Journal of the European Ceramic Society xxx (xxxx) xxx

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Journal of the European Ceramic Society

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

Review article

A review of 3D printed porous ceramics

Feng Zhang *, Zongan Li, Mengjia Xu, Shiyan Wang, Na Li, Jiquan Yang
School of Electrical and Automation Engineering, Jiangsu Key Laboratory of 3D Printing Equipment and Manufacturing, Nanjing Normal University, Nanjing 210023,
China

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

Keywords: Three-dimensional (3D) printing of ceramics has gained widespread attentions in recent years. Many excellent
3D Printing reviews have reported the printing of ceramics. However, most of them focus on printing of dense ceramics or
Porous ceramics general ceramic aspects, there is no systematical review about 3D printing of porous ceramics. In this review
Bone tissue engineering
paper, the 3D printing technologies for fabricating of porous ceramic parts are introduced, including binder
Energy application
jetting, selective laser sintering, direct ink writing, stereolithography, laminated object manufacturing, and in­
direct 3D printing processes. The techniques to fabricate hierarchical porous ceramics by integrating 3D printing
with one or more conventional porous ceramics fabrication approaches are reviewed. The main properties of
porous ceramics such as pore size, porosity, and compressive strength are discussed. The emerging applications
of 3D printed porous ceramics are presented with a focus on the booming application in bone tissue engineering.
Finally, summary and a perspective on the future research directions for 3D printed porous ceramics are
provided.

1. Introduction
Porous ceramics, combining the advantages of ceramic material and
cellular structure, can find many applications in the field of tissue en­
gineering [1–3], catalyst support [4], high temperature filtering mem­
brane [5,6], and energy storage and conversion [7,8]. Conventional
methods to fabricate porous ceramics include replica, sacrificial tem­
plate, direct foaming, gel casting, and freeze casting etc. [9–11]. How­
ever, most of these processes are either complicated in procedure or not
able to fabricate porous ceramic with arbitrary-desired geometry and
organized structures. In recent years, additive manufacturing (also
known as 3D printing) has emerged as a novel approach to build com­
plex shaped ceramic parts. The processes involved include inkjet print­
ing (IJP) [12–16], direct ink writing (DIW) [2,17,18], stereolithography
(SLA) [19,20], selective laser sintering (SLS) [21,22], fused deposition
ceramics (FDC) [23,24], laminated object manufacturing (LOM) [25,26]
and binder jetting (3DP) [27,28]. 3D printing enables to fabricate
ceramic components of arbitrary shapes and extreme complex structures
which are quite challenging for conventional approaches. Although 3D
printing of ceramics has been reviewed in several exceptional articles
[29–32], the literature summaries about 3D printing of porous ceramics
are very limited and not well surveyed. Thus, the purpose of this liter­
ature study is to investigate the state-of-the-art 3D printing technologies
that are used to fabricate porous ceramics with special architecture
designs.
Porous materials can be divided into three categories: macroporous-,
mesoporous-, and microporous-materials according to the pore size
defined by IUPAC. Typically, pores less than 2 nm are defined as mi­
cropores, pores in the range between 2 nm and 50 nm are defined as
mesopores, and macropores are those size more than 50 nm. However,
such categorized micro-, meso- pores are extremely challenging to
replicate in real world and the applications of these micro pores are
unclear. So, here the pores are re-defined as large pores (pore diameter,
d > 100 µm), medium pores (1 µm < d < 100 µm), and small pores (d <
1 µm) [33]. Depending on the particular applications, different pore size
may be desired. Additionally, porous ceramics can be sorted into open
porous ceramics and closed porous ceramics in the view of whether the
pores are interconnected or independently separated by pore walls.
Open porous ceramics are critical in situation where the pores are used
to transport masses, nutrients and other applications where pores need
to be accessible. In contrast, the pores in closed porous ceramics are not
accessible, the gas phase is confined within the pore walls. These closed
pores can significantly enhance the insulation capability of the structure.
The pores of object can be formed by 3D printing as well as by
traditional process routes such as replica, direct foaming, sacrificial
templating, and freeze casting etc. [9]. Among these processes, freeze

* Corresponding author.
E-mail address: fengzhan@njnu.edu.cn (F. Zhang).

https://doi.org/10.1016/j.jeurceramsoc.2022.02.039
Received 19 August 2021; Received in revised form 31 October 2021; Accepted 20 February 2022
Available online 23 February 2022
0955-2219/© 2022 Elsevier Ltd. All rights reserved.

