Int J Applied Ceramic Tech - 2022 - Dong - Additive Manufacturing of Silicon Nitride Ceramics A Review of Advances and

Received: 19 May 2022 Revised: 7 July 2022 Accepted: 11 July 2022
DOI: 10.1111/ijac.14162
REVIEW ARTICLE
Additive manufacturing of silicon nitride ceramics:

A review of advances and perspectives
Xingjie Dong1,2 Jianqin Wu1,2 Honglin Yu3 Qing Zhou1,2 Wenqing Wang1,2
Xueqin Zhang1,2 Lu Zhang1,2 Ling Li3 Rujie He1,2
1 State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing, China
2 Institute of Advanced Structure Technology, Beijing Institute of Technology, Beijing, China
3 Shandong Industrial Ceramics Research & Design Institute Co. Ltd., Zibo, China
Correspondence
Ling Li, Shandong Industrial Ceramics Abstract
Research & Design Institute Co. Ltd., Zibo Silicon nitride (Si3 N4 ) ceramic has been widely applied in various engineering
255000, China.
Email: [email protected] fields. The emergence of additive manufacturing (AM) technologies provides an
innovative approach for the fabrication of complex-shaped Si3 N4 ceramic com-
Rujie He, State Key Laboratory of
ponents. This article systematically reviews the advances of the AM of Si3 N4
Explosion Science and Technology,
Beijing Institute of Technology, Beijing ceramic in recent years and forecasts the potential perspectives in this field. This
100081, China. review aims to motivate future research and development for the AM of Si3 N4
Email: [email protected]
ceramic.
Funding information
National Natural Science Foundation of KEYWORDS
China, Grant/Award Numbers: 51772028, additive manufacturing, ceramic, silicon nitride
91960102; Open Project of State Key
Laboratory of Explosion Science and
Technology, Grant/Award Number:
QNKT22-15
1 INTRODUCTION Since 1950s, the increasing demand for the use of Si3 N4
ceramic has led to the continuous development of its man-
Silicon nitride (Si3 N4 ) ceramic has been widely applied in ufacture methods.11,12 Initially, the traditional fabrication
military, mechanical engineering, aerospace, and biomed- of Si3 N4 ceramic includes dry pressing combined with
ical fields, such as missile radomes,1 rocket nozzles,2 tur- pressureless sintering13,14 or hot-pressing sintering,15,16
bine and automotive engine components,3 tool bits,4 wear- and cold isostatic pressing (CIP) followed by gas pres-
resistant bearings, hip or knee endoprosthetic implants, sure sintering,17–19 and so on. Although Si3 N4 ceramic
and dental implants,5 owing to its promising combined prepared by these conventional technologies have high
properties of excellent mechanical properties, thermal density and good mechanical properties, they generally
shock resistance at elevated temperatures, good dielec- require a post-machining treatment (such as grinding,
tric properties and biocompatibility6–10 (as shown in cutting, and machining20 ), which is both expensive and
Figure 1). At present, the demand for high-performance difficult due to various high-cost machining tools and
complex-shaped Si3 N4 ceramic components in different the inherent brittleness of ceramic. Subsequently, many
applications is increasingly urgent, which has attracted the traditional near-net-shape fabrication methods begin to
interest of many researchers. appear for Si3 N4 ceramic, such as injection molding21,22
Int J Appl Ceram Technol. 2022;19:2929–2949. wileyonlinelibrary.com/journal/ijac © 2022 The American Ceramic Society. 2929
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2930 DONG et al.
also lead to difficulties in densification after AM. There-

