure. The mass ratio
of each phase after sintering was calculated according to reaction (1),
and is shown in Table 2.
3.4. Mechanical properties
The mechanical properties of S-1250, S-1300, S-1350 and S-1400
were measured by a three-point bending strength test. The results are
shown in Fig. 14. The bars were tested perpendicular to the x-y-plane in
mechanical tests. The results showed that the bending strength of the

5501
R. Chen et al. Journal of the European Ceramic Society 41 (2021) 5495–5504

Fig. 13. The schematic synthetic reaction process of oxidation of silicon nitride at high temperature.

Table 2
Mass ratio of each phase after sintering.
Sample Si3N4(%) SiO2(%) YAG (%)

S-1250 63.7% 26.9 % 9.4 %

S-1300 53.8% 37.0 % 9.2 %
S-1350 30.1% 61.3 % 8.6 %
S-1400 32.2% 59.1 % 8.7 %

Table 3
Porosity of each phase after sintering.
Sample Open porosity(%)

S-1250 44.0 %
S-1300 38.0 %
S-1350 17.7 %
S-1400 18.1%

Fig. 14. Bending strength of Si3N4-SiO2 ceramics sintered at different

samples varies from 19 to 77 MPa. With the increase in temperature, the temperatures.
flexural strength gradually increased. The bending strength of S-1350
reached the maximum value of 77 ± 5 MPa. As more and more Si3N4 was expressed by the following formula:
oxidized to SiO2, the density of the sample increased. However, the
( )2 /[( )2 ]
flexural strength of S-1400 decreased to 45 ± 5 MPa. The reason for this t20 = 1-r2 1 − r2 + 4r2 sin2 φ (3)
variation may be that the content of SiO2 had decreased.
Where φ is electrical thickness, r is interface reflection coefficient. The
3.5. Dielectric properties electrical thickness can be expressed as:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅/
φ = 2πh ε − sin2 θ λ0 (4)
The dielectric properties of Si3N4-SiO2 ceramics were measured at
8.2–18 GHz. Fig. 15 shows the real permittivity and the tangent loss of
the sample. The dielectric constant reflects the difficulty of dielectric Where h is theoretical structure thickness of the radome, ε is dielectric
polarization, and the tangent loss represents the signal attenuation when constant of the material, λ0 is wavelength of incident electromagnetic
the electromagnetic wave passes through the material [31]. wave and θ is the angle of incidence. The optimum wall thickness for­
The power transfer coefficient t0 and electrical thickness can be mula of the radome is:

5502
R. Chen et al. Journal of the European Ceramic Society 41 (2021) 5495–5504

Fig. 15. Dielectric constant of Si3N4-SiO2 ceramics, (a) The real permittivity, (b)The dielectric loss.

/ √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
average ε value of samples increased from 3.11 to 3.57. In the same
h = λ0 2 ε-sin2 θp (5)
waveband, the real permittivity reached a maximum at 1350 ℃ and the
minimum at 1250 ℃. The increase of ε value was related to the full
Where θp is the Brewster angle. It can be seen that a change of the
densification of the sample. Additionally, the tangent loss decreased
dielectric constant will lead to a change in wall thickness, resulting in
with the increase of temperature. Generally, lower tan δ means better
the imbalance of the radome electrical thickness and cause a decline in
transmission rate, which can reduce the attenuation of electromagnetic
transmittance. In addition, the permittivity also determines the wall
waves when transmitted in the material. In other words, S-1400 had the
thickness tolerance. This brings great difficulties in the processing of
lowest dielectric loss tangent, which indicated that it could be a po­
structural parts. As the loss tangent becomes larger, the energy is con­
tential transparent material.
verted into heat during the process of passing through the radome.
Therefore, in order to achieve the minimum reflection and maximum
transmission, the new high temperature wave transmission material 3.6. Complex-shaped Si3N4-SiO2 ceramic parts fabricated by DLP
must have low dielectric constant and loss tangent (ε < 4,tanδ < 0.01) to
obtain ideal transmission [32–36]. The complex-shaped ceramic green body could be fabricated via the
As the sintering temperature increased from 1250 ℃ to 1400 ℃, the DLP method and then sintered into ceramic parts. Fig. 16 (a) shows the

Fig. 16. (a) The Si3N4-SiO2 ceramic with lattice structure, micrograph images of three structures: (b) 21 %, (c) 40 %, (d) 59.2 %.