Please cite this article as: Feng Zhang, Journal of the European Ceramic Society, https://doi.org/10.1016/j.jeurceramsoc.2022.02.039
F. Zhang et al.
casting can be regarded as sacrificial templating where ice crystals are
used as templates. The pores can exist in an object in one scale, or in
multiple scales. For example, most 3D printing processes are able to
construct macroscale pores. As shown in Fig. 1, the pore can regularly be
formed in the shape of square, cylindrical, and spherical etc. or any other
user defined shapes (Fig. 1(d)). 3D printing can also be utilized to
fabricate synthetic template for conventional replica processing route.
The pore size of each process is dependent on several particular factors
in the process. For instance, the pore size of the replica fabricated porous
ceramics strongly depends on the pores in the original matrix, while the
pore size by 3D printing is defined by the parameters of the printing
process and resolution limitation of the specific printing technology.
Fig. 1(c) shows a representative model of scaffold normally fabricated
using DIW. Although most of the previous researches on ceramic 3D
printing put focus on fabrication of dense ceramic parts or scaffold with
dense struts, the promising aspect is that 3D printing can be integrated
with direct foaming [34–36], sacrificial templating [37,38], and freeze
casting [39] to fabricate hierarchical porous ceramic structures. As
shown in Fig. 1(b), macro pores can be created using 3D printing, while
medium or small pores can be formed with assisting of a conventional
method such as freeze casting, direct foaming, partially sintering etc.
Fig. 1(e)-(f) demonstrate typical porous ceramic parts fabricated using
3DP, DIW, and SLS respectively. As summarized in the following sec­
tions, 3DP, DIW, and SLS are the most popular techniques for porous
Fig. 1. Porous materials with (a) regular periodic pores that can be 3D printed; (b) hierarchical pores with periodic pores and stochastic pores in the pore wall/
column of periodic pores; (c) scaffold normally seen in DIW; (d) example of a designed porous structure; (e) typical 3D scaffold made by 3DP [40]; (f) typical
woodpile structure made by DIW [41]; (g) typical 3D scaffold made by SLS [42].
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ceramics fabrication.
This review paper provides a comprehensive literature survey about
fabrication of porous ceramics by innovative 3D printing technologies.
The scope of this review targets to those studies that are intended to
obtain a porous ceramic structure (e.g., scaffold, lattice, honeycomb,
aerogels, hierarchical porous structures by combining 3D printing with a
conventional porous ceramics fabrication method). Those literatures
that do not intend to fabricate a porous ceramic part is out of the scope in
this review. Particularly, the printed porous ceramics are reviewed in
terms of their pore types, pore sizes, porosity, pore distribution and
resultant properties.
2. 3D printing processes for porous ceramics
Theoretically, all applicable additive manufacturing technologies (e.
g., material jetting, material extrusion, vat photopolymerization, binder
jetting, and selective laser sintering) can be used to fabricate porous
ceramics. However, each of the 3D printing technologies has its partic­
ular resolution. Table 1 summarizes the resolution of typical 3D printing
processes that are used for ceramic structure fabrication. It should be
noted that digital light processing (DLP) and two-photon polymerization
(TPP) are two derivative technologies of SLA. Although the resolution
normally represents the minimum possible feature of the process can
build, the pore size cannot be accurately controlled beyond the
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Table 1 phosphates (CaP) [59], tricalcium phosphates (TCP) [60], and biphasic
Resolution of the main 3D printing processes and their porous material con­ calcium phosphate (BCP) [61] have been used for 3DP. The medium
struction ability. pore size is in the range of 10–30 µm, while the printing can realize the
Processes Accuracy Output material References large pores in ~300–500 µm. Tarafder et al. reported the printing of TCP
IJP High (10–80 µm) Regular cellular structures [12–16]
scaffolds for bone tissue engineering [62]. The maximum compressive
DIW Low (c.a. >100 µm) Spanning structures [43,44] strength of scaffold with 500 µm designed pores sintered in microwave
SLA High (10–100 µm) Periodic structures [19,20] furnace is much larger than that sintered in conventional furnace. The
DLP High (5–50 µm) Periodic structures [45,46] presence of both micro- and macropores facilitated osteoid-like new
TPP Very high (<1 µm) Microscale periodic structures [47–49]
bone formation when tested in femoral defects of rats. Fig. 3 shows a
LOM Medium (c.a. 50 µm) Regular cellular structures [25,26]
SLS Low (c.a. >100 µm) Porous structures [21,22] typical 3DP printed porous ceramic part. As indicated, one of the
3DP Low (c.a. >100 µm) Porous structures [27,28] prominent features of 3DP printed part is the very rough surface due to
the porosity in case large particle powder is used. This rough surface,
although undesired in many applications where good surface finish with
resolution of the process. And only a portion of these processes can be high-performance is needed, can be beneficial for the cell seeding in
integrated with traditional non-printing porous ceramic fabrication bone tissue engineering.
methods to produce hierarchical porous ceramics. Printing of silicon oxycarbide (SiOC) ceramics with ordered porosity
using preceramic polymers (PPs) as precursor was also reported by 3DP
2.1. Binder jetting (3DP) [63,64]. The polymer powder was glued together by binder jetting, and
later fired to form ceramics. In the work of printing wollastonite
Initial attempts to produce porous ceramics employing 3D printing (CaSiO3)-based silicate bioceramic parts, the binder plays a dual role as
technology come from powder bed-based processes such as 3DP and SLS both non-sacrificial binder and reactants with the powder to produce
due to their porous feed stock in nature. In the 3DP process, an inkjet bioceramic phase. The fabrication of porous ceramics by indirectly using
printer head is used to selectively deposit liquid binder onto a powder PPs offers an innovative strategy with multiple advantages including the
bed (Fig. 2). The binder glues the powder together to form into a easy process of polymer. PPs can be converted to ceramic by a controlled
designated shape. A new layer of powder is then recoated onto the heat treatment [65]. The organic elements in the precursors are elimi­
previous layer. The process is repeated layer by layer until the object is nated through pyrolysis. During the pyrolysis, C-H bonds break with
complete. In ceramic binder jetting (CBJ), various types of binders can release of gases such as H2, CH4 etc., leaving an inorganic, amorphous
be used to print on the ceramic powder bed forming a ceramic-binder phase with carbon-free phase. Polymer derived ceramics (PDC) have
composite. The composite can be post processed to get a resulting been extensively explored in recent years [65,66].
porous object. To fabricate shaped porous ceramics, 3DP is a very In summary, 3DP is a quite straightforward method for fabrication of
intuitive method [50]. As in 3DP, the powder bed is porous in nature. porous ceramic parts. However, the mechanical strength of the 3DP
These pores will increase the surface accessibility of the scaffold struc­ fabricated porous ceramics needs to be improved. Because of the ho­
ture for the liquid medium. However, the resulting structure and the mogeneous nature of powder bed, it is difficult to adjust the micro
corresponding properties of the porous ceramic will significantly depend porosity once a particular powder is selected.
on the content of binders, the sintering strategy, as well as the charac­
teristic of the powder such as particle size, shape, composition, and 2.2. Direct ink writing (DIW)
distribution [51,52]. For example, larger ceramic particles have lower
surface-volume ratio and larger pores, thus resulting in a more homo­ Direct ink writing, or robocasting is a 3D printing technique to
geneous ceramic part. It has been found that orientation and new layer extrude paste like, non-Newtonian fluidic material with shear thinning
spreading delay time significantly influence the dimension accuracy, material [67]. The critical condition using this process is to form a
compressive strength, and porosity of the samples [53]. Due to the printable ink with required storage modulus and loss modulus. The ink is
inherent capability to fabricate porous structures, 3DP has been widely extruded from the deposition nozzle at high shear stresses and needs to
applied to print porous ceramic scaffolds for bone tissue engineering self-support when lands onto the substrate. DIW is one of the most
[40,51,54–56]. Various bioceramics material such as hydroxyapatite popular material extrusion technologies. Compared to other material
(HA) [57], apatite–wollastonite (A-W) glass ceramic [58], calcium deposition technique such as material jetting, DIW has a much lower
requirement on ink material preparation, and the material feeding vol­
ume per nozzle is much higher than IJP. Besides, currently most
inkjet-printed ceramics are limited to small and thin ceramic structures
due to the very dilute ink used and solvent evaporation mechanism.
Fig. 4 shows the schematic of IJP and DIW respectively. As can be seen
from the figure, IJP is featured with discontinuous droplet while DIW
has a continuous filament connecting the nozzle tip and substrate. Thus,
inkjet-printed ceramics are commonly dense. Conversely, DIW of
macro-porous ceramics are widely investigated due to its filament
spanning capability [17,18,44], which benefits the fast creation of ver­
satile scaffolds. The pore sizes within the printed scaffolds are defined by
the parameters of the printing process such as diameter of the extrusion
nozzle, span between extrusion lines, and the printing path planning
[34]. One of the drawbacks using DIW for ceramic parts fabrication is
the slow drying process after the ceramic structure is printed. Huang
et al. demonstrated the fabrication of porous and strong bioactive glass
(13− 93) scaffolds using freeze extrusion fabrication [68,69]. The
freezing condition benefits the retention of the external shape and in­
ternal architecture of the as-formed constructs. Shao et al. developed a
3D gel printing process to fabricate porous HA scaffolds for bone tissue
Fig. 2. Schematic diagram of the 3DP process. engineering [70]. In a particular example, hierarchical porous scaffolds

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Fig. 3. 3DP fabricated scaffolds: top view (left) and side view (right) on the sintered channel test part with a diameter of 7.8 mm. The dimensions of the channels
range between 447 ± 37 µm in the z direction and 569 ± 33 µm in the x direction [3].

Fig. 4. Schematic of direct material deposition techniques: (a) Inkjet printing; (b) Direct ink writing [74].

were prepared by DIW of mesoporous bioactive glass (MBG) [71]. Large
pores of several hundred microns were formed by plotting, whereas
meso pores of ~5 nm can be found in the filament. Recently, DIW of PPs
was also reported [72]. A silicone resin preceramic polymer was used,
and a metal catalyst was used to help the resin cross linking process.
Graphene oxide (GO) was added to the ink to reduce the shrinkage of
preceramic polymer during pyrolysis. Porous scaffolds with strut
diameter as slim as ~120 µm were fabricated. The compression strength
of the resulting scaffolds with the addition of 0.1 wt% GO is of ~3.1 MPa
for a total porosity of ~64 vol%. Furthermore, 3D printing of hierar­
chical and tunable porous polymer-derived SiOC was reported by using
sacrificial polymeric microbeads [37]. Gómez et al. investigated the use
of DIW and partial sintering in a spark plasma sintering (SPS) furnace to
fabricate silicon carbide (SiC) scaffolds with a hierarchical pore
structure. 3D porous SiC structures with total porosity in the range of
64–85% are achieved from nanosized SiC powders [73]. As shown in
Fig. 5, the macro-pores (in the range of 500–700 µm) are defined by the
patterned structure, in the mean while the meso-pores (<50 nm) are
formed in the struts. The focus of review in this section will not be those
porous ceramics with pores formed by the extrusion lines only, it is not
possible to cover the full range of work in this area as there are too many
of them. Rather, we explore DIW of porous ceramics using novel mate­
rial and DIW of hierarchical porous ceramics (e.g., ones with pores that
are also formed in the extrusion line) by combination of DIW and con­
ventional approaches (e.g., emulsion, freeze casting, sacrificial
template).

Fig. 5. Images of plain β-SiC scaffold (sintered at 1700 ◦ C) showing a representative view of large channels (a), the surface of a rod with macro-pores (b) and the
faceted SiC grains on the surface of the rod at higher magnification (c) [73].