fore, till now, there have been relatively few reports on AM
of Si3 N4 ceramic.
Fortunately, the research on the AM of Si3 N4 ceramic
has received more and more attentions recently, and
attempts have been on the rise. AM technologies of Si3 N4
ceramics mainly include (1) powder bed fusion (includ-
ing selective laser sintering [SLS], and selective laser
melting [SLM],43–49 and so on), (2) photopolymerization
(usually including stereolithography apparatus [SLA],50
laser-induced slip [LIS] casting,51 digital light processing
[DLP],52–65 liquid crystal display [LCD],66,67 and so on);
(3) material extrusion (usually including direct ink writ-
ing [DIW] or robocasting,68–74 fused deposition modeling
[FDM],75–79 and so on); and (4) other AM technologies
(including binder jetting [BJ],80–85 3DP,86–89 and laminated
object manufacturing [LOM]90–94 ). Schematics of the pre-
vious AM technologies for Si3 N4 ceramic are illustrated in
Figure 2.
FIGURE 1 Properties and applications of Si3 N4 ceramic Here, therefore, we aim to summarize the advances of
AM of Si3 N4 ceramic as systematically and comprehen-
sively as possible and forecast future potential perspec-
and gel-casting.23,24 These methods are usually combined tives. In this review, the advances of AM technologies of
with pressureless sintering to produce Si3 N4 ceramic parts, Si3 N4 ceramic will be described in Section 2, and the per-
which avoid the trouble of post-mechanical processing to spectives will be introduced in Section 3. The authors hope
a certain extent. However, the need for molds still makes that this review will provide a deep insight into the AM of
these methods time-wasting and limited for producing Si3 N4 ceramic.
high-complex-shaped Si3 N4 ceramic components. There-
fore, novel advanced manufacturing technologies for Si3 N4
ceramic are deemed necessary to develop. 2 ADVANCES
Additive manufacturing (AM), also known as 3D print-
ing (3DP) or solid freeform fabrication, refers to the process 2.1 Powder bed fusion
of combining materials to fabricate components from 3D
models layer-by-layer. AM has attracted great attentions Powder bed fusion technology mainly includes SLS and
due to its obvious advantages in recent years. Apart from SLM. They create 3D parts through the application of laser
the enormous time and cost savings, AM has part and energy to powder beds via the CAD description of the part
production flexibility. Because there are no tooling con- geometry, as shown in Figure 2A. The difference between
straints, parts with complex shapes can be made in a SLS and SLM is that the temperature at which the laser
single piece.25 Moreover, the more complicated a prod- irradiates the powder is higher or lower than the melting
uct’s structure is, the more clear the benefits of AM point of the powder. The advantage of SLS/SLM is that
become. Therefore, the emergence of AM technologies there are many materials they can use, including polymers,
provides an innovative technological approach for the metals, ceramics, gypsum, nylon, and other powders. How-
fabrication of complex-shaped ceramics. Currently, typ- ever, the main drawback of SLS/SLM techniques is the
ical oxide ceramics (such as Al2 O3 ,26,27 ZrO2 ,28–30 etc.), residual stresses from rapid heating followed by the solidi-
precursor-derived ceramics (such as SiOC,31,32 SiCN,33,34 fication during the manufacturing, which could introduce
etc.), bio-ceramics (such as hydroxyapatite,35,36 calcium cracks or even entire structural failure.95
phosphate,37,38 etc.), and even some ceramic matrix SLS/SLM of Si3 N4 ceramic is extremely challenging due
composites (such as SiCw /Al2 O3 ,39,40 Csf /SiC,41,42 etc.) to poor sinterability caused by the low absorption of laser
have been successfully prepared by using various AM beam energy. Therefore, Minasyan et al.43 proposed an
technologies. However, compared to other ceramic materi- indirect approach to fabricate Si3 N4 -based ceramic parts
als, Si3 N4 ceramics have a high refractive index, which will with complex geometry by SLS. First, SLS of silicon powder
lead to difficulties in forming during the photopolymeriza- provided a needed shape, and then the nitridation of the
tion AM process. Besides, its strong covalent bonding can as-shaped silicon parts aimed at the fabrication of Si3 N4
DONG et al. 2931
F I G U R E 2 Schematics of additive manufacturing (AM) technologies for Si3 N4 ceramic: (A) selective laser sintering (SLS)/selective laser
melting (SLM); (B) stereolithography apparatus (SLA); (C) laser-induced slip (LIS); (D) digital light processing (DLP), liquid crystal display
(LCD); (E) direct ink writing (DIW) (robocasting); (F) fused deposition modeling (FDM); (G) binder jetting (BJ); (H) 3D printing (3DP); (I)
laminated object manufacturing (LOM)
ceramic component. They investigated the influences of not high enough, resulting in poor mechanical proper-
laser current, point distance, and exposure time on the ties. Moreover, the indirect SLS/SLM method is usually
morphology, density, and mechanical properties of the sin- cumbersome and time-consuming. Wei et al.45 directly fab-
tered Si3 N4 ceramic samples. The result showed that the ricated a pre-sintered Si3 N4 ceramic with a porosity of 80%
SLS–3D printed Si parts reached a geometrical density of by SLS in the air atmosphere. They found that the bond-
82%, a Vickers hardness of 11.8 GPa, and a compressive ing of the SLS–3D printed Si3 N4 ceramic depended on
strength of 432 MPa, respectively. In their further work,44 microvilli and nanowires on its surface, which is shown in
core–shell-structured MoSi2 /(10–13 wt.%)Si powders were Figure 3B (reproduced with permission from Ref. [45] 2019
used for the fabrication of MoSi2 /Si3 N4 cellular mesostruc- Elsevier). This bonding mechanism was significantly dif-
tures by the same indirect method, as shown in Figure 3A ferent from that of metals or oxide ceramics.96,97 Although
(reproduced with permission from Ref. [44] 2019 Else- they directly manufactured porous Si3 N4 ceramic by
vier). The silicon shell of core–shell-structured MoSi2 /Si SLS, the mechanical properties of the as-prepared porous
powder served as a binder phase that provided the rele- Si3 N4 ceramic were poor and could only satisfy the
vant laser absorption, whereas the MoSi2 core provided the following posttreatment requirements. Therefore, Wang
mechanical durability. Although their work transformed et al.46 attempted to fabricate high-strength Si3 N4 ceramic
MoSi2 /Si lattices into MoSi2 –Si3 N4 ceramic composites, antenna windows via SLS with CIP after debinding before
the theoretical amounts of Si3 N4 after nitridation were final sintering. The strength of the SLS–3D printed Si3 N4
2932 DONG et al.
F I G U R E 3 (A) Selective laser melting (SLM) fabrication procedure for MoSi2 –Si3 N4 ceramic lattice, (B) bonding mechanism of Si3 N4
ceramic depended on microvilli and nanowire on its surface, (C) Si3 N4 –SiC/SiO2 composite part fabricated by selective laser sintering (SLS)
and sol infiltration (SI), (D) flexural strengths of the Si3 N4 –SiC/SiO2 composites subjected to various infiltration and heat-treatment cycles,
(E) hemispherical green bodies and sintered Si3 N4 ceramic housing, (F) SLS fabrication procedure proposed for a dense Si3 N4 ceramic coating
on titanium substrate. Source: (A) Reproduced with permission from Ref. [44] 2019 Elsevier; (B) reproduced with permission from Ref. [45]
2019 Elsevier; (C) reproduced with permission from Ref. [47] 2021 Elsevier; (D) reproduced with permission from Ref. [47] 2021 Elsevier; (E)
reproduced with permission from Ref. [48] 2019 MDPI; and (F) reproduced with permission from Ref. [49] 2020 Elsevier
ceramic after sintering at 1750◦ C without CIP was only After the six silica–SI and heat treatment cycles, the flex-
12 MPa. After one CIP treatment, however, the strength ural strength of the Si3 N4 –SiC/SiO2 composite reached
of the SLS–3D printed Si3 N4 ceramic increased signifi- 42.4 MPa, which is much higher than that obtained with-
cantly to 225 MPa. Moreover, after two CIP treatments, the out infiltration (as shown in Figure 3D (reproduced with
strength of the SLS–3D printed Si3 N4 ceramic increased permission from Ref. [47] 2021 Elsevier)). Therefore, Both
even more markedly to 592 MPa. The result showed that CIP and SI treatment after SLS are helpful to improve the
the strength of the SLS–3D printed Si3 N4 ceramic could mechanical properties of the Si3 N4 ceramic.
be greatly improved by CIP after debinding. In addition There are also some reports on the functional appli-
to the previous study, Yu et al.47 prepared Si3 N4 –SiC/SiO2 cation of the SLS–3D printed Si3 N4 ceramic. Qi et al.48
ceramic composites using SLS and sol infiltration (SI) pro- successfully prepared gradually thickened hemispheri-
cessing. SLS was used to print the green ceramic body of cal Si3 N4 ceramic housings based on SLS. The printed
the desired part with complex shapes. SI process increased hemispherical green bodies and the sintered Si3 N4 ceramic
the density and improved the mechanical properties of housing are shown in Figure 3E (reproduced with permis-
the resulting Si3 N4 –SiC/SiO2 composites. A photograph of sion from Ref. [48] 2019 MDPI). They expected to utilize
the Si3 N4 –SiC/SiO2 composite part is shown in Figure 3C SLS to achieve batch production of deep-sea pressure-
(reproduced with permission from Ref. [47] 2021 Elsevier). resistant floatation spheres with Si3 N4 ceramic material.
DONG et al. 2933
Zanocco et al.49 produced a dense Si3 N4 ceramic coating

on a biomedical grade commercially pure titanium (cp-Ti)
substrate by SLS, as shown in Figure 3F (reproduced with
permission from Ref. [49] 2020 Elsevier). This technology
may achieve rapid osseous fixation while resisting bacteria.
The dual benefits of an Si3 N4 ceramic coating are related
to its RNS surface chemistry and slowed kinetics that
favor osseointegration while inhibiting bacteria. This study
had reference significance for the research of additively
manufactured Si3 N4 ceramics in the field of biomedicine.
2.2 Photopolymerization
As the earliest form of AM, photopolymerization technol-

ogy fabricates 3D parts by selectively solidifying the liquid
resin in ceramic slurry through a photopolymerization
reaction (except LIS casting).98 The photopolymerization
technology of ceramics is one of the most promising F I G U R E 4 (A) Stereolithography apparatus (SLA)–3D printed
ceramic AM technologies that have been developed Al2 O3 –Si3 N4 gradient ceramic in complicated shape, (B)
in recent years due to its fast printing speed and high laser-induced slip (LIS)–3D printed Si3 N4 green body and its
precision.99 According to the principle of formation cross-section microstructure. Source: (A) Reproduced with
and the control system, photopolymerization can be permission from Ref. [50] 2020 Elsevier and (B) reproduced with
subdivided into SLA and DLP. permission from Ref. [51] 2017 Goeller
2.2.1 Stereolithography apparatus (SLA)