5503
R. Chen et al.
Si3N4-SiO2 ceramic parts after printing, degreasing and sintering. The
sintering temperature was 1350 ℃ and the porosity was 21 %, 40 % and
59.2 % respectively. The three lattice structures were observed by a
metallographic microscope, as shown in Fig. 16(b–d). At one magnifi­
cation of SEM, it can be seen that the distance between adjacent pores
becomes shorter with an increase in porosity. The results showed that
the complex shape Si3N4 ceramics was successfully prepared by
combining DLP method with high temperature treatment.
4. Conclusions
Complex ceramic structures were successfully prepared using DLP
three-dimensional printing technology. The influence of sintering tem­
perature on the physical properties, phase composition, microstructure,
bending strength and dielectric properties of ceramics were explored.
The sample composed of Si3N4, SiO2, and a small amount of yttria-
alumina. As the sintering temperature increased, the content of SiO2
first increases and then decreases, reaching 61.3 % at 1350 ℃. From
1250 ℃ to 1350 ℃, the density of ceramics increased from 1.60 g/cm3
to 1.76 g/cm3. Flexural strength of S-1350 reached 77 ± 5 MPa. In the
electromagnetic wave band of 8.2− 18 GHz, the materials had good
electromagnetic wave absorption ability. A combination of 3D printing
and heat treatment was used to prepare broadband wave-transmitting
ceramics. Forinstance, we aim to fabricate complicated ceramic mate­
rials more efficiently by using 3D printing technology. This method can
be further extended in the preparation of other functional ceramic sys­
tems with complex structures.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgment
The authors gratefully acknowledge the National Natural Science
Foundation of China (Grant No. 51802319), the Technology and Engi­
neering Center for Space (NO. CSU-QZKT-2019-04), the National Key
Research and Development Program of China No. 2018YFB1106600 and
the Youth Innovation Promotion Association of Chinese Academy of
Science (2021160).
References
[1] F.L. Riley, Silicon nitride and related materials, J. Am. Ceram. Soc. 83 (2) (2000)
245–265.
[2] J. Zhang, J.W. Chen, H.J. Wang, High performance porous wave-transmitting
silicon nitride ceramics by gel-casting technique, Key Eng. Mater. 512-515 (2012)
869–872.
[3] C.B. Cheng, R.H. Fan, K.L. Yan, K. Sun, Q.L. Qian, Fabrication and property of
porous silicon nitride ceramics with Y2O3-Yb2O3 additions, Key Eng. Mater. 655
(2015) 6–10.
[4] T. Nishimura, M. Mitomo, H. Suematsu, High temperature strength of silicon
nitride ceramics with ytterbium silicon oxynitride, J. Mater. Res. 12 (01) (1997)
203–209.
[5] A.J. Pyzik, D.R. Beaman, Microstructure and properties of self-reinforced silicon
nitride, J. Am. Ceram. Soc. 76 (11) (2010) 2737–2744.
[6] Yang Xuejin, Li Bin, Zhang Changrui, Wang Siqing, Liu Kun, Fabrication and
properties of porous silicon nitride wave-transparent ceramics via gel-casting and
pressureless sintering, Mater. Sci. Eng. A 663 (2016) 174–180.
[7] Kumar Kishore, Nagaveni Kandi, Surya Thallapalli, Rao Prakash, Chilakalapalli,
Development of silicon nitride-based ceramic Radomes-A review, Int. J. Appl.
Ceram. Technol. 12 (5) (2015) 909–920.
[8] Jie Ma, Shangli Dong, Junjie Ding, Biao Zhang, Feng Ye, Mechanical, dielectric
properties and thermal shock resistance of porous silicon oxynitride ceramics by
5504
Journal of the European Ceramic Society 41 (2021) 5495–5504
gas pressure sintering, Mater. Sci. Eng. A Struct. Mater. Prop. Misrostruct. Process.
635 (21) (2015) 1–5.
[9] Y. Zhao, Y. Zhang, H. Gong, H. Sun, Q. Li, Gas pressure sintering of BN/ Si3N4
wave-transparent material with Y2O3-MgO nanopowders addition, Ceram. Int. 40
(8) (2014) 13537–13541.
[10] R. Fischer, Si3N4 and Si2N2O for high performance radomes, Mater. Ence Eng. 71
(85) (1985) 265–272.
[11] R.-G. Duan, G. Roebben, J. Vleugels, O.Vd. Biest, Thermal stability of in situ
formed Si3N4-Si2N2O-TiN composites, J. Eur. Ceram. Soc. 22 (14) (2002)
2527–2535.
[12] F. Chen, F. Cao, H. Pan, K. Wang, Q. Shen, J. Li, S. Wang, Mechanical and dielectric
properties of silicon nitride ceramics with high and hierarchical porosity, Mater.
Des. 40 (9) (2012) 562–566.
[13] Li Xiangming, Zhang Litong, Yin Xiaowei, Fabrication and Properties of Porous
