Ceramics International 48 (2022) 32–41

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

Fabrication and properties of Si2N2O-Si3N4 ceramics via direct ink writing

and low-temperature sintering
Qiao Jiang a, Daoyuan Yang a, *, Huiyu Yuan a, **, Rui Wang a, Mingxuan Hao a, Weili Ren a,
Gang Shao a, Hailong Wang a, Junyan Cui a, Jianhui Hu b
a
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou, China
b
Ruitai Materials Technology Co, Ltd, China

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

Keywords: Direct ink writing (DIW) and low-temperature sintering methods were applied to prepare Si2N2O-Si3N4 ceramics
DIW for radome materials. Lattices of Si-SiO2 green body were printed by DIW with 78 wt % solid portion of water-
Si-SiO2 slurry based Si-SiO2 slurry, in which silicon particles and silica fume were used as the solid portion and Methylcellulose
Low-temperature sintering
(HPMC) was used as the dispersant. Effects of HPMC addition on stability and silica fume content on rheological
Si2N2O-Si3N4 ceramics
properties of the slurry were studied, respectively. The pseudoplastic mechanism of the slurry was analyzed. The
Dielectric properties
Si-SiO2 green bodies were sintered at 1250 ◦ C–1400 ◦ C in nitrogen. The effect of temperature on phase
composition, microstructure, mechanical and dielectric properties of samples was investigated. With the HPMC
addition of 0.12 wt% and the silica fume proportion of 30 wt% in solid portion, a stable and pseudoplastic slurry
with the yield stress of 110.9 Pa was obtained, which is suitable for DIW. With the decrease of initial holding
temperature, more N2 enters the sample and reacts with silicon and silica fume, promoting the generation of
Si2N2O and Si3N4. The optimal condition yields Si2N2O-Si3N4 ceramics with apparent porosity of 42.73%,
compressive strength of 24.7 MPa, dielectric constant of 4.89 and loss tangent of 0.0054. It is found that
columnar Si3N4 comes from a direct reaction between silicon and N2, and fibrous Si2N2O is mainly generated by
the reaction between silicon, SiO(g), and N2 through the chemical vapor deposition mechanism. Good dielectric
properties are achieved due to high porosity, high proportion of Si2N2O phase and no residual silicon.

1. Introduction 3D printing or additive manufacturing, based on digital models,

Si3N4 is one of the radome materials with a good comprehensive
performance, such as the high strength, the good chemical stability, and
the low thermal conductivity, but the dielectric constant is relatively
high, which hinders its development as the radome material [1,2].
Si2N2O has a low dielectric constant, and the design and preparation of
Si2N2O-Si3N4 ceramics have become one of the research hotspots to
develop the high-performance radome materials [3–5]. The ceramic
reaction system composed of Si3N4 and SiO2 is often adopted to prepare
Si2N2O ceramics. Due to the strong covalent bond and low diffusion
coefficient of Si3N4, the sintering temperature is generally higher than
1500 ◦ C, leading to high manufacturing costs. What’s more, Si2N2O
phase in products tends to decompose at a temperature over 1400 ◦ C,
which results in poor dielectric properties [6], so it is necessary to find a
low-temperature processing for the preparation of the Si2N2O ceramics.
stacks materials layer by layer to produce three-dimensional objects
under the control of computer. In recent years, It has been widely
developed in the fields of metals, ceramics, and polymer materials
because of its flexible process, short manufacturing cycle and high
precision. At present, there has been a variety of 3D printing technolo­
gies that can produce ceramics with porous and complex structures, such
as selective laser sintering (SLS), stereolithography (SLA), laminated
object manufacturing (LOM), fused-deposition ceramics (FDCs), direct
ink writing (DIW), etc. [7–10]. Compared with other methods, DIW
extrudes ceramic slurries with the suitable rheology to form green
bodies, which does not require laser, ultraviolet light or even heating.
The use of a high solid-content slurry with a little organic binder can
reduce volume shrinkage caused by drying and sintering processes.
Ceramic powders currently used for DIW have included silicon oxide
(SiO2), silicon carbide (SiC), boron carbide (B4C), alumina (Al2O3),