complicated shape without macro defects was obtained
SLA is relatively mature and the first AM technology to after debinding and sintering. This study provided a design
appear and achieve commercial application. During SLA, and fabrication strategy for multi-ceramic FGM based on
the slurry is selectively cured (from point to line, from line SLA–3DP technology.
to surface) by a point light source that comes from a laser. Like most AM processes, the printing process of LIS is a
The platform and print parts are placed in the slurry tank. layer-by-layer process, in which the CAD data of the part
After each layer is formed, the platform is lowered a cer- to be built is written in the individual layers, as shown in
tain distance. The curing process is repeated to prepare a Figure 2C. What is different between LIS and SLA is that
complete ceramic part, as shown in Figure 2B. the solvent of the LIS slurry is removed by local evapora-
Xing et al.50 fabricated an Al2 O3 –Si3 N4 functionally tion, which is achieved by intense laser radiation writing
graded material (FGM) part using SLA. They designed the desired geometry in a freshly deposited layer of slurry.
six groups of ceramic slurries, with an Si3 N4 content gra- With subsequent repetition of the steps of layer deposi-
dient of 20 vol.%, to realize the uniform transition from tion and laser drying, a part is built. The advantages of
Al2 O3 to Si3 N4 , as shown in Figure 4A (reproduced with LIS are that it avoids the hassle of having polymers in
permission from Ref. [50] 2020 Elsevier). The SLA param- the slurry and enables larger cured thickness. Lüchtenborg
eters were adjusted because the contents of Si3 N4 had et al.51 introduced the LIS process using Si3 N4 slurry as
significant effects on the slurries’ curing performance and an example. The process was designed to generate volu-
rheological behavior. They proposed a modified formula minous ceramic parts employing the layer-wise buildup
to evaluate the relationship between the actual minimum of parts with a layer thickness larger than .5 mm. Si3 N4
voidage of mixtures and the viscosities of their correspond- green body generated by the LIS process and the cross sec-
ing pastes and established a mathematical relationship tion of a green body are shown in Figure 4B (reproduced
between the Si3 N4 content and the curing thickness with permission from Ref. [51] 2017 Goeller). Although the
of paste. The FGM green body was printed in a layer microstructure of the parts produced with LIS revealed
thickness of 40 μm through a series of optimized laser flaws like pores and delaminations, the density of Si3 N4
power and scanning speed parameters for each group of ceramics after sintering had reached up to 99.4%, and the
slurry. Finally, a dense Al2 O3 –Si3 N4 gradient ceramic in 4-point flexural strength reached up to 323 MPa.
2934 DONG et al.
F I G U R E 5 (A) Digital light processing (DLP)–3D printed Si3 N4 ceramic cuboid, honeycomb, and lattice structures from preceramic
polymers, (B) TEM images and cure depth of Si3 N4 powders with different oxidation times, (C) TEM micrographs of raw Si3 N4 powder and
sample 1150◦ C-1 h, (D) DLP-3D printed Si3 N4 ceramic part, which used Si3 N4 powder coated with Al2 O3 –Y2 O3 sintering additives by chemical
co-precipitation method. Source: (A) Reproduced with permission from Ref. [52] 2019 John Wiley and Sons; (B) reproduced with permission
from Ref. [54] 2022 Elsevier; (C) reproduced with permission from Ref. [55] 2019 Elsevier; (D) reproduced with permission from Ref. [59] 2022
Elsevier
2.2.2 Digital light processing (DLP) (as shown in Figure 5A (reproduced with permission
from Ref. [52] 2019 John Wiley and Sons)). The 3-point
DLP is an AM technology developed on the basis of SLA. flexural strength of the DLP–3D printed Si3 N4 ceramic
Its forming direction is opposite to SLA. During DLP, the cuboid bars was measured to be 57.3 ± 8.7 MPa. The
slurry is selectively cured by a space light source that comes compressive strength values of the 2D-structured Si3 N4
from a UV light device. Usually, the UV light device is ceramic honeycomb and 3D-structured Si3 N4 ceramic lat-
below the slurry tank. The scraper spreads back and forth, tice were 65.5 and 5.12 MPa, respectively. Although the
and the platform rises and falls according to the preset pro- route of polymer-derived ceramic–based DLP is relatively
gram. Finally, the curing is conducted layer by layer, and a easy when printing, the mechanical property of the final
green body is obtained. The schematic diagram of the DLP ceramic is relatively low owing to the relatively low density
process is shown in Figure 2D. after pyrolysis. In recent years, most researchers have used
Wang et al.52 proposed and demonstrated, for the first ceramic slurry–based DLP to prepare high-performance
time, AM of simple and complex-shaped Si3 N4 ceramic Si3 N4 ceramic. However, there are still two main difficul-
components using DLP and pyrolysis from preceramic ties with DLP–3D printed Si3 N4 ceramic: (1) The curing
polymers polysilazanes. Simple Si3 N4 ceramic cuboid, 2D- thickness of the DLP–3D printed Si3 N4 slurry was not high
structured Si3 N4 ceramic honeycomb, and 3D-structured enough, and (2) the density of the DLP–3D printed Si3 N4
Si3 N4 ceramic lattice with high precision were fabricated ceramics after sintering was also not ideal.
DONG et al. 2935
Li et al.53 studied the rheology and curability characteri- result showed that the dispersion, wettability, and curing
zation of photosensitive slurries for DLP of Si3 N4 ceramic. thickness of Si3 N4 slurry were all improved by adding suit-
The study showed that the viscosity of Si3 N4 photocurable able silane coupling agents. Yang et al.58 first oxidized the
slurries was greatly affected by ambient temperature. Si3 N4 powder and then modified the oxidized powder with
With the temperature increased, the viscosity decreased the silane coupling agent. The oxidation process could
obviously. More importantly, they also proved that the effectively raise the curing thickness and stability of Si3 N4
Si3 N4 slurry had a lower curing ability when compared slurry. Additionally, modification by KH560 enabled the
with oxide ceramic slurries because of the large refractive improvement of the rheological properties and wettability
index and absorbance of Si3 N4 slurry. Therefore, improv- of Si3 N4 slurry. The result showed that the curing behav-
ing the curing ability of Si3 N4 ceramic slurry attracted ior and the rheological properties of Si3 N4 slurry could be
extensive research. One of the solutions was to use surface effectively enhanced by the oxidation process and silane
oxidation to attach an amorphous SiO2 layer to the surface coupling agent. In addition to oxidation treatment and
of Si3 N4 powder. Li et al.54 modified the surface of Si3 N4 surface modification of Si3 N4 powder, Li et al.59 put for-
powders through oxidation with different times (30, 60, ward coating the surface of Si3 N4 powder with Al2 O3 –Y2 O3
90, and 120 min) in order to reduce the refractive index sintering additives by chemical co-precipitation method.
difference between the ceramic particle surface and Finally, Si3 N4 ceramic was successfully fabricated by DLP
photosensitive resin. The reaction between Si3 N4 and O2 (as shown in Figure 5D (reproduced with permission from
during oxidation process can be shown in the following Ref. [59] 2022 Elsevier)). The result showed that when the
reaction: content of Al(NO3 )3 and Y(NO3 )3 solutions was 20 ml/100-
g Si3 N4 , the curing thickness of the slurry prepared with
Si3 N4 (s) + 3O2 (g) → 3SiO2 (s) + 2N2 (g) (1) the coated Si3 N4 powder, which was 47.9 ± 1.2 μm, was
nearly 13% higher relative to the slurry prepared with
TEM images and curing thickness of Si3 N4 powders with raw powder. These previous studies were all through the
different oxidation time are shown in Figure 5B (repro- additional treatment of Si3 N4 powder to improve the cur-
duced with permission from Ref. [54] 2022 Elsevier). Com- ing properties and rheological properties, factors such as
pared with raw ceramic powder without any oxidation, particle inherent property (color, size), resin, dispersant,
the light absorbance of the oxidized Si3 N4 was apparently and photoinitiator could also affect the curing properties
lower and decreased as prolonging the oxidation time. and rheological properties of Si3 N4 slurries. Liu et al.60
The result showed that the curing thickness increased as investigated the mechanism of how the powder color and
the light absorption of ceramic powder decreasing. Huang particle size affected the curing ability of Si3 N4 slurries.
et al.55 also oxidized Si3 N4 powder at different tempera- Zou et al.61 compared the curing behavior of different func-
tures and times (1150◦ C-1 h, 1150◦ C-3 h, 1200◦ C-1 h, and tional groups and RI of resin monomer, and the dispersion