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F. Zhang et al.
2.2.1. Combining DIW with freeze casting
Freeze casting (also known as ice templating) is a relatively new
process for fabricating porous ceramics. This is a relatively inexpensive
and environment-friendly process. The first observation of cellular
structures resulting from the freezing of water can date back to more
than a century ago [75]. However, it wasn’t until 2001, when Fukasawa
created directionally porous alumina castings [76], that the idea for
using freeze-casting as a means of creating novel porous structures really
set sail. Since then, researches have grown considerably in this area.
Originally in this process, a ceramic suspension or slurry, with generally
low solids loading, is first frozen to form vehicle ice crystals, which often
connect with each other in dendritic shapes, surrounded by repelled
ceramic particles. After freeze drying, a process that sublimates the so­
lidified phase from the solid to the gas state under reduced pressure,
channels are created replicating the shape of the interconnected ice
crystals. The microstructure of the porous object can be tuned by slurry
concentration, slurry composition, particle size and freezing conditions.
Freeze casting has been used to fabricate various metal/ceramic, poly­
mer/ceramic hybrid materials with fine lamellar or brick-and-mortar
architectures [77–81].
Freeze casting has extensively been used to fabricate porous ceramics
[10,81–88]. DIW can integrate with freeze casting to print 3D porous
ceramics. Moon et al. developed an alumina/camphene ink using an
oligomeric polyester as dispersant, and extruded through a reduction die
with a diameter of 1 mm [39,89,90]. The solvent camphene was later
sublimated through the freeze-drying process. Since camphene is used as
solvent, the ink needs to keep molten when encapsulated in the syringe.
However, it can be solidified and sublimated at room temperature. By
integrating DIW with freeze casting, hierarchical porous structured can
be obtained (Fig. 6). First, the large pores can be realized through
printing. Second, the filament itself is also porous because of the solvent
templating, and the template can be easily removed by sublimation in
the air under room temperature. Since the pores are formed due to
solvent sublimation, this process yields hierarchical open pores. The
large pores are interconnected with pore sizes > ~150 µm by 600 µm,
while the medium-small pores are in the range of 1–20 µm, 0.3–5 µm,
and 0.3–4 µm respectively with corresponding alumina contents of
15 vol%, 20 vol%, and 25 vol%. The compressive strength increases
from 9.5 MPa to 29.3 MPa accordingly. Moreover, novel type of mac­
roporous ceramic scaffolds composing of hollow tubular filaments with
a highly microporous structure were also fabricated using 3D
co-extrusion (3D-CoEx) (Fig. 7). In a further study, UV curing-assisted
3D plotting of macroporous HA scaffolds comprised of microporous
hollow filaments was also reported [91].
Except freeze casting at room temperature using camphene, re­
searchers also investigated the creation of porous scaffolds by DIW using
low temperature freeze casting. Xiong et al. first reported the fabrication
of porous scaffolds for bone tissue engineering via low-temperature
deposition [92]. Poly(L-lactic acid) (PLLA) grains were dissolved into
Fig. 6. Schematic diagrams of 3-dimensional ceramic/camphene-based co-extrusion for the production of porous ceramic scaffolds with a biomimetic macro/micro-
porous structure: (a) the 3D-CoEx process and (b) porous ceramic scaffold with 3-dimensionally interconnected macropores and aligned micropores [39].
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dioxane and mixed up with TCP powder. The printing process is
accomplished in a refrigerator. The sublimation of dioxane in the post
freeze drying process formed micropores around the printed macro­
pores. Song et al. reported 3D printing of hierarchical and inter­
connected porous HA structure by integrating DIW with freeze casting
(Fig. 8) [93]. A purchased hot/cold plate was used as the freeze casting
platform for printing. The plate temperature was lowered in a given rate
of 1 ◦ C/min. Microscopic (below 10 µm) pores are formed from the
freeze casting process, and macroscopic (submillimeter to 20 mm level)
pores are formed from extrusion-based printing.
In general, integrating DIW with freeze casting provides a facile way
to fabricate hierarchical porous ceramics. However, the resolution and
efficiency of DIW technique is limited. Although the macro pores can be
realized by netting lines, the span of the line is restricted by the reso­
lution of the XY moving platform and the size of nozzle.
2.2.2. Combining DIW with emulsion and foams
Emulsion and foam templating is a traditional porous ceramics
fabrication approach. In this process, an oil-water/ceramic emulsion
suspension is formulated. After the foam is dried, a porous ceramic
object can be obtained. Emulsions and other foam agents have been used
to combine with 3D printing to prepare hierarchical porous structures
[34,35,94,95]. Mina et al. demonstrated the printing of hierarchical
porous ceramics by DIW of an emulsion/foam alumina ink [34]. The
mm-sized pores are controlled through the printing process while the
µm-sized pores can be tuned by the emulsification process parameters.
The types of pores (i.e., open porosity or closed porosity) can also be
controlled by adjusting the constitution of ink. For example, the Poly­
vinyl alcohol (PVA)-containing emulsion-templated structure exhibits
open porosity, while the emulsion-templated structure without addition
of PVA shows closed porosity (Fig. 9b). The ability to tailor the size and
types of pores allows the emulsion based DIW porous ceramic fabrica­
tion approach to be adopted in a vast range of applications from thermal
insulation which favors closed porosity to tissue engineering which
prefers open porosity that can facilitate the transport of nutrition.
Moreover, the printed structures show exceptionally high compressive
strength with relatively low densities. By introducing 60% closed
porosity within the filaments, the overall relative density decreased by
10% but the strength of the overall lattice kept unchanged. The research
also discovered that the printed samples with open porous filament with
interconnected pores achieved the best performance under compression.
Using particle-stabilized foam (PSF) ink, Muth et al. fabricated light­
weight ceramic architectures composed of closed-cell porous struts by
direct foam writing. The porous ceramic structures are patterned in the
form of hexagonal (Fig. 10) and triangular honeycombs, which are
composed of bending-, stretching-, bending-bending-, or
stretching-bending-dominated unit cells. Zhang et al. for the first time
prepared 3D complex-shaped porous ceramics by DIW of boehmite gel
foams [96]. The 3D printed hierarchical porous foams show tailored
F. Zhang et al.
Fig. 7. Schematic diagrams of 3-dimensional ceramic/camphene-based co-extrusion for the production of macroporous ceramics consisting of highly microporous
hollow filaments: (a) 3D-CoEx process using an initial feedrod consisting of a camphene core and ceramic/camphene shell and (b) macroporous ceramic scaffolds
consisting of highly microporous hollow filaments [89].
Fig. 8. Schematic of the 3D printing process combining freeze casting and extrusion. (a) Printing setup; (b) Printing process; (c) Freeze casting process; (d) Final HA
scaffold; (e) Laminar pore and HA structures [93].
pore structure in three levels: mm-scale pores formed by patterning of
filaments, micro-scale pores from bubble template, and nm-scale pores
in cell wall that can be adjusted by sintering temperature. Alison et al.,
3D printed complex-shaped hierarchical porous silica structures using
inks that consist of Pickering nanoemulsions and other microtemplates
[38]. The macroscopic complex shape and the large-scale cellular ar­
chitecture can be formed by the 3D printing process, while pores in a size
range varying from 10 to 100 µm can be obtained from larger droplets or
sacrificial polymer particles, whereas submicron pores can be generated
from particle-stabilized nanoemulsions.
Integrating DIW with emulsion and foam templating offers another
method to fabricate hierarchical porous ceramics by combining a 3D
printing technique with a traditional porous ceramic fabrication
method. While freeze casting can mostly produce open pores, the foam
agent method can form both open pores and closed pores, which
broadens the application of this method. However, comparing to freeze
casting based DIW, the material preparation of emulsion based DIW is
much more complicated and less environment-friendly. Except the DIW
based material extrusion method, fused deposition modeling (FDM) is
also applied to fabricate porous ceramics. In FDM, ceramics is usually
mixed with a polymer or binder to form into filaments, the filaments
then go through a heater nozzle to melt into extrudable paste for ink
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writing [41,97,98]. Printing ceramics using FDM seems less intuitive
than DIW due to the complex feedstock preparation process. However,
the solidification upon deposition characteristic of this process is a big
advantage which significantly reduces the dry time that is needed in
DIW.
2.3. Selective laser sintering (SLS)
SLS is a 3D printing process that uses high-power laser beam to
selectively irradiate the surface of a target powder bed [99]. After, the
material feeding process is quite similar to that of 3DP. A schematic
diagram of the SLS process is shown in Fig. 11. Unlike selective laser
melting (SLM), which melts the powder bed material using super
high-power laser, the laser power of SLS is just enough to fuse the par­
ticle together. Even though, it is still prohibitively challenging for SLS to
print ceramics due to the notoriously high melting points of ceramics (e.
g., alumina has a melting point of 2045 ◦ C, zirconia has a melting point
of 2715 ◦ C). Thus, a common practice to print ceramics with SLS is to
coat the matrix powder with a lower melting point material such as
polymers [30,100] The polymer is later removed during the sintering
process, or intentionally kept for mechanical strengthen purpose. Due to
the porous nature of powder bed and the fusion characteristic of SLS, the
F. Zhang et al. Journal of the European Ceramic Society xxx (xxxx) xxx

Fig. 9. (a) Processing schematics of hierarchical porous ceramics prepared by emulsion/foam templating and direct ink writing; (b) Schematic of the stabilization
mechanism of the emulsions/foams [34].

Fig. 10. 3D porous ceramic honeycombs. (a-b) Representative sintered hexagonal honeycomb; (c) Image of one node of the hexagonal honeycomb; (d) the resulting
microstructure [35].