* Corresponding author.
** Corresponding author.
E-mail addresses: yangdaoyuan@zzu.edu.cn (D. Yang), hyyuan@zzu.edu.cn (H. Yuan).

https://doi.org/10.1016/j.ceramint.2021.08.088
Received 27 May 2021; Received in revised form 21 July 2021; Accepted 9 August 2021
Available online 18 August 2021
0272-8842/© 2021 Published by Elsevier Ltd.
Q. Jiang et al.
silicon nitride (Si3N4), etc. and developing novel slurry systems has
become a primary task to broaden the application of DIW [11–15]. For
example, Yang et al. investigated 3D printing of complex alumina
ceramic parts via DIW using thermally induced solidification with
carrageenan swelling [16]. Cheng et al. prepared porous Si3N4-Si3N4
composite ceramics with excellent electromagnetic (EM)
wave-transparent performance using 3D printing technique combined
with the chemical vapor infiltration [17]. Manufacturing Si2N2O-Si3N4
ceramics via 3D printing techniques is beneficial to design the
complex-structure products, which could further improve its perfor­
mance as a radome material.
In this work, stable and shear-thinning slurries, consisting of silicon
particles, silica fume, Methylcellulose (HPMC), and water, were pre­
pared to produce the Si-SiO2 green body by DIW and the Si2N2O-Si3N4
ceramics were fabricated by nitration of the green body at a low sin­
tering temperature. Effects of HPMC addition on settlement stability of
slurry and silica fume content on rheological properties of slurry were
studied. Then, phase composition, microstructure, mechanical and
dielectric properties of samples sintered at different temperatures were
investigated. Optimum initial holding temperature was explored. This
work verified the feasibility of fabricating low dielectric constant
Si2N2O-Si3N4 ceramics by 3D printing and low-temperature sintering.
2. Experiment
2.1. Experimental process
The experimental process mainly includes preparation of the slurries,
printing of the green body, drying and sintering of the samples, as
schematically illustrated in Fig. 1a and b. Fig. 1c shows the lattice
structure of the green body, and the sintered sample is shown in Fig. 1d.
2.2. Raw materials
Silicon powder (Si 97 wt%) with D50 of 19.9 μm was used. Its phase
composition is shown in Fig. 2a. There is no obvious impurity phase, and
particles are irregular in shape (seen in Fig. 2b). Silica fume (SiO2 97.5
wt%) with D50 of 0.1 μm was used. Its XRD pattern shown in Fig. 2c
indicates an amorphous phase. Particle agglomerates are spherical as
shown in Fig. 2d. The average particle size of the agglomerates is 2.75
Fig. 1. (a) A schematic process for the direct ink writing of Si2N2O-Si3N4 ceramics, (b) 3D printed porous structure, (c) profile of the green body, (d) profile of the
sintered sample.
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Ceramics International 48 (2022) 32–41
μm. Methylcellulose (HPMC, industrial purity), in powder form, is used
as a dispersant. The purity of N2 is 99.9999%.
2.3. Preparation of slurry
HPMC powders were dissolved in water to make a solution with a
mass concentration of 0.425 wt%. After adding the silica fume, the
mixture was mechanically stirred for 10 min, then silicon was added and
the stirring lasted for 30 min until slurry became a gel state. The slurry
with solid portion of 78 wt% and HPMC solution portion of 22 wt% was
prepared, and the proportion of silica fume in the solid phase was
changed from 15 wt% to 35 wt%. The slurry was stirred under vacuum
to remove air bubbles, preventing extruded filaments from breaking
during the printing process and reducing defects of the printed bodies.
Finally, the slurry was ready for use.
2.4. Settlement experiment
The function of HPMC was evaluated and the content of HPMC was
optimized to provide the basis for the preparation of HPMC slurry, and
settlement experiments were conducted. The slurries with a solid
portion of 20 wt% (14 wt% silicon, 6 wt% silica fume) and a HPMC
solution portion of 80 wt% were employed to settle for 5 h. The HPMC
concentration was varied as follow, 0 wt%, 0.04 wt%, 0.08 wt%, 0.12 wt
% and 0.16 wt%, and the relative settlement height, defined as the ratio
of the height of solid-phase after settlement to the initial height of the
slurry, was calculated.
2.5. Rheology measurement
A rotary viscometer was applied to measure the rheological prop­
erties of slurries at room temperature. The apparent viscosity and shear
stress of slurry at a shear rate ranging from 1.04 s− 1 to 20.9 s− 1 were
obtained. The data was recorded after the rotor rotated 20 rounds at
each speed, and the average of three test results was used. The Herschel-
Bulkley model, as shown in Eq. (1), was introduced to fit shear stress-
shear rate curve to get the yield stress of the slurries.
τ = τy + K⋅γn (1)
Q. Jiang et al. Ceramics International 48 (2022) 32–41