1200◦ C-1 h). TEM micrographs of raw Si3 N4 powder and effect of three commercial dispersants was investigated
the sample 1150◦ C-1 h are shown in Figure 5C (repro- systemically. Wu et al.66,67 also studied the influence of
duced with permission from Ref. [55] 2019 Elsevier). At type and content of photosensitive resin and dispersant
the exposure energy of 500 mJ/cm2 , the curing thickness on Si3 N4 slurries for LCD mask stereolithography (an AM
of the raw Si3 N4 powder was 34 μm. After oxidation, the technology similar to DLP). Cao et al.62 investigated the
curing thicknesses of the sample 1150◦ C-1 h, 1150◦ C-3 h, effect of initiators on the curing effect of Si3 N4 slurries.
1200◦ C-1 h, and 1200◦ C-1 h increased by 8, 13, 17, and Their findings revealed that choosing right component
34 μm compared to raw Si3 N4 powder, respectively. This is type and content could help improve the performance of
because both the light absorbance and refractive index of Si3 N4 slurries to some extent.
the oxidized Si3 N4 powder reduced. Adding surface mod- For the density issue of Si3 N4 ceramic, Rao et al.63 also
ifiers was another way to increase the curing thickness of fabricated dense Si3 N4 ceramic by combining DLP with
Si3 N4 slurry. Liu et al.56 prepared Si3 N4 slurry with 45 vol.% field-assisted sintering through using CeO2 as sintering
solid loading successfully by using KH560 and Darvan as additive. They considered that the grain boundary slipping
the surface modifier and the dispersant, respectively. They played a dominating role in the densification process of
demonstrated that surface modification of submicro-Si3 N4 DLP–3D printed Si3 N4 ceramic. During the field-assisted
powder could be used to improve the rheological behav- sintering, CeO2 sintering additive segregated in the grain
ior and the curing ability of Si3 N4 slurry effectively. They boundaries and insoluble in the Si3 N4 grains. Finally,
also studied the effects of the silane coupling agent, which a dense Si3 N4 ceramic with good mechanical properties
was directly used as the surface modifier and dispersant, was fabricated. Therefore, the density of Si3 N4 ceramics
on the rheological property, stability, wettability, and cur- after photocuring may be controlled by the content and
ing performance of the Si3 N4 slurry in another paper.57 The composition of rare-earth elements.
2936 DONG et al.
F I G U R E 6 (A) Digital light processing (DLP)–3D printed SiAlON ceramic with complex architecture, (B) a broadband microwave
transparent Si3 N4 –SiO2 composite ceramic complex structures fabricated by DLP and sintering in air atmosphere, (C) the schematic synthetic
reaction process of oxidation of Si3 N4 at high temperatures. Source: (A) Reproduced with permission from Ref. [64] 2020 MDPI; (B)
reproduced with permission from Ref. [65] 2021 Elsevier; and (C) reproduced with permission from Ref. [65] 2021 Elsevier
In addition to the previously mentioned literature, there of Si3 N4 -based materials with excellent mechanical and
are some reports on DLP–3D printed Si3 N4 -related materi- dielectric properties by photopolymerization technology.
als. Altun et al.64 manufactured a variety of Si3 N4 -based
ceramic parts, SiAlON ceramics, with complex architec-
ture by DLP (as shown in Figure 6A (reproduced with per- 2.3 Material extrusion
mission from Ref. [64] 2020 MDPI)). The obtained SiAlON
ceramic bodies with a relative density of 99.8% exhibited Material extrusion is an AM process, in which material
a biaxial strength of 764 MPa and a hardness of 1500 is selectively deposited by extrusion from a nozzle. It is
(HV10). Chen et al.65 fabricated a broadband microwave also an early and widely used AM technology. Material
transparent complex structure Si3 N4 –SiO2 composite with extrusion has the advantages of low cost, many applica-
excellent performance through DLP and sintering in air ble material systems, simple and convenient operation.
atmosphere (as shown in Figure 6B (reproduced with per- According to the curing method, material extrusion can be
mission from Ref. [65] 2021 Elsevier)). The strength of divided into normal temperature extrusion and hot extru-
Si3 N4 –SiO2 ceramic sintered at 1350◦ C was 77 ± 5 MPa. The sion. Normal temperature extrusion mainly includes DIW
relative permittivity of the as-prepared Si3 N4 –SiO2 ceramic or robocasting, whereas hot extrusion mainly includes
was within the range of less than 4, and the loss tan- FDM.
gent could be below than .003. These results showed that
the DLP–3D printed Si3 N4 –SiO2 ceramic exhibited excel-
lent wave-transparent performance. Besides, they also 2.3.1 Direct ink writing (DIW) or
elaborated the synthetic reaction process of oxidation of robocasting
Si3 N4 at high temperatures, which is shown in Figure 6C
(reproduced with permission from Ref. [65] 2021 Else- DIW or robocasting builds 3D parts by stacking filaments
vier). This work provided a reference for the preparation layer by layer into a set route through a nozzle, as shown
DONG et al. 2937
F I G U R E 7 (A) Cross section of a direct ink writing (DIW)-3D printed Si3 N4 /MoSi2 multilayer green sample, (B) Si3 N4 green parts with
controllable shape and architecture for biomedical applications, (C) robocasting-3D printed highly porous Si3 N4 scaffolds with a pattern of
macroporous cavities of 650–700 μm, (D) DIW-3D printed three complex-shape porous Si2 N2 O ceramics strengthened by directional β-Si3 N4 ,
(E) formation mechanism of Si2 N2 O and Si3 N4 at 1250◦ C, (F) UV-assisted DIW and the as-prepared SiC/Si3 N4 composites. Source: (A)
Reproduced with permission from Ref. [69] 2011 John Wiley and Sons; (B) reproduced with permission from Ref. [70] 2016 John Wiley and
Sons; (C) reproduced with permission from Ref. [71] 2020 Elsevier; (D) reproduced with permission from Ref. [72] 2020 Elsevier; (E)
reproduced with permission from Ref. [73] 2022 Elsevier; (F) reproduced with permission from Ref. [74] 2022 Elsevier
in Figure 2E. DIW employs relatively low solid loading et al.70 prepared Si3 N4 ceramic with controllable shape and
ceramic ink as the raw material, whereas robocasting uses architecture for biomedical applications using a robocast-
high solid loading ceramic paste as the raw material.100 ing technique (as shown in Figure 7B (reproduced with
They can make parts from different materials because permission from Ref. [70] 2016 John Wiley and Sons)).
they have a variety of sizes of nozzles. Apart from that, Two samples (including macro-porous part and solid part)
their cost is relatively low. But the printing accuracy of were prepared after hot isostatic pressing sintering. As-
DIW or robocasting is not high enough, which also lim- fabricated solid samples in the shape of beams showed a
its their development in the preparation of Si3 N4 ceramic flexural strength of 552 ± 68 MPa. Samples with a macrop-
components with high accuracy. orous grid-like architecture (porosity = 56.5%; pore width
Cappi et al.68 prepared an aqueous Si3 N4 ink with a solid = 350 μm) showed a flexural strength of 89 ± 11 MPa.
loading of 30 vol.% and manufactured high-performance Their research indicated that robocasting combined with
complex-shaped Si3 N4 ceramics by DIW successfully. The hot isostatic pressing sintering provided a viable manufac-
sintered Si3 N4 ceramic part had a density of 3.18 g/cm3 , turing approach to create Si3 N4 implants with controllable
a hardness value (HV .2) of 17, and a fracture tough- shape and architecture for orthopedic and dental surgery
ness KIC of 4.4 MPa m1/2 , respectively. In their further applications. Similarly, Sainz et al.71 fabricated highly
study,69 they obtained dense and delamination-free Si3 N4 porous Si3 N4 scaffolds by robocasting with a pattern of
and MoSi2 samples as well as multilayer parts (as shown macroporous cavities of 650–700 μm (Figure 7C [repro-
in Figure 7A [reproduced with permission from Ref. [69] duced with permission from Ref. [71] 2020 Elsevier]).
2011 John Wiley and Sons]) by adjusting the aqueous Si3 N4 The potential application of robocasting–3D printed Si3 N4
and MoSi2 inks. Their study showed the high potential scaffold for bone regeneration was demonstrated. In addi-
of DIW for producing complex-shaped non-oxide ceram- tion to the previous research reports, there are also some
ics and even multifunctional parts in one process. Zhao reports on Si3 N4 related materials by DIW. Jin et al.72
2938 DONG et al.
fabricated three complex-shaped porous Si2 N2 O ceram- printed green pieces could be removed and sintered to
ics strengthened by directional β-Si3 N4 using DIW, as densities and strengths comparable to those achieved by
shown in Figure 7D (reproduced with permission from traditional ceramic processing methods. This work had ref-
Ref. [72] 2020 Elsevier). The mechanical properties of the erence significance for FDM fabrication of Si3 N4 ceramic