SLS fabricated objects usually possess a high porosity [100–102]. The
pores are commonly eliminated by infiltrating with a second phase or
densified through isostatic pressing. The ability to fabricate porous ob­
ject using SLS inspired researchers to investigate the potentials of using
it for biomedical tissue engineering [103–108]. Three-dimensional
porous scaffolds with good dimensional accuracy and complex archi­
tecture were fabricated by SLS using calcium phosphate (Ca-P)/poly
(hydroxybutyrate-co-hydroxyvalerate) (PHBV) nanocomposite loaded
with bovine serum albumin (BSA) [109]. The encapsulation efficiency of
BSA in the scaffolds and in vitro BSA release were studied by tuning SLS
parameters such as laser power and scan spacing. Furthermore, a real
human proximal femoral condyle model was obtained from computer
tomography (CT) scans and then converted to scaffold with a pore size of
2 mm and a strut size of 2.5 mm. The scaffold was produced by SLS with
40% scale-down (Fig. 12) [42]. This osteoconductive nanocomposite
with customized architecture, controlled porosity and totally inter­
connected porous structure showed sustained release behavior of oste­
ogenic growth factor and provided a promising route towards bone
tissue engineering.
SLS is a facile approach to fabricate porous ceramics. Except directly

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F. Zhang et al.
Fig. 11. Schematic diagram of the SLS process.
using ceramic powder as feedstock, SLS is also able to fabricate bimodal
porous ceramic structures using ceramic hollow spheres [102,110,111].
However, one of the drawbacks of SLS fabricated porous part is its poor
mechanical strength. Thus, many researchers used mechanical strong
biopolymers and other strength-aiding nanomaterial as the binder for
SLS fabricated porous ceramics. Tan et al. fabricated 3D scaffolds of
polyetheretherketone (PEEK)/HA biocomposite using SLS [112]. Mix­
tures of PEEK/HA powders with different weight percentages were
Fig. 12. (a) Sintered Ca–P/PHBV nanocomposite porous structures based on the following models: salamanders, elevated icosidodecahedron and snarl (from left to
right) (b) three-dimensional model of a human proximal femoral condyle reconstructed from CT images and then processed into porous scaffold using cubic cells; (c)
sintered Ca–P/PHBV nanocomposite proximal femoral condyle scaffold [42].
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produced by physically blending pure PEEK and HA powders using a
roller-mixer. Gao et al. reported the use of graphene to improve the
mechanical properties of nano-58S bioactive glass for bone repair and
regeneration [113]. Feng et al. mixed PEEK, biodegradable PLLA, and
β-TCP to fabricate multi-material scaffold using SLS [114]. The degra­
dation of PLLA formed a myriad of pores on the closed membrane
generated during the melting and solidification of PEEK material，these
pores enable the permittivity of body fluids into the wrapped β-TCP. The
group of Shuai did a bunch of excellent researches by engineering the
SLS fabricated bioceramics through mixing various low-dimensional
nanomaterial (e.g., mixing boron nitride with TCP, mixing carbon
nanotube/graphene with diopside) [115]. By adding these
low-dimensional nanomaterial, the drawbacks of the bioceramics such
as brittleness, low toughness get improved.
2.4. lithography-based ceramic manufacturing (LCM)
Vat photopolymerization is a 3D printing technology in which pho­
tocurable resin is polymerized by light layer by layer, it is commonly
known as stereolithography. Stereolithography can be divided into laser
scanning stereolithography (SLA), mask image projection stereo­
lithography (MIPSL), and two photon polymerizations (TPP). They are
generally known as vat photopolymerization (VPP), one of the seven
types of 3D printing technologies [116]. In laser scanning SLA, a fine
laser is guided over the photopolymer surface using a galvanometer to
cure the resin material (Fig. 13(a)). It should be noted that in the
schematic, the laser is directed to the resin surface from the top, thus, it
is a top-down type SLA. Instead of using laser spot to scan over the resin
surface layer by layer, MIPSL can cure a layer in one exposure by
F. Zhang et al.
Fig. 13. Schematic diagrams of three approaches to photopolymerization processes: (a) top-down laser scanning SLA; (b) bottom-up MIPSL; (c) TPP.
projection an image that represents the cross section of the object
(Fig. 13(b)), thus, is much faster. The schematic shows a bottom-up type
MIPSL as the projection comes from the bottom of vat. TPP fabricates the
most delicate part as only an extremely localized focal volume of two
photons will be solidified (Fig. 13(c)), the feature printed can be as small
as sub-micron. Conventionally stereolithography process is used to print
polymers for rapid prototyping. Now researchers have explored the
using of stereolithography as a method for fabricating ceramics due to its
fast speed, high accuracy, as well as versatile material selections, this
method to fabricate ceramics is often termed ceramic stereolithography,
or lithography-based ceramic manufacturing [117–119]. Here, the focus
is placed to discuss the ceramic stereolithography technologies used for
the fabrication of porous ceramics.
2.4.1. Resin-ceramic composite
Generally, there are two approaches to fabricate ceramic structures
using vat photopolymerization. One is printing resin-ceramic composite
(i.e., using SLA, MIPSL), the other is printing with PPs. Doping ceramic
particles into photo-curable resin could be a route to fabricate porous
ceramics. Professor Chen’s group at the University of California have
developed an integrated MIPSL/tape casting process to fabricate
ceramic parts [120,121]. Dielectric capacitor printed using commercial
photocurable resin Flex mixed with silver decorated Pb(Zr,Ti)O3 (PZT)
nanoparticles can reach a capacitance of 63 F/g at the current density of
0.5 F/g. In another project, they printed piezoelectric element for ul­
trasonic sensing using a composite of BaTiO3 powder and photocurable
resin, the resin was then burned out with gradually elevated debinding
temperatures (at a rate of 1 ◦ C/min, and held for 30 min respectively at
200 ◦ C, 300 ◦ C, 400 ◦ C and 500 ◦ C). After debinding, irregular and
interconnected pores were formed. The debinded part can be further
sintered upon needs. Recently, many researchers have reported the
printing of biocomposites for bone tissue engineering using ceramic
stereolithography [122,123], mostly by DLP technology due to the fast
layer-curing-by-one-exposure process. Cao et al. fabricated porous
scaffolds of ZrO2/HA composite [124]. The composite material shared
good biocompatibility of HA and excellent mechanical strength of ZrO2.
Liu et al. prepared HA bone scaffolds using the DLP method [125]. The
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Journal of the European Ceramic Society xxx (xxxx) xxx
scaffolds have pore sizes between 300 and 600 µm with porosity about
49.8%, and possess compressive strength of 15.25 MPa. Yao et al. suc­
cessfully fabricated high performance HA ceramics by DLP [123]. It was
found that the sintering atmosphere of wet CO2 can dramatically
improve the densification process and lead to better mechanical prop­
erties. Also, A p-cell triply periodic minimum surface (TPMS) structure
with a porosity of 74% achieved compressive strength of 4.09 MPa. Wei
et al. fabricated osteoinductive calcium phosphate ceramics with high
precision and controllable 3D structures using DLP technology [126].
The average compressive strength of the ceramics with 64.5% porosity
reached 9.03 MPa. Li et al. printed HA/TCP bone scaffold using DLP
based stereolithography process [45]. The fabricated biomimetic
HA/TCP scaffolds possess hierarchical porous features with microscale
pores (diameter: ~20–1000 µm) and interconnected tiny pores (<5 µm)
induced by polymer burnout during post-processing (Fig. 14). Meng
et al. successfully prepared a Harversian bone-mimicking scaffold with
integrated hierarchical bone structure via digital laser processing [46].
The precursor slurry is composed of akermanite (AKT) bioceramic
powder, 45S5 bioactive glass, and photosensitive resin. The compressive
strength and porosity of scaffolds can be well controlled by altering the
parameters of the Haversian bone–mimicking structure. Introducing
micropores into the ceramic strut by polymer burnout is difficult to
control due to the mixing quality of resin and ceramic particles.
Nonuniform mixing can cause the mechanical failure of the sintered
ceramic part, while uniform mixing leads to homogeneous micro pores
that is not beneficial for performance of the porous ceramics which
usually requires bioinspired pores [127]. An interesting work is pro­
posed by Choe et al., which proposed camphene/photopolymer solu­
tions as a novel pore-forming agent for the photocuring-assisted
manufacturing of porous ceramics [128]. Solid camphene was dissolved
in photocurable monomer hexanediol diacrylate (HDDA) at room tem­
perature, and mixed with alumina to form an alumi­
na/camphene/HDDA mix. The mix was frozen at − 2 ◦ C to allow the
growth of camphene-rich crystal, and then photopolymerized using a
DLP engine. This results a ceramic composite with camphene-rich
crystals surrounded by photopolymerized alumina/HDDA walls.
Dendrite-like pores were formed after removing the camphene-rich
F. Zhang et al. Journal of the European Ceramic Society xxx (xxxx) xxx

Fig. 14. Schematic diagram of 3D-printed HA/TCP scaffold with bioinspired hierarchical porous structure. (a) A nude mouse long bone image; (b) microscopy of
printed green part of biomimetic HA/TCP scaffold; (c) microscope and SEM images of biomimetic HA/TCP scaffold with micro- and submicron-scale pores after
sintering; and (d) the developed 3D printing process for the fabrication of HA/TCP scaffold with hierarchical porous structure [45]. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 15. Additive manufacturing of the preceramic photopolymer [130].