Fig. 2. Phase composition and micromorphology of the raw materials: (a) and (b) for silicon, (c) and (d) for silica fume.

Where τ is the shear stress, τy is the yield stress, K is the consistency shown in Fig. 3. The temperature was firstly raised to 1250 ◦ C, 1300 ◦ C,
index, and n is the flow index. 1350 ◦ C, and 1400 ◦ C holding for 1 h respectively, and then raised to
1400 ◦ C holding for 3 h. Holding at 1400 ◦ C for 3 h allowed the grains to
grow and form interwoven structures, enhancing mechanical properties.
2.6. Sample preparation For the sake of convenience, the samples are represented by the corre­
sponding initial holding temperatures in the following text, such as the
Table 1 lists the printing parameters to process the slurries. The 1250 ◦ C sample, the 1300 ◦ C sample, the 1350 ◦ C sample, and the
printer uses compressed air to supply a stable pressure to push the slurry 1400 ◦ C sample.
from a barrel into an extrusion screw. Then the screw rotated to make
the slurry shear thinning and the slurry was extruded from the nozzle.
The nozzle moved precisely under the control of sliced code and fila­
ments were stacked layer by layer to form objects on the substrate. To
make the green body react with N2 as much as possible, the lattice
structure shown in Fig. 1b was designed.
Once the printing was completed, the printed body was left at room
temperature for 24 h, and then dried at 80 ◦ C for 10 h. The green body
had no apparent cracks and was sintered in nitrogen with a flow rate of
120 ml/min. The furnace was flushed with N2 for 30 min to remove air
before annealing. Due to the exothermic reaction between the green
body and N2, excessively high annealing temperature may yield the local
temperature of the sample over 1412 ◦ C, causing silicon particles to
melt. To avoid molten silicon decreasing the diffusion rate of N2, the
sample was firstly held at a low temperature for 1 h. Four different initial
holding temperatures were used and the heating rate was 5 ◦ C/min, as

Table 1
The printing parameters of the direct ink writing
process.
Parameter Value

Nozzle diameter 1.5 mm

Layer height 1.05 mm
Printing speed 60 mm/s
Infill percentage 80%
Fig. 3. Schematic diagram of the sintering process.