as-prepared composite were greatly improved due to the components. However, build defects could be encountered
addition of high-aspect-ratio β-Si3 N4 grains. This study in improperly built FDM–3D printed parts. Wu et al.76
provided a reference for fabricating high-performance suggested that warm isostatic pressing (WIP’ing) at tem-
anisotropic complex-structured ceramics. Jiang et al.73 pre- peratures above 70◦ C might be effective in the elimination
pared Si2 N2 O–Si3 N4 ceramics for radome materials by of build defects. However, after sintering, it was seen from
DIW combined with low-temperature sintering. Strictly the low fracture strength and the fracture surface features
speaking, Si2 N2 O–Si3 N4 ceramics was achieved through that the defects were still not completely healed. Although
indirect AM. First, the lattice of Si-SiO2 green body was WIP’ing was successful in visibly removing internal voids
printed via DIW, then the Si2 N2 O-Si3 N4 ceramic was suc- in FDM-3D printed parts, their strength was still limited.
cessfully prepared after the green body was sintered in Therefore, further investigations on the effects of pres-
nitrogen at a relatively low temperature. The formation sure and temperature would be suggested. Rangarajan
mechanism of Si2 N2 O and Si3 N4 at 1250◦ C is shown in et al.77 explored the rheological and mechanical proper-
Figure 7E (reproduced with permission from Ref. [73] ties required for a successful FDM feedstock material. At
2022 Elsevier). The as-obtained Si2 N2 O–Si3 N4 ceramic had 185◦ C, the viscosity of filament feedstock with 55 vol.% was
an apparent porosity of 42.73%, a compressive strength measured to be less than 50 Pa s in the shear rate range
of 24.7 MPa, a dielectric constant of 4.89, and a loss of 70–1128 s−1 . They also verified the ratio of the value of
tangent of .0054, respectively. Excellent dielectric prop- pressure to drive the extrusion to the filament buckling
erties were achieved due to the high porosity, the high stress, ΔP/σE , must be <1.1 for efficient pumping during
proportion of Si2 N2 O phase, and no residual silicon. Nor- FDM. It was necessary to quantitatively understand the
mally, almost all DIW research of Si3 N4 ceramic was relationship between ΔP and flow, geometric, and mate-
based on Si3 N4 inks. However, DIW has high require- rial rheological parameters for greater flow control during
ments for the rheology of ceramic ink. Clarkson et al.74 FDM. In their further paper,78 dense, homogenous, near-
created SiC/Si3 N4 composites through UV-assisted DIW of net-shape Si3 N4 parts were fabricated by using proper
a ceramic powder (Si3 N4 )–preceramic polymer (polycar- build parameters and printing routes. They identified and
bosilane) suspension, as shown in Figure 7F (reproduced characterized build parameter–dependent heterogeneities
with permission from Ref. [74] 2022 Elsevier). By cou- and defects that arise from the FDM process and evaluated
pling UV and DIW, the requirements for ink rheology were the effects of build orientation on the mechanical proper-
largely reduced to a certain extent. This article provided a ties of structural Si3 N4 parts made by FDM. The results
reference for the preparation of complex-shaped ceramic showed that mechanical properties of Si3 N4 parts were
composites by combining different AM techniques. isotropic. Therefore, the mechanical properties of Si3 N4
parts in specific directions could be enhanced by doping
the FDM filament feedstock with β-Si3 N4 seed particles.
2.3.2 Fused deposition modeling (FDM) Similarly, McIntosh et al.79 proved that warping of parts
became a serious problem when using an all-aligned road
FDM process is a hot extrusion forming process, which vector build strategy (i.e., all 0◦ or all 90◦ road vectors).
involves heating wire composed of ceramic powder and In contrast, using alternating +45◦ /−45◦ crosshatched
polymer and extruding through a nozzle followed by solid- road vectors could avoid warping. A schematic represen-
ification onto a forming table into the desired geometry. tation of warpage effects that resulting from is shown in
The basic process of FDM is shown in Figure 2F. FDM Figure 8B (reproduced with permission from Ref. [79] 2008
also has the advantages of material extrusion. However, the John Wiley and Sons). Meanwhile, this article indicated
shortcoming of the low part surface accuracy is also obvi- the FDM process could be utilized to create advanced
ous due to volume expansion during heating. In addition to multifunctional ceramic components.
this, the residue of FDM filament during heating can cause
nozzle blockage.
Agarwala et al.75 produced complex-shaped Si3 N4 parts 2.4 Other additive manufacturing
with high green density and high performance by FDM technologies
successfully, as shown in Figure 8A (reproduced with
permission from Ref. [75] 1996 The University of Texas In addition to the aforementioned AM technologies, BJ
at Austin). It was shown that the binder in FDM–3D and LOM were also reported to fabricate Si3 N4 ceramic.
DONG et al. 2939
F I G U R E 8 (A) Fused deposition modeling (FDM)-3D printed complex-shaped Si3 N4 parts with high green density, (B) schematic
representation of warpage effects. Source: (A) Reproduced with permission from Ref. [75] 1996 The University of Texas at Austin and (B)
reproduced with permission from Ref. [79] 2008 John Wiley and Sons
2.4.1 Binder jetting (BJ) mechanical properties and porosity, Lurie et al.83 analyzed
the effects of porosity and pore shapes on the elastic prop-
The procedure for the BJ of ceramic is presented in erties of Si3 N4 ceramic obtained by BJ and pressureless
Figure 2G. During BJ, the roller spreads the ceramic pow- reaction sintering. Silicon green bodies in powder bed after
der of the powder tank under the nozzle. After that, the BJ and Si3 N4 ceramic samples after sintering is shown
nozzle jets the binder to the predetermined areas. Then, in Figure 9A (reproduced with permission from Ref. [83]
the forming platform descends to a certain height, so back 2017 Springer). They found that the low elastic modulus of
and forth. Finally, a 3D ceramic green body is formed on the ceramics was mostly determined by the shape of the
the forming platform. BJ has many potential advantages. pores and their volume fraction. However, evaluation of
For example, it can work with virtually any powdered feed- the strength of the ceramic was a much more complicated
stock and can incorporate FGMs.101 However, the density problem, because it was difficult to establish a quantitative
of parts made with BJ is usually very low. Therefore, most correlation between the changes in the elastic and strength
researchers use BJ to prepare porous Si3 N4 ceramics. properties of porous materials in the general case. Xiao
Rabinskiy et al.80 fabricated Si3 N4 ceramics by indirect et al.84 synthesized a (SiCw –Si3 N4w )/(Si3 N4 –SiC) compos-
AM technology. First, they created silicon green body using ite via BJ, nitridation process, and a subsequent chemical
BJ, and then porous Si3 N4 ceramic was obtained using vapor infiltration (CVI) process. They studied the effects of
pressure less reaction sintering. However, the porosity of whiskers content on the mechanical properties. Compared
the as-sintered Si3 N4 sample reached up to 70%, result- to the bulks without whiskers, the result showed that the
ing in poor mechanical properties. In another paper,81 flexural strength increased by 63.6% when the SiCw content
they investigated the effects of different types of binders was 3 wt.%. In addition to the poor mechanical proper-
on porosity and properties of samples. The results proved ties of Si3 N4 parts prepared by indirect BJ technology, this
that denser and stronger specimens were prepared using method also had many other limitations. Therefore, Cheng
a binder based on epoxy, compared to the water-based et al.85 prepared Si3 N4 ceramics by direct BJ and stud-
binder. The porosity of the porous Si3 N4 sample prepared ied the effects of the deposition time and heat treatment
with epoxy-based binders was reduced to 30%–40%. They of CVI on the microstructure and properties of porous
proposed to further reduce the porosity of green bodies Si3 N4 –Si3 N4 composites. With increasing the deposition
and improved mechanical properties by additional com- time, the weight and density of porous Si3 N4 –Si3 N4 com-
paction of green bodies.82 After additional compaction, the posite increased and the porosity decreased. In the future,
porosity of the porous Si3 N4 ceramic decreased from 30%– it is hoped that more research should focus on direct BJ
40% to 15%–25%, and the flexural strength increased from preparation of Si3 N4 ceramic.
53 ± 2 to 77 ± 5 MPa, respectively. The results showed that 3DP not only has a similar jetting process to BJ but also
the method of additional compaction was of great help has the same advantages and disadvantages (Figure 2H).