10
F. Zhang et al.
crystals through freeze-drying. The HDDA was removed after sintering
at 1555 ◦ C for 2.5 h. By integrating ceramic stereolithography with
freeze casting, this method provides the potential to fabricate hierar­
chical porous ceramic structures.
2.4.2. Preceramic polymers (PPs)
3D printing of photopolymerizable PPs is another technique that can
be used to fabricate macroscopic porous structure [129–131]. In this
technique, photocurable resins are used to print the structure as nor­
mally used in the conventional stereolithography [131]. Unlike tradi­
tional resin, this specific resin can be pyrolyzed later at high temperature
to convert the polymer into ceramic. As shown in Fig. 15, the preceramic
polymer is filled in a vat for the typical projection based stereo­
lithography process. First, the moving stage is lowered to a gap height
corresponding to one layer thickness to be cured (Fig. 15(a)) and moves
upward to release the component from the vat, before lowering again to
continue the layer-by-layer fabrication (Fig. 15(b)). When the 3D
component is completed, it is removed from the moving stage (Fig. 15
(c)). Finally, the SiOC ceramic microcomponent (black in Fig. 15(d)) is
obtained after pyrolysis at 1000 ◦ C of the preceramic 3D component
(gray in Fig. 15(d)). The lateral resolution of the print is as small as
40 µm, and the z-axis resolution is 25 µm. Almost at the same time in
another work [129], stereolithography printed SiOC honeycomb struc­
ture exhibits a compressive failure strength of 163 MPa with a density of
0.8 g/cm3. It proves that the periodic printed ceramic architectures are
inherently more mechanically efficient than a random ceramic foam.
Except the silica-based PPs, porous ZrOC ceramics with octet truss
structure was also reported [132], showing great potential of PDC by
utilizing various PPs.
2.4.3. Ultrafine ceramic lattices by two photon polymerization
Except those macroscale structures fabricated using LCM, complex
3D microstructures with nanoscale feature can also be fabricated using
photopolymerization process. TPP was used to fabricate delicate poly­
mer template and then coated with alumina (Al2O3) layers of different
thicknesses using atomic layer deposition (ALD) [47–49]. In this pro­
cess, micro lattice structures were first printed using two-photon ster­
eolithography, the pores in the lattice can be as small as sub-micron.
After printing, the micro lattice was coated with a thin alumina film by
ALD (or other chemical deposition approaches such as chemical vapor
deposition [133]). The thickness of the ALD coating can be adjusted
from 5 nm to 60 nm, leading to different relative density and yield
strength. Then the polymer was etched away in O2 plasma, yielding a
Fig. 16. Computer-aided design models (Upper) and SEM images (Lower) of examined cellular microarchitectures (scale bars: 10 µm) [47].
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Journal of the European Ceramic Society xxx (xxxx) xxx
micro ceramic lattice composed of hollow ceramic tubes [134]. Fig. 16
presents modeled and printed truss structures as well as shape optimized
honeycombs. As shown, the printed bar of truss is only ~1 µm. The
trusses can reach compressive strength of 55 MPa for a density of
~0.42 g/cm3. While, the optimized honeycomb exhibits 280 MPa for a
density of ~0.81 g/cm3. This impressive compressive strength exceeds
all natural and engineering materials with a density below 1 g/cm3
(density of water). Besides using TPP to print polymer replica template
for chemical deposition of ceramics, TPP can also be adopted to directly
fabricate PDC structures [135–137]. For example, Brigo et al. achieved
the conversion of TPP shaped preceramic polymer into crack-free SiOC
nanoscale components [138]. 3D specific geometry with fine details
down to 450 nm and rapidly printing structures up to 100 µm in height
were fabricated. It should be noted that for TPP technology, only
pre-ceramic polymeric materials can be used due to the subsurface
curing characteristic of this process. Doping ceramic particles into
photopolymer will not work for TPP.
2.5. Laminated object manufacturing (LOM)
LOM was developed and commercialized by the California-based
Helisys Inc. (now Cubic Technologies). During the LOM process, layers
of plastic, paper or thin metal sheet are fused or laminated together
using heat and pressure, and then cut into the desired shape with a
computer-controlled laser or blade (Fig. 17). While LOM seems to be an
unsuitable method to fabricate ceramics, like many other 3D printing
processes, the feasibility of fabricating ceramic parts using LOM was still
reported [139,140]. In the ceramic-LOM, thin sheets of alumina were
prepared by tape casting using a customized process. The slurry was
produced by mixing the alumina powder with an organic binder system
using a ball mill. The ceramic tape-casts sheet was placed onto a glass
plate for the first layer fabrication. The sequential sheets were then
placed onto the first layer one layer a time by hand. The ceramic-LOM
provides another way to fabricate complex shape ceramics. However,
the reported researches are mainly for dense ceramics as there is a
lacking of mechanism to produce pores. Even for macropores, it should
be very difficult to construct due to the “cut-then-remove” characteristic
of this process. Recently, LOM has also been used to fabricate porous
ceramics by integrating with freeze casting [141]. As shown in Fig. 18
[142], after the prepared slurry is supplied and scraped by a doctor
blade, A cryo-panel with internal circulation of refrigerant is used to
freeze the laminated layer. The laser beam is then used to cut and gasify
the contour of the frozen slurry layer. In this way, the cross-section of the
F. Zhang et al.
Fig. 17. Schematic diagram of the LOM process.
object can be formed. After the part printing is finished, it is placed for
freeze drying. It is worth to mention that, the compressive strength in
Z-direction (layer stacking direction) of the sintered parts made by
layer-by-layer freezing is much higher than that of holistic freezing (e.g.,
Fig. 18. (a) Diagram of the manufacturing steps of frozen slurry LOM; (b-c) The cross-sectional morphologies of sintered parts fabricated by layer-by-layer freezing
with alumina content (b) 50 wt% and (c) 60 wt% [142].
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freeze casting ceramic suspensions in a Teflon mold as a whole). This is
due to the much smaller ice templates formed in layer-by-layer freezing.
Zhang et al. integrated mesh template with LOM to fabricate ceramics
with regular micron scaled pore structures [143]. A layer of mesh was
laid on the platform, a layer of ceramic slurry was then scrapped over the
nylon mesh and dried by an infrared heater, finally the slurry impreg­
nated mesh went through the common LOM process using a laser cutter.
The nylon mesh was later removed in the sintering process leaving a
pore network. Another example of LOM fabricated porous ceramics was
reported by Travitzky et al. In their work, oxide as well as nonoxide
ceramics were processed into single-sheet, corrugated structures, and
multilayer ceramics [144,145]. Sintering of an oxide-loaded preceramic
paper in air results in highly porous products, with the porosity shape
and distribution templated by the pulp fiber used in papermaking. In
general, although LOM of porous ceramics seems to be vagarious, many
attempts have been implemented to realize the fabrication of porous
ceramics using LOM. More literature about LOM of ceramics including
those of porous ceramics can be found in a recently published review
article [146].
2.6. 3D printing-based templating method
Another approach to produce porous ceramic is based on indirect
utilizing 3D printed moulds as templates [147–149]. In this approach,
3D printed scaffolds are served as sacrificial template. Unlike commonly
known sacrificial template technique that uses dispersed sacrificial
phase which homogeneously distributed throughout the matrix. 3D
printed sacrificial template is able to be casted with ceramic slurry. By
F. Zhang et al.
removing sacrificial template through sintering, an inverse shape of the
original 3D printed template can be obtained. Schumacher et al.
impregnated inkjet printed wax moulds with calcium phosphate ceramic
slurry to prepare macroscopic porous ceramics of various pore patterns.
The wax inkjet printing allows to fabricate CaP-ceramic into scaffolds
with high geometry accuracy and adjustable mechanical strength by
different ceramic material and pore geometry [150]. Sabree et al.
fabricated highly porous ceramic scaffolds from a 70% SiO2–30% CaO
glass powder using stereolithography based template, serving as the
loss-mold for gel-casting [147]. The mould was burned out in air at
550 ◦ C for 2 h. The various sintered wallastonite scaffolds had an in­
ternal porosity of approximately 42% with pores in the range
300–600 µm (Fig. 19(b-d)). The mean crushing strength of the scaffolds
is between 10 and 25 MPa. Tu et al. used FDM printed PVA material as
mold template to gelcast high-loading of SiC [151]. After the SiC was
gelled, the PVA template was removed by liquid drying using a poly­
ethylene glycol (PEG) aqueous solution (Fig. 19e). The benefit of using
3D printed molds to replicate the ceramic parts lies in that it alleviates
Fig. 19. (a) Original mould fabricated by stereolithography, filled mould and final sintered 400scaf scaffold structure showing shrinkage after sintering; (b-d) SEM
images showing a general view of the scaffolds’ structure and morphology. All scaffolds have been sintered at 1200 ◦ C [147]. (b) 300scaf, (c) 400scaf, (d) 600scaf; (e)
Liquid drying process of gelled silicon carbide green body [151].
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the challenge of formulating proper ceramic inks for 3D printing,
because the preparing of a ceramic slurry that can be used for gel-casting
or other kinds of casting is much easier compared to that can be viable
for 3D printing. However, it is important to select good-to-remove
template material. As discussed previously, the photocurable polymer
is generally difficult to debind. Furthermore, in the 3D printing-based
template method, the printed sacrificial template stays in a bulk state
unlike in the resin homogeneously mixed with ceramic particles in the
LCM process. It remains unknown which process is easier for sintering
processing.
2.7. 3D printed ceramic aerogels
Aerogel is a synthetic porous material derived from a gel in which the
liquid component is substituted by a gas phase [152,153]. Aerogels can
be prepared by various drying techniques such as freeze drying, super­
critical drying, or ambient-temperature drying in certain condition. The
materials can be used to prepare aerogels are versatile, including
F. Zhang et al.
carbon, polymers, metals, oxides, and non-oxide ceramics etc. [154,
155]. Ceramic aerogels and porous ceramics are similar in that they are
both porous structures. However, only those are prepared from a gel
through sol-gel method or other gel preparation process can be called
ceramic aerogels according to the definition of aerogel. Silica aerogel is
one of the most investigated type of ceramic aerogel partially due to the
facile preparation of silica sol [156], thus, controlling of gel process.
Saeed et al. demonstrated the printing of silica aerogels using laser
illumination. A laser beam of 532 nm was directed through the cut-out
holes of 3D letters to gel the solution composed of tetraethyl orthosili­
cate (TEOS), hexanedioldiacrylate, Eosin Y and amine [157]. Zhao et al.
printed pure silica aerogel object by DIW. The ink used for DIW contains
silica aerogel particles suspended in a sol with silica nanoparticles. The
silica sol is activated with ammonia vapor after printing to bind the
aerogel particles and fill the interstitial voids with silica gel (Fig. 20).
Wang et al. demonstrated a thermal-solidifying DIW strategy to prepare
silica aerogels with complex architectures. The solidification of silica
inks is facilely realized by thermal-solidifying [158]. Farrell et al. pre­
pared 3D complex silicate aerogels by three photochemical approaches:
mold irradiation, DLP 3D printing, and TPP [159]. It should be noted
that it is the first TPP-based 3D printing of ceramic aerogel (Fig. 21),
which may find applications such as nanosatellite, as well as isolation of
miniature electronic devices. With the above discussion, it is straight­
forward to know that 3D printing of ceramic aerogels is a facile way to
prepare hierarchical porous ceramic structures.
In short, 3D printing of porous ceramics have been massively real­
ized using different techniques and for sure will be continuously
explored. A comparison of the representative techniques is provided in
Table 2, with a focus on some of the hierarchical porous ceramic
fabrication technique and novel approaches.
Fig. 20. Additive manufacture of silica aerogel by direct ink writing. (a) Schematic diagram of the direct ink writing process, (b) 3D lotus flower of silica gel printed
through a conical nozzle. Photographs of the hydrogel (c) before solidification, (d) after ammonia-vapour-induced gelation and (e) after drying [156].
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3. Applications of 3D printed porous ceramics
The applications of porous ceramics are quite broad. For example,
the porous ceramics can be used in the applications such as mechanical
damping, thermal insulation, energy storage and conversion, environ­
mental remediation, and biological engineering [161,162]. However,
for most applications, the need to fabricate porous ceramics with 3D
printing is in doubt or still in discovery. Although there are several
advantages to fabricate porous ceramics using 3D printing as discussed
previously, the most pronounced advantage is its complex shape and
architecture creation capability. Thus, to understand where 3D printed
porous ceramics is necessary, the best way is to find where shaped and
structure-organized porous ceramics is needed. With no doubt, bone
tissue engineering is one of them due to the porous characteristic of
nature bone and anatomical difference of each individual. Another
benefit of using 3D printing to prepare porous ceramics is its ability to
create organized and ordered pores, instead of random pores,
well-ordered microscale pores can effectively increase the performance
of the fabricated porous ceramics. However, only a few 3D printing
techniques can produce pores in several micron scale. Furthermore,
when the microscale feature is fabricated, the macroscale size of the part
is usually quite small, which greatly limited its applications. This section
of review will mainly focus on the emerging application of porous ce­
ramics in bone tissue engineering with some review in the area of energy
and environmental remedy. The requirement of pore size, pore shape,
interconnectivity, porosity, and mechanical property on bone tissue
engineering will be discussed. Those properties of porous ceramics can
be applied to other application scenarios as well.
3.1. Bone tissue engineering
One of the most promising application of porous ceramics is in bone
tissue engineering [51]. For instance, the synthetic HA bone scaffold can
F. Zhang et al. Journal of the European Ceramic Society xxx (xxxx) xxx