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Q. Jiang et al.
2.7. Characterization
Phase composition of the raw materials and samples was measured
by XRD (Philips X′ Pert Pro, Philips). Rheological properties of the
slurries were tested with a rotary viscometer (RVDV-1T, Fangrui). The
microstructure was observed by SEM (EVOHD 15, ZEISS) and TEM
(TalosF 200S, FEI). Apparent porosity and bulk density were measured
by the Archimedes method. The compressive strength of the sintered
samples was tested by a universal testing machine. Flexural strength of
the samples was tested by the three-point bending method (with a span
of 40 mm, and sample size of 60 mm × 20 mm × 20 mm). The dielectric
properties of the samples were tested by the short-circuit waveguide
method (with a diameter of 8 mm and a thickness of 1.5 mm).
3. Results and discussion
3.1. Stability of slurry
Fig. 4 shows the relationship between HPMC addition and relative
height of Si-SiO2 slurry after settlement. When the addition of HPMC is
0.12 wt%, the relative height of slurry is largest, and good dispersion
stability is achieved because HPMC reaches saturated adsorption on the
surface of particles and forming steric barriers prevents particle
agglomerating [18]. HPMC with an addition of lower or higher than
0.12 wt% makes powders agglomerate. Slurries with good dispersity can
be smoothly and uniformly squeezed out, while easy flocculation of
slurry will block the nozzle and interrupt the printing process. There­
fore, it is determined that the optimal addition of HPMC is 0.12 wt%.
3.2. Rheology of slurry
Fig. 5a and b shows the effect of shear rate on viscosity and shear
stress of the slurries with the solid portion of 78 wt%, the HPMC addition
of 0.12 wt%, and the silica fume content of 15–35 wt%. As the shear rate
increases, the viscosity of the slurry decreases, showing a shear-thinning
behavior. An increase in the shear stress is observed with increasing the
shear rate. Because the internal bonding density of slurry increases with
the increase of silica fume content, viscosity and shear stress increase. As
shown in Table 2, the yield stress of slurry with the silica fume content of
15–35 wt% is between 28.0 MPa and 143.6 MPa. As the silica fume
content increases, the yield stress increases, indicating that the ability to
resist deforming is enhanced. And the flow index n of each slurry is less
Fig. 4. Relationship between the HPMC addition and the relative height of Si-
SiO2 slurry after settlement.
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Ceramics International 48 (2022) 32–41
than 1, indicating that the slurry is a pseudoplastic type. Such a pseu­
doplastic slurry would flow in a shear-thinning manner when the
applied shear stress exceeds the yield stress, and maintain deposited
shape after extrusion.
Because of the low yield stress and poor shape retention, the slurry
with 15 wt% or 20 wt% silica fume content tends to collapse and deform,
as shown in Fig. 6a and b. Compared with 25 wt%, the yield stress of
slurry with 30 wt% silica fume content increases significantly to 110.9
Pa (see Table 2), which is enough to support subsequent layers without
collapse or deformation. As shown in Fig. 6d, the extruded filaments are
uniform and the structure of the printed body is well maintained.
However, when the content reaches 35 wt%, the high yield stress is not
conducive to uniform extrusion of the slurry, and the poor forming effect
is observed, as shown in Fig. 6e. In conclusion, the slurry with the silica
fume content of 30 wt% possesses the obvious shear-thinning behavior,
appropriate yield stress and best forming effect, so it is finally selected
for further DIW.
3.3. Pseudoplastic mechanism of slurry
The Si-SiO2 slurry composing of silicon, silica fume, HPMC and water
show good dispersity. The silica fume has natural hydroxyl groups on
the surface, which adsorbs H2O through hydrogen bondings, but the
hydrogen bonding between silica fume can cause agglomeration, as
shown in Fig. 7a. HPMC is used to adjust the flocculation state of par­
ticles and the structure is shown in Fig. 7b. Hydrophilic groups on mo­
lecular chains of HPMC interact with H2O on the surface of silica fume
by hydrogen bondings and steric hindrance layers are formed, which
prevents particles from contacting each other. As shown in Fig. 7c, Silica
fume, HPMC and H2O are connected forming a three-dimensional
network structure by hydrogen bondings. Silicon powders can be
encapsulated by the network and a strong gel state is achieved. Once the
network is destroyed, H2O adsorbed on the powder surface is released,
and the molecular chains tend to flow directionally under external shear
force, the viscosity of the slurry decreases. The network structure can be
rebuilt after the shear force is removed, leading the viscosity and yield
stress to restore. In addition, pressure from subsequent layers is
dispersed throughout the network, thus the slurry can maintain a uni­
form and intact shape. This pseudoplasticity facilitates successful
extrusion and stacking of the slurry [19].
3.4. Phase composition
The phase composition of samples under the different initial holding
temperatures is shown in Fig. 8. The Si2N2O phase is detected in all
samples, indicating that the green body reacts with flowing N2. The
dominant crystal phase in the 1400 ◦ C sample is Si phase, while that in
other samples is Si2N2O phase. The intensity of Si phase decreases with
the decrease of initial holding temperature and the Si phase disappears
in the 1250 ◦ C sample. The Si3N4 phase is generated in 1350 ◦ C, 1300 ◦ C,
and 1250 ◦ C samples and no crystal SiO2 is observed in all samples.
Fig. 9a–c shows the microstructure and EDS line scanning results of
the 1400 ◦ C sample. The microstructure is very dense and pores with a
radius of more than 10 μm are rarely found in Fig. 9a. Many large par­
ticles show a transgranular fracture and some dimples appear on the
fracture surface, which reflects that the strength of matrix is high [20,
21]. And there are brittle fractures and a small amount of ductile frac­
ture observed. In Fig. 9b, no crack is observed at the boundary between
the large particle and the matrix. The line scanning data in Fig. 9c shows
that the large particles are silicon. Si2N2O may be generated in the
matrix due to the decrease of Si content and increase of O and N content.
The N content in the matrix is similar to that at the boundary of silicon
particles, but the Si content decreases with the increase of O content,
which may be due to silica in the matrix.
According to the EDS of the 1350 ◦ C sample in Fig. 9d and f, the O
content is as high as 35.2% in area B, exceeding that in the Si2N2O phase,
Q. Jiang et al. Ceramics International 48 (2022) 32–41