in improving the mechanical properties of porous Si3 N4 Actually, 3DP is another name for BJ.
ceramic, which also confirmed that the mechanical prop- Li et al.86 fabricated porous Si3 N4 ceramic using tech-
erties of the as-sintered Si3 N4 ceramic strongly depend on niques of oxidation-bonding combined with sol–gel infil-
their porosity. To further study the relationship between tration sintering (OB–IS), cold-pressing combined with
2940 DONG et al.
F I G U R E 9 (A) Silicon green bodies in powder bed after binder jetting (BJ) and Si3 N4 ceramic samples after sintering, (B) 3D printed
Si3 N4 part, (C) Si3 N4 –SiOC ceramic with a complex shape by 3D printing (3DP) combined with direct nitridation and polymer infiltration and
pyrolysis (PIP), (D) complicated shapes of green tapes and Si3 N4 samples before and after sintering, (E) SEM images of Si3 N4 samples sintered
by hot pressing (HP) and spark plasma sintering (SPS). Source: (A) Reproduced with permission from Ref. [83] 2017 Springer; (B) reproduced
with permission from Ref. [88] 2015 Elsevier; (C) reproduced with permission from Ref. [89] 2017 Springer; (D) reproduced with permission
from Ref. [91] 2015 Elsevier; and (E) reproduced with permission from Ref. [93] 2006 Elsevier
pressureless sintering (CP–PS), and 3D-printing combined Si3 N4 part is shown in Figure 9B (reproduced with permis-
with pressureless sintering (3DP–PS). Comparing Si3 N4 sion from Ref. [88] 2015 Elsevier). They investigated the
ceramics prepared by the other two techniques, the Si3 N4 effects of SiC nanowires on the microstructure, dielectric
ceramic by 3DP–PS possessed a high porosity of 68% due to properties, and an absorption of the Si3 N4 –SiC ceramic.
the incompact stack of Si3 N4 particles in the preform. The The result showed that the lowest reflection coefficient of
porous Si3 N4 ceramic by 3DP possessed excellent dielec- Si3 N4 –SiC ceramic with 10.5-wt.% SiC attained 57 dB at
tric properties while showing poor mechanical properties the sample thickness of 2.3 mm, which indicating 99.999%
(a flexural strength of 13 MPa, and a fracture toughness of electromagnetic (EM) wave power was absorbed. This
of .3 MPa m1/2 , respectively) due to the high porosity. paper demonstrated that SiC nanowires–reinforced Si3 N4 –
Therefore, they used CVI to improve the mechanical prop- SiC ceramic was a promising EM absorbing material. In
erties of the porous Si3 N4 ceramic in another study.87 After their further article,89 twinned SiC nanowires–reinforced
CVI for 40 h, the mechanical properties of the porous Si3 N4 –SiOC composites (as shown in Figure 9C [repro-
Si3 N4 ceramic were greatly improved (a flexural strength duced with permission from Ref. [89] 2017 Springer]) were
of 95 MPa, and a fracture toughness of 2.4 MPa cm1/2 , successfully fabricated through a joint process of 3DP,
respectively) because of the increase in the connection direct nitridation, and PIP. The author not only designed
strength among Si3 N4 particles, whereas the dielectric complex-shaped Si3 N4 –SiOC ceramic but also investigated
properties were reduced slightly due to the slight decrease its EM shielding and mechanical properties. With the
in porosity. The result showed that porous Si3 N4 ceramic increase of the infiltration cycle number, the porosity went
manufactured by 3DP combined with CVI was an excellent down from 70% to 21%, the average SET (the total loss of
wave-transparent material. In addition to CVI, another the EM interference shielding) rose from 2 to 35 dB with
possible way to enhance the mechanical properties of a lower SER (the reflection loss) of 7 dB and higher SEA
3DP Si3 N4 ceramic is to synthesize ceramic matrix com- (the absorption loss) of 28 dB. It was indicated that more
posites. Duan et al.88 fabricated twinned SiC nanowires than 99.9% of the EM energy was reflected and absorbed,
reinforced Si3 N4 composite by the combination of 3DP and and only less than .1% of the EM energy was transmitted.
polymer infiltration and pyrolysis (PIP). The as-prepared Meanwhile, the flexural strength reached 63 MPa. These
DONG et al. 2941
results demonstrated that the SiC nanowires–reinforced Si3 N4 samples. Si3 N4 samples sintered by SPS exhibited a
Si3 N4 –SiOC ceramic was a promising EM shielding and higher fracture toughness (8.1 ± .3 MPa m1/2 ), whereas a
structural material. This paper provided a reference for lower strength (650 ± 23 MPa) than that sintered by HP
the structural–functional integration of additively manu- (7.6 ± .4 MPa m1/2 , 725 ± 26 MPa). In addition to improving
factured Si3 N4 ceramic. performance by increasing density, Pope et al.94 designed
three microstructural variants (second-phase interface
compositions, FGMs, and oriented microstructures) to
2.4.2 Laminated object manufacturing enhance the properties of the multilayer Si3 N4 structure.
(LOM) The results confirmed that all three methods could play a
role in improving mechanical properties. Among the three
LOM forms parts by sheets as raw material. The basic structural design methods (second-phase interface com-
process of LOM is shown in Figure 2I. In this process, positions, FGMs, and oriented microstructures), interface
individual sheets are rolled onto the forming platform, the design is the most common method, because the intro-
binder is laid down on the sheet, and another sheet is then duction of interfacial second-phase materials improved
rolled onto the binder, fusing the two layers together. A performance while considering the designability.
laser then cuts the cross-sectional outline of the part only
one layer in thickness into laminated sheets. The process
is then repeated with successive layers. The excess mate- 3 PERSPECTIVES
rial supports the part during the process and is removed
during post-processing.102 This method offers considerable Based on the previous summary of the current advances
savings in cost and time. The key processing steps in the of AM technologies of Si3 N4 ceramic, prospects are fore-
preparation of LOM Si3 N4 components include Si3 N4 tape casted.
fabrication, green shape forming using LOM, post-LOM
processing, and densification.90
Rodrigues et al.90 demonstrated that LOM was a viable 3.1 Densification and strengthening
method for preparing functional Si3 N4 ceramic with good
physical and mechanical properties. The room tempera- As we all know, Si3 N4 ceramic is difficult to densify
ture and high temperature (1260◦ C) flexural strengths of because of the covalent nature of Si–N bonding. Moreover,
Si3 N4 ceramic were in the range of 700–900 and 360– some AM techniques are prone to a lot of defects during the
400 MPa, respectively, and the fracture toughness averaged manufacturing process, which will also affect the density
from 5.5 to 7.5 MPa m1/2 , which were comparable to and mechanical performance of the ceramic products.
those reported for conventionally prepared Si3 N4 ceramics. During AM, it is important to quantitatively characterize
Domestic Liu et al.91 also proved the feasibility of prepar- and analyze the defects within ceramic. X-ray-computed
ing Si3 N4 ceramic components by aqueous tape casting tomography (X-CT) can provide adequate information on
in combination with LOM. Complicated shapes of green the defect distribution of the material. Lüchtenborg et al.51
tapes and Si3 N4 samples before and after sintering and sec- generated Si3 N4 ceramic green bodies with high particle
tion view of the Si3 N4 components are shown in Figure 9D packing density using LIS casting. Meanwhile, a whole
(reproduced with permission from Ref. [91] 2015 Else- sample and a bending bar were characterized using μCT
vier). A relatively high density (∼93.7%) and good strength to determine density and local pore distribution, as shown
(∼475 MPa) of the sintered components were obtained. in Figure 10A (reproduced with permission from Ref. [51]
Park et al.92 fabricated a complex-shaped Si3 N4 part with 2017 Goeller). In the μCT scan of an entire sample, pores
aligned whisker seeds using LOM. CIP was used to make with a hemispherical shape and larger flat areas of flaws
dense ceramic components. The results showed that the were visible. The diameter of these pores reached 420 μm
body was sintered to 98.5% of theoretical density, and the and delaminations or cracks located parallel to each other
Vickers hardness was 13.9 ± .3 GPa. The fracture tough- and parallel to the layers. The porosity of the part was
ness values parallel and perpendicular to the stacking calculated to be .41% ± .47%. In the μCT scan of a bending
direction were 6.1 ± .4 and 5.2 ± .2 MPa m1/2 , respec- bar sample, large and small pores were detected, and the
tively. Zhang et al.93 prepared Si3 N4 samples through largest pore has a diameter of 420 μm. A large part of the
aqueous tape casting, laminating, hot pressing (HP), and reason for the low number of defects in LIS is that there