Fig. 21. TPP of ceramic silica aerogels. (a) Printed and calcined cubic lattice and (b) zoom-in side views. (c) Top view and (d) zoom in. (e) A space shuttle and (f)
zoom-in side views [159].

Table 2
Properties summary of typical 3D printed porous ceramics.
Ref. Printing techniques Pore types Pore sizes Porosity Material Compressive Structure
strength

[34] DIW + Open/closed hierarchical Several μm to mm ~83.4% alumina ~15 MPa 3D woodpile
emulsion pores
[35] Direct foam writing Closed pores ~20 µm 94% (net total alumina ~1 MPa honeycomb
porosity) (Triangle foam)
[160] DIW + Open hierarchical pores Several μm to mm ~81% alumina ~1.75 MPa honeycomb
Capillary suspension (in-plane)
[39] Ceramic/camphene Open hierarchical pores 0.3 µm to half mm 77% alumina ~9.5 MPa 3D woodpile
extrusion
[72] DIW + Open pores Several mm ~64% SiOC ~2.51 MPa Scaffold
Preceramic polymer (out-of-plane)
[47] TPP Open pores Several μm ~80% alumina 280 MPa 3D honeycomb
[134] TPP Open pores 1–2 µm ~91.5% alumina ~36.5 MPa 3D
nanolattices
[129] SLA of Preceramic polymer Open pores Several mm ~81.9% SiOC ~30 MPa 3D
Microlattice
Several mm ~84.6% ~47.6 MPa honeycomb
[130] SLA of Preceramic polymer Open pores Several mm ~93.1% SiOC ~0.686 MPa 3D scaffold
[131] SLA of Preceramic polymer Open pores Several mm – SiOC ~19.08 MPa 3D lattices
[128] DLP + Freeze casting Open hierarchical pores 2.5–4.6 µm ~51.9% alumina ~265 MPa honeycomb
(micropore)
[147] SLA printed mould + gel Open pores 300–600 µm ~42% CaO- 10–25 MPa 3D scaffold
casting SiO2
[142] LOM + Open pores – ~58% alumina ~16 MPa –
Freeze casting

be used to repair segmental defect in long bones [163]. Especially, bone
tissue engineering is space limited and aesthetic favored since the bone
shape and structure of each individual is different. Thus, 3D printing of
porous bioceramic structures potentially offers a good solution for this
application. However, to make good use of this application, several
perquisites need to be satisfied. First, the bone scaffold needs to be
biocompatible. Second, the bone scaffold needs to be degradable, and
the degradation rate should match the rate of bone growth. Third, to
permit tissue in-growth and function, an open porosity of ~50% is
required, and the pore size needs to be at least 100 µm [163,164].
Subsequent studies also show that better osteogenesis can be achieved
with pores greater than 300 µm [147]. This pore size can easily be
realized through many 3D printing technologies such as SLA, DIW, IJP,
and 3DP not to mention the universal methods in traditional processing
routes. In fact, nature bone is made of cancellous bone and cortical bone.
The inner part is cancellous with 50–90% porosity, while the dense out
layer cortical bone has a porosity of less than 10 vol%. Thus, it’s
essential to be able to fabricate hierarchical porous bioceramics. Even­
tually, it is important to couple porosity, pore size and mechanical
properties. While large, interconnected pores are favored by direct