Fig. 5. Relationship between the shear rate and (a) viscosity and (b) shear stress of the slurries.

tendency. According to the research of R.V. Giridhar [22], SiO(g) can be

Table 2
produced under active oxidation conditions, seen in reaction (2). The
Rheological parameters of slurries fitted with Herschel-Bulkley model.
partial pressure of SiO(g) (p(SiO)) is much higher than p(O2) in the
Silica fume content(wt%) Yield stress(Pa) n Si-N-O system, and the partial pressure of oxygen (p(O2)) for stable
15 28.0 0.414 existence of Si2N2O phase at 1250 ◦ C ranges from 10− 7.5 MPa to 10− 6.4
20 41.2 0.423 MPa. A stable Si2N2O phase can be generated because p(O2) is 10− 7
25 71.4 0.453
MPa. Residual oxygen may be consumed and a small amount of Si2N2O
30 110.9 0.481
35 143.6 0.471 can be generated by reaction (3) during the heating process. Fibrous
Si2N2O can be generated by the chemical vapor deposition mechanism
among Si, SiO(g), and N2, seen in reaction (6). In the area where p(O2) is
which illustrates the sample contains silicon and silica in addition to lower than 10− 7.5 MPa, Si directly reacts with N2 generating Si3N4
Si2N2O, and the green body is not completely nitrided. However, there is phase, seen in reaction (8). Although the reaction (4) shows that Si3N4
no residual silicon or silica in 1250 ◦ C sample because the atomic ratio of reacts with SiO(g) and N2 generating Si2N2O, it must overcome a higher
Si-N-O is close to 2:2:1 based on the EDS of area C in Fig. 9e and g. The reaction barrier compared with reaction (6). The reaction (5) and (7)
element analysis data are consistent with the XRD data which show the indicate that SiO2 could react with Si or Si3N4 generating Si2N2O.
1250 ◦ C sample is mainly composed of Si2N2O and contains a small However, there is a little chance of contact between SiO2 and Si3N4
amount of Si3N4 phase, forming the expected phase composition for because p(O2) is higher than 10− 7.5 MPa and the amount of generated
radome materials. This work shows that reducing the initial holding Si3N4 is very small, so the silica mainly reacts with Si and N2 through
temperature is conducive to adequate nitriding of Si-SiO2 green body reaction (5). It can be seen from Fig. 10 that the reaction (5) is easier to
and provides a suitable approach for the low-temperature preparation of occur than the reaction (6). Besides, only a small amount of Si2N2O is
Si2N2O-Si3N4 ceramics. generated by the reaction of Si, SiO(g) and N2 because (p(SiO)) is much
lower than the partial pressure of N2. To sum up, Si2N2O is mainly
3.5. Reaction mechanism analysis generated by the reaction of silicon with silica particles and N2.
Overall, the reaction mechanism of green body and N2 at 1250 ◦ C can
Table 3 lists possible reactions in the sintering process. Standard be analyzed as follows: p(O2) decreases and the silica fume is decom­
Gibbs free energies of reactions (3)–(7) generating Si2N2O change with posed producing SiO(g) when O2 is consumed in flowing N2. SiO(g)
temperature as shown in Fig. 10 and they are all negative meaning that escapes, N2 diffuses into the sample along pore channels and reacts with
Si2N2O can be spontaneously generated at 1200 ◦ C–1500 ◦ C. Reaction the silicon and silica particles to generate Si2N2O. Continuous penetra­
(3) has the strongest tendency, while reaction (7) has the weakest tion of N2 promotes the generation of Si2N2O and Si3N4. However, when

Fig. 6. Forming result of the slurries with different silica fume contents.