spark plasma sintering (SPS). SEM images of the Si3 N4 was no photosensitive resin in the paste required for LIS.
samples by HP and SPS are shown in Figure 9E (repro- Diener et al.103 investigated the influence of DIW printing
duced with permission from Ref. [93] 2006 Elsevier). Both patterns on residual pore sizes and pore distributions
HP and SPS were proved to be effective for densifying by X-ray microtomography and tried to establish the
2942 DONG et al.
F I G U R E 1 0 (A) μCT reconstruction of a scan of a whole Si3 N4 sample and a part of a bending bar, (B) μCT image of a cross section taken
at the middle of sintered bars manufactured using different printing patterns, (C) the microstructures of fabricated (SiCw –Si3 N4w )/(Si3 N4 –SiC)
composite and the bending strength, out-plane (⊥) and in-plane (//) compressive strengths of the composites with different SiCw contents, (D)
the effects of the SiC mass fraction and the addition of Al2 O3 and mullite fibers on the properties of the Si3 N4 –SiC/SiO2 composites. Source:
(A) Reproduced with permission from Ref. [51] 2017 Goeller; (B) reproduced with permission from Ref. [103] 2021 Elsevier; (C) reproduced
with permission from Ref. [84] 2018 Elsevier; and (D) reproduced with permission from Ref. [47] 2021 Elsevier
relationship between the residual pore structure and the twinned SiC nanowires by 3DP and PIP to improve
printing parameters. μCT image of a cross section taken at both the real and the imaginary parts of permittivity.
the middle of sintered bars manufactured using different They demonstrated that SiCNWs –Si3 N4 ceramics had a
printing patterns is shown in Figure 10B (reproduced with superior microwave-absorbing ability. Xiao et al.84 inves-
permission from Ref. [103] 2021 Elsevier). No clear effect tigated the effect of SiCw content on the mechanical
on the final pore characteristics of Si3 N4 bars fabricated performance of porous (SiCw –Si3 N4w )/(Si3 N4 –SiC) com-
using different printing patterns was observed. However, posite by BJ and CVI. The microstructures of the as-
adjusting the distance between adjacent filament centers fabricated (SiCw –Si3 N4w )/(Si3 N4 –SiC) composite and the
and changing the ink rheology can help reduce the final flexural strength, out-plane (⊥) and in-plane (//) com-
porosity of sintered Si3 N4 parts. In summary, we can pressive strengths of the composites with different SiCw
achieve the purpose of densification and strengthening contents are shown in Figure 10C (reproduced with per-
through defect characterization and controlling. mission from Ref. [84] 2018 Elsevier). The flexural strength
During sintering process, the density of the as-obtained increased monotonously in the interval from 0 to 3 wt.%,
Si3 N4 ceramic is generally difficult to be completely dense which indicated that SiCw presented a good strengthen-
by pressureless sintering. Generally, pressure sintering, ing effect in this range. In addition to fiber-reinforced
reaction sintering, CVI, SPS, and HP are used to promote ceramic matrix composites, Yu et al.47 successfully man-
the densification of Si3 N4 ceramic. Table 1 lists and com- ufactured Si3 N4 –SiC/SiO2 composite part by SLS and
pares the relative density, strength, and fracture toughness infiltration processes and investigated the effects of the
of Si3 N4 ceramics prepared by different AM technologies. SiC mass fraction and the addition of mullite fibers on the
The reason for the higher density and strength of properties of the Si3 N4 –SiC/SiO2 composites. Figure 10D
Si3 N4 prepared by LIS and LOM was high curing thick- (reproduced with permission from Ref. [47] 2021 Else-
ness and applied pressure, respectively. Another approach vier) showed that with an increase in the mass fraction
to strengthening and toughening was to prepare Si3 N4 - of SiC, the flexural strength of the samples increased
based ceramic composites by adding a second phase to the maximum value of 42.45 MPa at 48.5-wt.% SiC
into the Si3 N4 ceramic matrix. Duan et al.88 fabricated first and then decreased. The flexural strength of the
porous Si3 N4 composites reinforced with in situ–formed Si3 N4 –SiC/SiO2 composites improved significantly with
DONG et al. 2943
T A B L E 1 Comparison of the relative density, strength, and fracture toughness of Si3 N4 ceramics fabricated by different additive
manufacturing (AM) techniques
Fracture
AM Relative Strength toughness
Material technology Posttreatment density (%) (MPa) (MPa m1/2 ) Ref.
Si3 N4 –SiC/SiO2 SLS Sol-infiltration 92.05 42.4a – 47
b
Si3 N4 LIS Pressure sintering 99.4 323 – 51
Si3 N4 DLP Pyrolysis 88.43 57.3 ± 8.7a – 52
Si3 N4 DLP Pressure sintering 95 – 5.82 ± .42 56
Si3 N4 DLP Pressureless sintering 85.4 ± .3 149.2 ± 1.9a – 59
Si3 N4 DLP Field-assisted sintering 95.8 – 6.57 ± .07 63
Si3 N4 –SiO2 DLP Pressureless sintering 82.3 77 ± 5a – 65
Si2 N2 O–Si3 N4 DIW Reaction sintering 57.27 16.9a 24.7c – 73
Porous Si3 N4 BJ Pressureless sintering 60 − 70 53 ± 2a – 82
Porous Si3 N4 3DP CVI 63.98 47 ± 2a – 86
Porous Si3 N4 3DP Pressureless sintering + 39 95a 2.4 87
CVI
Si3 N4 LOM Pressure sintering 93.7 475a – 91
Si3 N4 LOM HP 99.72 725 ± 26 a
7.6 ± .4 93
SPS 99.78 650 ± 23a 8.1 ± .3
Abbreviations: 3DP, 3D printing; BJ, binder jetting; CVI, chemical vapor infiltration; DIW, direct ink writing; HP, hot pressing; LIS, laser-induced slip; LOM,
laminated object manufacturing; SLS, selective laser sintering; SPS, spark plasma sintering.
a
Three-point flexural strength.
b
Four-point flexural strength.
c
Compressive strength.
the addition of mullite fibers, and the incorporation of the mechanical properties; however, there are only a few stud-
mullite fibers played an important role in improving the ies on the EM properties and biological properties of
mechanical properties of the Si3 N4 –SiC/SiO2 composites. additively manufactured Si3 N4 .
Usually, there are mainly two types of AM technologies Chen et al.65 studied the effect of sintering temperature
for fiber-reinforced Si3 N4 ceramic matrix composites: indi- on the real permittivity and the tangent loss of Si3 N4 –SiO2
rect AM and direct AM. The indirect AM methods first (as shown in Figure 11A (reproduced with permission from
prepare the Si3 N4 ceramic green body by common AM Ref. [65] 2021 Elsevier)). The real permittivity reached
technologies, then fabricate the composite green part via a maximum value at 1350◦ C and the minimum value at
in situ reactions, and finally sinter to obtain the final 1250◦ C, and the tangent loss decreased with the increase
body. Different from indirect AM, direct AM methods of temperature. Lower tan δ means better transmission
including fabrication of fiber reinforced Si3 N4 ceramic rate, which indicated that Si3 N4 –SiO2 could be a potential
matrix composite green part by various AM technologies, transparent material. Cheng et al.85 indicated the excellent
debinding, and sintering. Whether indirect AM or direct EM wave-transparent performance of porous Si3 N4 –Si3 N4
AM, the introduction of high-strength, high elasticity composite ceramics (as shown in Figure 11B (reproduced
fibers (including short and continuous fibers) as rein- with permission from Ref. [85] 2015 Elsevier)). When the
forcements is an effective method to improve the tough- CVI processing time was increased from 0 to 12 h, the
ness and reliability of Si3 N4 ceramics.104 In the future, dielectric constant gradually increased from 1.72 to 3.60;
AM of fiber-reinforced Si3 N4 ceramics will have broad however, the dielectric loss always remained less than .01.
prospects due to its excellent material properties and wide After heat treatment, the dielectric constant got a slight
application. increase from 3.60 to 3.70 with the dielectric loss still main-
taining lower than .01. Duan et al.89 also investigated EM
interference shielding properties of Si3 N4 –SiOC compos-
3.2 Functional design ites. A schematic illustration of the shielding mechanism
in Si3 N4 -SiOC ceramics is shown in Figure 11C (repro-
Si3 N4 ceramic has excellent EM properties and bio- duced with permission from Ref. [89] 2017 Springer).
logical properties. Most researchers only focus on its Zanocco et al.49 also produced an antibacterial and
2944 DONG et al.
F I G U R E 1 1 (A) Dielectric constant of Si3 N4 –SiO2 ceramics, (B) dielectric properties in 8.2–12.4 GHz of porous Si3 N4 –Si3 N4 composite
ceramics, (C) schematic illustration of the shielding mechanism in Si3 N4 –SiOC ceramics, (D) schematic draft of osteoblast and bacteria
interactions at the biomolecular interface with Si3 N4 . Source: (A) Reproduced with permission from Ref. [65] 2021 Elsevier; (B) reproduced
with permission from Ref. [85] 2015 Elsevier; (C) reproduced with permission from Ref. [89] 2017 Springer; and (D) reproduced with
permission from Ref. [49] 2020 Elsevier
osteogenic Si3 N4 coating on an orthopedic titanium sub- 3.3 Structure–function integration