Si3N4 Ceramic with High Porosity, J. Mater. Sci. Technol. 28 (12) (2012)
1151–1156.
[14] Ching Wai-Yim, Mo Shang-Di, Chen Yu, Calculation of XANES/ELNES spectra of all
edges in Si3N4 and Si2N2O, J. Am. Ceram. Soc. 85 (1) (2002) 11–15.
[15] J. Luo, K. Zhang, G. Wang, W. Han, Fabrication of fine-grained Si3N4-Si2N2O
composites by sintering amorphous nano-sized silicon nitride powders, J. Wuhan
Univ. Technol. Sci Ed 21 (3) (2006) 97–99.
[16] G. Gundiah, G.V. Madhav, A. Govindaraj, M.M. Seikh, C.N.R. Rao, Synthesis and
characterization of silicon carbide, silicon oxynitride and silicon nitride nanowires,
J. Mater. Chem. 12 (5) (2002) 1606–1611.
[17] M. Pavese, M. Valle, C. Badini, Effect of porosity of cordierite preforms on
microstructure and mechanical strength of co-continuous ceramic composites,
J. Eur. Ceram. Soc. 27 (1) (2007) 131–141.
[18] T.A. Pham, D.P. Kim, T.W. Lim, S.H. Park, D.Y. Yang, K.S. Lee, Three-dimensional
SiCN ceramic microstructures via nano-stereolithography of inorganic polymer
photoresists, Adv. Funct. Mater. 16 (9) (2010) 1235–1241.
[19] H. Shao, D. Zhao, T. Lin, J. He, J. Wu, 3D gel-printing of zirconia ceramic parts,
Ceram. Int. 43 (16) (2017) 13938–13942.
[20] C. Kzab, B. Rha, C. Gdab, C. Xbab, B. Dfa, Effects of fine grains and sintering
additives on stereolithography additive manufactured Al2O3 ceramic-
ScienceDirect, Ceram. Int. 47 (2) (2020) 2303–2310.
[21] M.L. Griffith, J.W. Halloran, Freeform fabrication of ceramics via
stereolithography, J. Am. Ceram. Soc. 79 (10) (2010) 2601–2608.
[22] K. Hu, Y. Wei, Z. Lu, L. Wan, P. Li, Design of a shaping system for stereolithography
with high solid loading ceramic suspensions, 3D Print. Addit. Manuf. 5 (4) (2018)
311–318.
[23] R.J. Huang, Q.G. Jiang, H.D. Wu, Y.H. Li, S.H. Wu, Fabrication of complex shaped
ceramic parts with surface-oxidized Si3N4 powder via digital light processing based
stereolithography method, Ceram. Int. 45 (4) (2018) 5158–5162.
[24] Y. Yang, X. Song, X. Li, Z. Chen, C. Zhou, Q. Zhou, Y. Chen, Recent progress in
biomimetic additive manufacturing technology: from materials to functional
structures, Adv. Mater. 30 (36) (2018) 1–34.
[25] R.J. Huang, Q.G. Jiang, H.D. Wu, Y.H. Li, W.Y. Liu, X.X. Lu, S.H. Wu, Fabrication of
complex shaped ceramic parts with surface-oxidized Si3N4 powder via digital light
processing based stereolithography method - ScienceDirect, Ceram. Int. 45 (4)
(2019) 5158–5162.
[26] L.J. Gauckler, H.L. Lukas, G. Petzow, Contribution to the phase diagram Si3N4-AlN-
Al2O3-SiO2, J. Am. Ceram. Soc. 58 (7-8) (2010) 346–347.
[27] C. Cao, C. Wang, Z. Zhao, Optimization of curing behavior of Si3N4 UV resin for
photopolymerization 3D printing, Iop Conf. Ser. Mater. Sci. Eng. 678 (2019)
012–013.
[28] X.M. Hou, K.C. Chou, X.J. Hu, H.L. Zhao, A new measurement and treatment for
kinetics of isothermal oxidation of Si3N4, J. Alloys. Compd. 459 (1–2) (2008)
123–129.
[29] H. Liang, Y. Zeng, K. Zuo, X. Xia, D. Yao, J. Yin, The effect of oxidation on the
mechanical properties and dielectric properties of porous Si3N4 ceramics, Ceram.
Int. 43 (7) (2017) 5517–5523.
[30] J. Suri, L.L. Shaw, Liquid phase sintering of Si3N4/SiC nanopowders derived from
silica fume, Ceram. Int. 40 (7) (2014) 9179–9187.
[31] M. Srinivasan, P. Ramasamy, Computational Modeling on the Influence of the
Schmidt Number on Second Phase Impurities SiC, Si2N2O and Si3N4 in Grown mc-
Silicon for PV Applications, Silicon 10 (2017) 1077–1085.
[32] S. Qiang, C. Fei, Y. Faqiang, Z. Lianmeng, Progress on new type high temperature
ceramic missiles radome materials, Mater. Sci. Eng. R Rep. 20 (9) (2006) 1–4.
[33] I.E. Suzdal’tsev, Radio-transparent ceramics: yesterday, today, tomorrow, Refract.
Ind. Ceram. 55 (5) (2015) 377–390.
[34] D.ı ́az Aranzazu, Hampshire Stuart, Characterisation of porous silicon nitride
materials produced with starch, J. Eur. Ceram. Soc. 24 (2) (2004) 413–419.
[35] A. Popova, M. Christov, A. Vasilev, Inhibitive properties of quaternary ammonium
bromides of N-containing heterocycles on acid mild steel corrosion. Part I:
Gravimetric and voltammetric results, Corros. Sci. 49 (8) (2007) 3290–3302.
[36] A. Kumar, S. Sharma, G. Singh, Measurement of dielectric constant and loss factor
of the dielectric material at microwave frequencies, Prog. Electromagn. Res. 69
(2007) 47–54.