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Q. Jiang et al.
Fig. 7. Pseudoplastic mechanism of slurry: (a) hydrogen bonding between silica fume and H2O, agglomeration of silica fume; (b) HPMC structural formula; (c)
network structure formed by interaction among components of slurry.
Fig. 8. XRD pattern of the samples under different initial holding temperatures.
the silicon and silica on the surface of the green body directly react with
N2 at 1300 ◦ C, the volume expands so that micropores are closed,
resulting in a part of silicon not in contact with N2. Due to more intense
nitridation and more obvious volume expansion at 1350 ◦ C and 1400 ◦ C,
there are fewer pore channels for N2 to enter the sample and more silicon
fails to be nitrided. Furthermore, the local temperature of the sintered
sample may exceed 1412 ◦ C and the molten silicon blocks the pore
channels [24]. In short, the number of the open pore channels in the
sample is closely related to the nitriding temperature, affecting the
contact degree between N2 and silicon. Even though reactions between
the green body and N2 proceed slowly at a low temperature, there are
still many pore channels in the sample and SiO(g) can escape in time,
which is beneficial to the diffusion of N2 and generation of Si2N2O.
Therefore, at the relatively low initial holding temperature of 1250 ◦ C,
Si-SiO2 green body is completely nitrided and Si2N2O-Si3N4 ceramics
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Ceramics International 48 (2022) 32–41
without residual silicon is successfully prepared.
3.6. Post-sintering properties
Fig. 11a shows the linear shrinkage rate in the X (plane direction of
layers) and Z (Stacked direction of layers) directions of samples with the
different initial holding temperatures. It can be seen that the linear
shrinkage rate decreases with the increase of the initial holding tem­
perature and the lowest linear shrinkage rate is obtained in 1400 ◦ C
sample. This is because many silicon particles are not in contact with N2
at such a high initial holding temperature, and they undergo self-
sintering and coarsening, so that the volume shrinkage is not obvious.
The 1250 ◦ C sample without residual silicon has the largest linear
shrinkage rate in the X and Z directions, which is 5.46% and 6.69%,
respectively. Due to the close contact between layers in the Z direction
under the gravity, the shrinkage presents an anisotropic characteristic
and the linear shrinkage in the X direction is lower than that in the Z
direction.
The apparent porosity and bulk density of samples under the
different initial holding temperatures are shown in Fig. 11b. It is obvious
that as the initial holding temperature increases, the apparent porosity
decreases, and the bulk density increases. Because N2 fully enters the
sample and mesophase SiO(g) escapes, leaving many pores [26], the
1250 ◦ C sample shows the largest porosity and smallest bulk density,
which are 42.73% and 1.56 g/cm3, respectively. Fig. 11c shows that the
compressive and flexural strength of samples increases as the initial
holding temperature increases. Due to the ductile fracture of a large
number of silicon particles, the compressive and flexural strength of the
1400 ◦ C sample is highest. The high porosity leads to the low
compressive and flexural strength of the 1250 ◦ C sample, which is 24.7
MPa and 16.9 MPa, respectively.
3.7. Microstructure and formation mechanism
As shown in Fig. 12a and b, there are large gaps over 200 μm between
extruded filaments of the green body. Powders are uniformly stuck and
micropores are observed in filaments. Fig. 12c and d shows the fracture
Q. Jiang et al. Ceramics International 48 (2022) 32–41

Fig. 9. Sample morphology and EDS analysis: (a), (b) and (c) for the 1400 ◦ C sample; (d) and (f) for the 1350 ◦ C sample; (e) and (g) for the 1250 ◦ C sample.

suggest that the composition of the fibers is mainly Si2N2O.