strate. The Si3 N4 coating showed concurrent osteogenic
and antibacterial behaviors similar to those observed in In addition to realizing the functional design of materi-
bulk Si3 N4 bioceramic implants. A schematic draft of als, the biggest feature of AM is that it can achieve flexible
osteoblast and bacteria interactions at the biomolecular design of structures, which has also attracted the attention
interface with Si3 N4 is shown in Figure 11D (reproduced of a large number of researchers.
with permission from Ref. [49] 2020 Elsevier). Zhao et al.70 DLP-based additively manufactured Al2 O3 ceramic lat-
fabricated Si3 N4 implants with a fibrous surface morphol- tice structures (CLSs) with different structural configura-
ogy or surface roughness by DIW, which had been found to tions were in the work of Zhang et al.105 They designed
have a beneficial effect in endowing Si3 N4 implants with and fabricated three structural configurations of body-
antibacterial activity. Sainz et al.71 manufactured 3D-Si3 N4 centered cubic, octet, and modified body-centered cubic,
scaffolds intended for bone tissue engineering by DIW. as shown in Figure 12A (reproduced with permission
They demonstrated the feasibility of 3D-Si3 N4 printed from Ref. [105] 2022 Taylor and Francis Ltd.). Moreover,
materials as robust scaffolds with a high bioactivity and the effect of structural configuration on the mechanical
affinity for proteins and confirmed its potential applica- properties and failure modes of CLS was systematically
tion for bone tissue engineering. Compared to mechanical studied in their work. Minasyan et al.44 also additively
properties, EM and biological properties require Si3 N4 manufactured mesostructured MoSi2 –Si3 N4 ceramic lat-
components to have a certain porosity. At present, most tice through an SLM approach (as shown in Figure 12B
researchers usually use material extrusion technology to (reproduced with permission from Ref. [44] 2019 Else-
additively manufacture porous Si3 N4 . These techniques vier)). However, they only cared about the parameters of
not only have the disadvantage of low precision but also the SLM process, particularly the laser current, which have
result in lower mechanical properties of the final sample. a significant effect on the internal and external architec-
Therefore, realizing the functional design of mechanical ture of the lattices. The effect of structure on performance
properties, EM and biological properties at the same time needs to be further explored. In a word, AM can not
through other AM techniques or adding pore-forming only realize complex-shaped ceramic components but also
agents will be the focus of many researchers in the realize the structural and functional design of ceramic.
future. For detailed reports on additively manufactured ceramic
DONG et al. 2945
F I G U R E 1 2 (A) Three Al2 O3 ceramic structural configurations of body-centered cubic (BCC), octet, and modified body-centered cubic
(MBCC), (B) mesostructured MoSi2 –Si3 N4 ceramic lattice and SEM images of MoSi2 –13-wt.% Si lattices sintered at different laser currents.
Source: (A) Reproduced with permission from Ref. [105] 2022 Taylor and Francis Ltd. and (B) reproduced with permission from Ref. [44] 2019
Elsevier
structures and structure–function integration, please refer AC K N OW L E D G M E N T S

to another review.106 With the deepening of research, it Financial supports from the National Natural Science
will be a hot topic for future research that achieves exter- Foundation of China (Grant nos. 51772028, 91960102), and
nal functional regulation by tailoring advanced structures the Open Project of State Key Laboratory of Explosion
(namely: structure–function integration). Science and Technology (Grant no. QNKT22-15) was also
sincerely appreciated.
4 SUMMARY ORCID
Rujie He https://orcid.org/0000-0003-2498-2363
Si3 N4 ceramic has been widely applied in military,
mechanical engineering, aerospace, and biomedical fields
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Received: 19 May 2022 Revised: 7 July 2022 Accepted: 11 July 2022

Additive manufacturing of silicon nitride ceramics:

also lead to difficulties in densification after AM. There-

Zanocco et al.49 produced a dense Si3 N4 ceramic coating

As the earliest form of AM, photopolymerization technol-

2.2.1 Stereolithography apparatus (SLA)

osteogenic Si3 N4 coating on an orthopedic titanium sub- 3.3 Structure–function integration

structures and structure–function integration, please refer AC K N OW L E D G M E N T S

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