15
F. Zhang et al.
osteogenesis, there is a limit for the total porosity of the structure to
grant it for load-bearing bones. Commonly cortical bone has a Young’s
modulus in the range of 1–20 GPa and a strength range of 1–100 MPa,
while cancellous bone possesses Young’s modulus 0.1 GPa and strength
1–10 MPa. Lin et al. proposed the homogenization-based topology
optimization algorithm that can provide precise control over scaffold
architecture design to achieve desired mechanical properties, the to­
pology optimization result is represented as a voxel image model [165].
The voxel representation then can be converted to standard tessellation
language (STL) format and 3D printed. The designed prototype was
realized by 3D inkjet printing techniques (Sanders ModelMaker2). The
advances of computational topology design and 3D printing technolo­
gies offers the possibility to create scaffolds with controlled architecture
[166].
The material for bone tissue engineering is versatile, including
apatite, silicates, bioactive glasses, and biological glass-ceramic, which
are generally called bioceramics [167]. The material for bone tissue
engineering needs to be biocompatible, degradable, and mechanically
strong. HA and TCP are the most commonly known apatite bioceramics
owing to their similar chemical composition to that of nature bone
[168]. However, apatite based bioceramics generally possess a poor
mechanical strength that cannot be used in load bearing applications.
Besides, HA has a slow degradation rate and poor mechanical strength as
well as fracture toughness. TCP has a fast degradation and better me­
chanical strength. However, they can still not be used for load-bearing
implants. Compared to apatite based bioceramics, silicates based bio­
ceramics have much improved mechanical strength. Wu et al. fabricated
a highly homogeneous silicate based bioceramic scaffold with a
pore-controlled structure and excellent mechanical properties [169].
The compressive strength of 3D-printed CaSiO3 (CS) scaffolds is around
120 times that of polyurethane templated CS scaffolds. Further, Yang
et al. demonstrated 3D printing of tricalcium silicate with controllable
pore channels [170]. Engineering of the topography on the surface of
scaffolds using apatite was also implemented to improve bone regen­
eration. Although bioactive silicate ceramics have much improved me­
chanical strength, their dissolution and degradation rate are usually too
high, causing a high pH value in the microenvironment affecting cell
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Journal of the European Ceramic Society xxx (xxxx) xxx
growth and their osseointegration ability [168]. Because of the
controllable chemical composition, and thus the rate of degradation, as
well as excellent mechanical strength, many bioactive glasses have been
utilized to prepare 3D scaffolds for bone tissue engineering, including
6P53B (composition in wt%: 52.7 SiO2, 10.3 Na2O, 2.8 K2O, 10.2 MgO,
18.0 CaO, 6.0 P2O5) [43,171], 45S5 (composition in wt%: 45 SiO2, 24.5
Na2O, 24.5 CaO, 6.0 P2O5) [172–175], 13–93 (composition in wt%: 53
SiO2, 6 Na2O, 12 K2O, 5 MgO, 20 CaO, 4 P2O5) [68,176,177], 58 S
(composition in wt%: 58 SiO2, 33 CaO, 9 P2O5) [113]. For example, Fu
et al. reported DIW assembly of highly porous glass scaffolds with a
periodic pattern (Fig. 22). With controlled sintering of the filaments,
anisotropic constructs similar to biological materials can be obtained
[43]. Tesavibul et al. fabricated precise 45S5 cellular structures using
DLP (Fig. 23). The resolution of the printing device is around 40 µm,
enabling the fabrication of orthopedic implant with accurate shape and
dimensions. Hua et al. manufactured 45S5 & BCP bioceramic scaffolds
with a diamond lattice structure similarly by DLP [178]. The sintering
curve is investigated to obtain optimized compressive strength.
In general, bone tissue engineering is one of the most promising
application for 3D printed porous ceramics. The eventual biological and
mechanical performance of the synthetic bone scaffold largely depends
on the material selection, pore size, interconnectivity, and porosity.
Even though much work has been done on the bone tissue engineering
using 3D printed porous ceramics, the availability of well-suited load
bearing bone scaffold is still quite scarce. Thus, further endeavors need
to be made to optimize the material selection and corresponding key
parameters tuning on the scaffold. Table 3 summarizes the various 3D
printed porous bioceramics for bone tissue engineering, with the ma­
terial, pore characteristics, and compressive strength listed for each
process.
3.2. Energy and other emerging applications
Another newly emerged application of 3D printed porous ceramics is
in the energy area. The porous structure can facilitate the mass transport
that is essential for the energy devices [152]. Many functional ceramics
can be used to print 3D complex structures and architectures. Unlike
Fig. 22. SEM images of (a) surface of
as-printed 6P53B glass scaffolds
through a 100 µm nozzle with a spacing
of 200 µm, inset showing the scaffold
after sintering; (b) surface of sintered
scaffolds with pores of 500 µm, inset
showing cross section of the sintered
scaffold; three-dimensional visualiza­
tion of the sintered 6P53B glass scaf­
folds using synchrotron X-ray micro
computed tomography. Images of (c)
sintered scaffolds with regular grids; (d)
a sectional view of the bonded glass
filaments [43].
F. Zhang et al. Journal of the European Ceramic Society xxx (xxxx) xxx

Fig. 23. Bioglass® parts fabricated by lithography-based additive manufacturing technology after sintering: (a) cylindrical cellular structure (scaffold) used for
compressive strength testing and (b) customized bone implant [173].

Table 3
Representative 3D printed porous bioceramics for bone tissue engineering.
Ref. Printing Material Pore sizes Porosity Compressive Structure Specific
techniques strength applications

[55] 3DP HA, BCP Tens of μm to mm ~60% 0.6–1.1 MPa 3D scaffold –

[3] 3DP HA 10–450 µm – ~22 MPa 3D scaffold –
[62] 3DP TCP ≤ 5 µm and 130–800 µm 40%− 60% 3–11 MPa 3D scaffold femoral defects of
rats
[54] 3DP HA 10–60 µm and 1.5–2 mm ~55.1% ~0.88 MPa 3D scaffold –
[57] 3DP HA 0.3–0.4 µm and ~20 µm ~50% 5–20 MPa 3D scaffold rats
(micropore)
[59] 3DP CaP – ~50% 1.3–8.4 MPa 3D scaffold –
[60] 3DP MgO/ZnO-TCP Several μm and 200 µm ~45.47% ~27.46 MPa 3D scaffold –
[64] 3DP Preceramic CaSiO3 < 50–100 µm(micropore) ~80% 1 MPa 3D scaffold –
[150] Wax inkjet BCP ~340 µm ~48.7% ~9.9 MPa 3D –
printing Scaffold
[43,171] DIW 6P53B bioactive 100–500 µm ~60% 136 MPa (bulk) Grid-like scaffold –
glass
[176] DIW 13–93 bioactive ~300 µm ~47% 86 MPa 3D woodpile –
glass
[68,69] DIW freeze 13–93 bioactive ~300 µm ~50% 140 MPa Grid-like scaffold –
glass
[93] DIW freeze HA 10 µm and 1–10 mm – 22 MPa Honeycomb –
[70] DIW HA ~350 µm ~52.26% 16.77 MPa Grid-like scaffold –
[71] DIW MBG ~1 mm ~60.4% 16.1 MPa 3D woodpile –
[174, DIW 45S5 bioactive ~250 µm ~63% 2–13 MPa 3D woodpile –
175] glass
[169] DIW CaSiO3 ~1 mm 65% 3.57 MPa 3D woodpile femur
defect of rat
[170] DIW Ca3SiO5 ~170 µm 61% 12.9 MPa 3D woodpile rabbit femoral
defects
[41] FDC PCL/HA ~765 µm ~26% 15.43 MPa Grid-like scaffold long goat femur
(bulk) bone
[45] DLP HA/TCP ≤ 5 µm and 20–1000 µm 20%− 80% 15 MPa Free-form structure rat long bone
[46] DLP AKT/45S5 400 µm (designed) 22%− 9.67–26.72 MPa bone–mimicking rabbit femoral
40.3% scaffolds defects
[173] DLP 45S5 500 µm 50% 0.33 MPa Free-form structure –
[124] DLP ZrO2/HA – 54.6% > 20 MPa Free-form structure –
[125] DLP HA 300–600 µm 49.8% 15.25 MPa Free-form structure –
[123] DLP HA ~1 mm 74% 4.09 MPa TPMS structure –
[126] DLP CaP ~620 µm 64.5% 9.03 MPa Free-form structure Beagle dog
[127] DLP freeze CaP 1–4 µm and 1 × 1.5 mm2 ~76.4% ~3.2 MPa Gyroid structure –
[108] SLS CaP-PHBV 0.8 mm (printed) ~62.6% 0.5–0.6 MPa 3D scaffold –
[107] SLS a-PC/HA 10–220 µm 77.36% 22 MPa 3D scaffold –
[113] SLS graphene/nano- ~1 mm – 48.65 MPa 3D scaffold –
58S
[114] SLS PEEK/β-TCP/PLLA ~450 µm – 17–33 MPa 3D scaffold bone defect of
rabbit

widely known structural ceramics (e.g., alumina, silica, zirconia), these devices. Sun et al. printed a 3D interdigitated microbattery architecture
functional ceramics can bring their particular physical and chemical (3D-IMA) using Li4Ti5O12 (LTO) as the anode material and LiFePO4
properties into the produced monoliths. And the 3D printed porous (LFP) as the cathode material [179]. The areal energy and power density
functional ceramics can promote the performance of the corresponding of the 3D micro battery is much higher than conventional counterparts