Table 3
Possible reactions in sintering process [22–25].
Si(s) + SiO2(s) = 2SiO(g)
4Si(s) + 2N2(g) + O2(g) = 2Si2N2O(s)
Si3N4(s) + 3SiO(g) + N2(g) = 3Si2N2O(s)
3Si(s) + SiO2(s) + 2N2(g) = 2Si2N2O(s)
Si(s) + SiO(g) + N2(g) = Si2N2O(s)
Si3N4(s) + SiO2(s) = 2Si2N2O(s)
3Si(s) + 2N2(g) = Si3N4(s)
Based on the above analysis, the formation mechanism of Si2N2O and
Si3N4 can be shown in Fig. 13. The metastable SiO(g) is generated and
(2) escapes when p(O2) decreases, providing channels for N2 to penetrate
(3)
the sample. The matrix Si2N2O is produced by adsorbing N2 at contact
(4)
(5) parts of silicon and silica particles. The silicon directly reacts with N2
(6) generating the columnar Si3N4 in the area where the SiO(g) escapes. At
(7) the same time, the silicon that does not contact with silica reacts with
(8) SiO(g) and N2 to generate the fibrous Si2N2O by the chemical vapor
deposition mechanism. The infiltration of N2 promotes the formation of
Si2N2O and Si3N4.

3.8. Dielectric properties

The dielectric property is one of the most important parameters for

Fig. 10. Standard Gibbs free energies of Si2N2O phase as a function of
temperature.
morphology of the 1350 ◦ C sample and a few pores are observed. There
are many columnar particles around pores and the EDS in Fig. 12e and f
shows that the phase composition of the columnar particles is Si3N4. The
columnar particles are entangled with nanofibers, improving the me­
chanical properties of sample [27]. Fig. 12g and h shows the fracture
morphology of the 1250 ◦ C sample. There are more pores on the fracture
surface than that of the 1350 ◦ C sample and clastic granules are tightly
combined. The EDS of the 1250 ◦ C sample shown in Fig. 9e indicates that
the clastic granules mainly consist of Si2N2O. In addition, the columnar
particles are also found around pores and overlapped together to form a
bridge structure, which is beneficial to improve the structural strength
[28,29]. For the 1250 ◦ C sample, a large number of fibers are generated
radome materials. The dielectric properties are usually characterized by
dielectric constant and loss tangent. The smaller the dielectric constant,
the less the reflection of electromagnetic wave on the material surface;
the smaller the loss tangent, the less the energy of electromagnetic wave
converted into heat through the material, and the better the trans­
mission performance of electromagnetic wave. Therefore, pursuing a
low dielectric constant and a loss tangent is the goal to develop high-
performance radome materials.
Fig. 14a and b shows the dielectric constant and loss tangent of the
1250 ◦ C sample without the residual silicon and the 1300 ◦ C sample with
a small amount of residual silicon. It can be seen that with the increase of
frequency, the dielectric constant decreases, while the loss tangent de­
creases first and then increases slightly. Both samples are mainly
composed of Si2N2O. Due to the spatial polarization and long relaxation
time of Si2N2O materials, the dielectric constant of samples decreases
with the increase of frequency. The dielectric constant and loss tangent
of the 1250 ◦ C sample are significantly lower than those of the 1300 ◦ C
sample. The 1250 ◦ C sample has a low dielectric constant and a loss
tangent at 1 MHz, which are 4.89 and 0.0054, respectively. Compared
with Si2N2O ceramics with a dielectric constant of 6.17 prepared by hot
pressing at 1500 ◦ C using Si3N4 and SiO2 by Tong Q [30], the
Si2N2O-Si3N4 ceramics prepared in this experiment has a lower dielec­
tric constant, showing excellent dielectric properties.
The dielectric properties of samples are mainly affected by the phase
composition and porosity [31]. The higher the porosity, the lower the
dielectric constant. The dielectric constant of composites generally fol­
lows Lichtenecker mixing law as shown in Eq. (9) [32]:
∑
n
Ln ε = Vi Ln εi (9)
i

around pores in Fig. 12i and the diameter of the fibers of about 50 nm or
Where ε is the dielectric constant of composites, Vi and εi represent the
150 nm is observed by TEM in Fig. 12j. The EDS data in Fig. 12k & l
volume fraction and dielectric constant of the component in composites,

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Q. Jiang et al. Ceramics International 48 (2022) 32–41

Fig. 11. Properties of samples: (a) linear shrinkage, (b) apparent porosity and bulk density, (c) compressive strength and flexural strength.

Fig. 12. Fracture morphology: (a) and (b) for the green body; (c), (d),(e) and (f) for the 1350 ◦ C sample; (g), (h), (i), (j), (k)and (l) for the 1250 ◦ C sample.

respectively. It can be seen that high dielectric constant components in
the composite will cause overall dielectric properties to deteriorate. The
order of dielectric constant among Si, Si3N4, and Si2N2O is Si > Si3N4 >
Si2N2O, so samples should avoid containing silicon.
The 1250 ◦ C sample has no impurity Si phase and is composed of
Si2N2O and Si3N4. Si2N2O with lower dielectric constant accounts for
88.2 wt%, calculated by the adiabatic method, and the apparent
porosity is 42.73%, so it has a low dielectric constant and a loss tangent.
Although the 1300 ◦ C sample contains 83.7 wt% Si2N2O phase and 10.7
wt% Si3N4 phase, the dielectric constant is significantly high because of

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Q. Jiang et al.
Fig. 13. Formation mechanism of Si2N2O and Si3N4 in the 1250 ◦ C sample.
Fig. 14. Dielectric properties of samples: (a) dielectric constant, (b) loss tangent.
the residual silicon and the low apparent porosity. The loss tangent
affected by the impurity silicon exceeds 0.01, and the dielectric prop­
erties are poor. Therefore, Si2N2O-Si3N4 ceramics with good dielectric
properties can be obtained by sintering Si-SiO2 green body at 1250 ◦ C for
1 h and subsequent annealing at 1400 ◦ C for 3 h.
4. Conclusions
In this work, lattices of Si-SiO2 green body were printed via the direct
ink writing technology and the Si2N2O-Si3N4 ceramics were successfully
prepared when the green body was sintered in nitrogen at relatively low
temperature. The following conclusions can be drawn:
(1) Stable Si-SiO2 slurries consisting of silicon powders, silica fume
and water can be achieved at 0.12 wt% addition of HPMC. When
the proportion of silica fume in solid portion is 30 wt%, the shear-
thinning slurry exhibits yield stress of 110.9 Pa and the best
printing result. Hydroxyl groups on the surface of silica fume and
hydrophilic groups of HPMC play an important role in pseudo­
plasticity of the slurry. The silica fume is dispersed by steric
hindrance and the spatial network is formed by hydrogen bond­
ings, so pseudoplastic behavior of the slurry is achieved and
works well for DIW.
(2) The reaction of silicon and silica with N2 is the main way to
generate Si2N2O, and the high porosity of the green body is
conducive to the diffusion of N2 and the complete reaction of the
green body. Relatively low initial holding temperature is
conducive to SiO(g) escape and N2 infiltration into the sample,
promoting the formation of Si2N2O and Si3N4. Two-step sintering,
first at 1250 ◦ C for 1 h and then at 1400 ◦ C for 3 h promotes Si-
SiO2 green body completely reacting with N2. And the Si2N2O-
Si3N4 ceramics with a dielectric constant of 4.89 and a loss
tangent of 0.0054 is fabricated. The apparent porosity and bulk
densities are 42.73% and 1.56 g/cm3, and the compressive and
flexural strengths are 24.7 MPa and 16.9 MPa, respectively.
(3) The fibers are interwound with the columnar Si3N4 particles,
enhancing the mechanical properties of the sample. The
columnar Si3N4 comes from the direct reaction between silicon
and N2, and the fibrous Si2N2O is mainly generated by the
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Ceramics International 48 (2022) 32–41
reaction between silicon, SiO(g), and N2 through the chemical
vapor deposition mechanism. The high porosity and high pro­
portion of Si2N2O phase without silicon contribute to the excel­
lent dielectric properties.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
Thanks for the financial support from the National Key R&D program
of China (2017YFB0310701) and Science and Technology Innovation
Fund of Henan for Outstanding Talents (17420051001), and the Young
top-notch talent of Zhengzhou University (125/32310189).
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