17
F. Zhang et al.
due to the high aspect ratio of electrodes prepared by DIW. Liu et al.
proposed the fabrication of LFP porous electrode using low-temperature
DIW [180]. The highly porous electrode structure contributed the
improvement of electrochemical performance. Except using porous
functional ceramics for electrochemical energy storage, 3D printed
porous ceramics have been reported for catalysis, sorption [181,182],
heat exchanger [183], static mixer [184], and environmental remedia­
tion. Jonhson et al., 3D printed a fully ceramic device for portable solar
desalination to tackle water scarcity from an energy and sustainability
perspective [185]. The 3D tailored porous silica structure combines
nanopores and microchannels exhibiting uniform water transport de­
livery and thermal insulation (Fig. 24). Tubío et al. synthesized a copper
supported Al2O3 catalytic system with a woodpile porous structure
[186]. The structure possessed exceptional mechanical strength, a high
surface-to-volume ratio, and controlled porosity. The Cu are immobi­
lized in the Al2O3 matrix to avoid the leaching of the metal into the
reaction medium. Zeolites are microporous, aluminosilicate minerals
that can accommodate a wide variety of cations, such as Na+, K+, Ca2+,
Mg2+ and others. Thakkar et al. fabricated 3D structured adsorbents for
CO2 removal [187]. By employing 3D printing technology, zeolite
monolith with various cross sections, channel sizes, and wall thickness
can be facilely fabricated. Couck et al. printed ZSM-5 scaffold using DIW
(in which they called 3DFD (Three Dimensional Fiber Deposition)) for
CO2, CH4, and N2 separation [188]. Lefevere et al. reported the printing
of ZSM-5 as structured adsorbent or catalyst. Liu et al. printed cellular
structure of lithium orthosilicate (Li4SiO4) for possible use as tritium
breeder units in fusion reactors [189]. The DLP technology printed
structures possess high phase purity and suitable and tailorable effective
Fig. 24. Highly insulative with effective water transport design. (a) Fabrication of the ceramic water transporter with tailored microchannels. (b) BET measurement
shows the high concentration of nanopores in the ceramic wick structure. (c) High water transport rate by varying the mesh spacing. (d) Optimized insulation height
corresponding to the water evaporation rate. (e) Digital image of the controlled environmental setup for seawater evaporation [185].
18
Journal of the European Ceramic Society xxx (xxxx) xxx
‘packing fraction’ for breeding application. In environmental protection,
3D printing of Pd-decorated hierarchically porous TiO2 scaffolds was
reported for the efficient treatment of highly concentrated 4-Nitrophe­
nol waste water [190]. The printed mm-sized interconnected channels
in the scaffolds benefits rapid mass and ion transportation, while the
abundant μm- and nm-sized pores on the surface of the scaffolds offer
adequate anchoring sites for Pd nanoparticles. Xu et al. prepared
whiskers-coated ceramic mesh structure by DLP. First, porous alumina
structure was printed using LCM [191]. The prepared alumina mesh
structure was then dipped into suspension of boron oxide to allow the
growth of aluminum borate whiskers. The combined all-ceramic mesh
structure can be efficiently used for oil/water separation. Tokahashi
et al. discussed the potential of porous ceramics fabricated by gelcasting
in mitigating environmental issues [192]. These porous ceramics can be
technically realized by 3D printing as well using various hybrid shaping
technologies discussed previously. Owing to the large surface area
served by porous ceramics, 3D printing can be chosen to fabricate heat
exchangers [183]. Many complex designs which cannot be produced
with any other technology are realized [193]. The detailed introduction
of porous ceramics from material aspects about these energy-based ap­
plications can be found in two recently published reviews [194,195].
Besides, in wireless communication field, 3D printed porous ceramics
are suitable to serve as the potential materials for dielectric antenna. By
controlling the printing process, both permittivity and loss tangent of
ceramic can be altered, which enriches the material of antenna. Huang
et al. printed ABS with different infill percentages to attain designable
permittivity [196]. But in consideration of the intrinsically low
permittivity of ABS, it is certain that porous ceramic can achieve larger
F. Zhang et al.
permittivity tuning range. In summary, the application of 3D printed
porous ceramics continuously emerges. However, it is important to
understand the advantages of 3D printing used in preparation of porous
ceramics in these areas to fully unlock the potential.
4. Conclusion and future perspective
This paper reviews the innovative 3D printing technologies for
fabrication of porous ceramics. Compared to traditional porous ceramics
fabrication processes, 3D printing enables the printing of porous ce­
ramics with both periodic pores and hierarchical porous structure. This
capability can further grant the fabrication of functional porous ce­
ramics with designed mechanical properties. Almost all 3D printing
technologies can be used to fabricate ultra large porous ceramics (pore
size > 300 µm), including SLS, FDC, DIW, IJP, SLA, LOM and 3DP.
However, it is still quite challenging to fabricate hierarchical porous
ceramic structures. Only a few 3D printing techniques can fabricate
hierarchical porous ceramics by combining with traditional porous ce­
ramics fabrication methods such as direct foaming, freeze casting.
Further, very less process is capable of further controlling the micro­
structure, for example, the pore size, pore shape, interconnectivity, and
gradient pores.
DIW is the most popular porous ceramics printing technique due to
the versatile material choices and easy-to-span process. Besides, multi­
ple tradition porous ceramic fabrication methods can be combined with
DIW. By combining 3D printing with conventional porous ceramics
fabrication routes, it is possible to fabricate hierarchical porous struc­
tures, such as by integrating freeze casting with DIW, combining direct
foaming with DIW, and coupling sacrificial templating with DIW.
However, the resolution of the DIW is limited. Powder bed-based ap­
proaches (i.e., 3DP and SLS) can innately produce porous ceramic
structures. SLS and 3DP are the two others frequently adopted porous
ceramics fabrication techniques due to their innate porous feedstock,
which makes pores easily formed. However, both processes yield coarse
feature and their capability to control the micro structure of the porous
ceramic needs to be explored and enhanced. Further, the mechanical
strength of porous ceramics fabricated using 3DP and SLS has to be
improved.
Using SLA and LOM to fabricate porous ceramics are relatively new.
SLA can fabricate the most precise part. The methods to produce porous
ceramics using SLA are versatile, including resin-ceramic composite
printing, preceramic polymer polymerization, and TPP of tiny lattice
templates. However, there are still some issues need to be tackled for
these processes. For example, the burning out of resin in ceramic particle
doped SLA generally has some leftover polymers, which can be toxic for
bone tissue engineering applications. The micropores generated through
resin burning out are difficult to control. Thus, printing of resin-ceramic
method is not good for fabricating hierarchical porous ceramics. Poly­
mer derived ceramic is a universal ceramic fabrication technique, it can
be used in most of the 3D printing processes such as stereolithography,
binder jetting, laminated object manufacturing, and selective laser sin­
tering. It can be used to fabricate well-ordered porous ceramics. The
polymer derived ceramics provides a supplement method for porous
ceramics fabrication. For example, the transform of SLA printed silica
into glass [197] can be similarly used to print bioactive glass by suitable
material engineering. However, polymer derived ceramics are quite
limited in the material availability. Although most 3D printing processes
can mainly be used to produce large pores (>100 µm), certain medium
even micro pores can be fabricated using stereolithography based 3D
printing.
Besides the great progress made in the process aspects, the applica­
tions of 3D printed porous ceramics are booming as well. The most
significant application of porous ceramics is in bone tissue engineering,
which uses 3D printing and bioceramics to fabricate 3D scaffold. How­
ever, current studies in 3D printing of artificial bone scaffold are still in
their infancy stage. The full potential to fabricate complex architecture
19
Journal of the European Ceramic Society xxx (xxxx) xxx
and porous structure needs to be unlocked with a further understanding
of the influence of critical pore parameters on the resultant properties. It
is expected that more applications of 3D printed porous ceramics will
emerge and it is important to think carefully in advance the benefit of
using 3D printing for each specific application.
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.
Acknowledgements
This work is financially supported from the startup funding at the
Nanjing Normal University. This work was also partially supported by
the Natural Science Fund for Colleges and Universities in Jiangsu
Province (No. 20KJA460004), the Key Technology RD Program of
Jiangsu Province (BE2018010-2&BE2018731), and the Natural Science
Foundation of Jiangsu Province (BK20190712).
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