RESEARCH ARTICLE
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3D Printing of Hollow Microspheres into Strong
Hierarchical Porous Ceramics
Wenlong Huo, Elena Tervoort, Silvan Gantenbein, Etienne Jeoffroy, Jinlong Yang,*
and André R. Studart*
Porous ceramics are demanded in a wide range of high-temperature,
biological and energy-related applications, but may show conflicting
properties or suffer from poor mechanical properties. Introducing pores at
different length scales has been shown to be a promising design strategy to
combine antagonistic performance parameters and reach high porosity
without severely compromising strength. Here, a cost-effective and simple
process to create strong, highly porous ceramics via direct ink writing of
suspensions of hollow microspheres into cellular architectures with pores at
three hierarchical levels is reported. X-ray diffraction, rheological
measurements, scanning electron microscopy, and mechanical tests are
conducted to thoroughly study the processing steps and morphology of the
printed hierarchical porous ceramics. The presence of pores at multiple length
scales increases significantly the mechanical strength of the porous structure,
providing a useful platform for the manufacturing of lightweight ceramics
from inexpensive and widely available feedstock materials.
1. Introduction
Ceramics with hierarchical porosity offer attractive properties for
mechanical, catalytic, filtration, and biomedical applications. [1]
When used as filters, bio-scaffolds, or catalytic substrates, such
hierarchical materials can be designed to combine in a single
structure, the small pores desired for a high specific surface area
with the large pores required to reach high permeability and
W. Huo, E. Tervoort, S. Gantenbein, E. Jeoffroy, A. R. Studart
Complex Materials
Department of Materials
ETH Zurich
Zurich 8093, Switzerland
E-mail: andre.studart@mat.ethz.ch
W. Huo, J. Yang
State Key Laboratory of New Ceramics and Fine Processing
School of Materials Science and Engineering
Tsinghua University
Beijing 100084, P. R. China
E-mail: jlyang@tsinghua.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/admt.202300065
© 2023 The Authors. Advanced Materials Technologies published by
Wiley-VCH GmbH. This is an open access article under the terms of the
Creative Commons Attribution-NonCommercial License, which permits
use, distribution and reproduction in any medium, provided the original
work is properly cited and is not used for commercial purposes.
DOI: 10.1002/admt.202300065
Adv. Mater. Technol. 2023, 2300065 2300065 (1 of 12) © 2023 The Authors. Advanced Materials Technologies published by Wiley-VCH GmbH
low pressure drop. These unique set
of properties can simultaneously en-
hance antagonistic performance param-
eters, such as the throughput and effi-
ciency of filtration membranes and cat-
alytic reactors or the tissue in-growth
rate and cellular adhesion in ceramic bio-
scaffolds. In terms of mechanical prop-
erties, hierarchical porous materials have
been explored by living organisms to cre-
ate structures of high mechanical effi-
ciency, the architecture of bamboo stems
being a prominent example.[2] Translat-
ing such hierarchical designs to syn-
thetic systems has allowed for the man-
ufacturing of lightweight materials with
unprecedented mechanical properties.[3]
Because of the brittle nature of ceram-
ics, strategies to enhance their mechan-
ical properties are crucial in any final ap-
plication.
While several processing routes have been proposed for the
manufacturing of porous ceramics,[1a,c,e,4] recent studies have
shown the potential of 3D printing of bespoke inks as a unique
approach to generate materials with pores at different length
scales.[3a,5] Direct ink writing is a particularly enticing technol-
ogy due to its low cost and multimaterial nature. [6] In this addi-
tive manufacturing approach, the printing toolpath creates open
channels at millimeter length scales, whereas constituents of
the ink give rise to sub-millimeter pores below the resolution
of the printer. Sub-millimeter macropores can be formed us-
ing emulsions and foams in a direct ink writing process.[5b,7]
In this case, the air bubbles and oil droplets of the ink serve
as templates for the creation of macropores upon drying and
sintering of the printed ceramic. In another approach, metal
particles have been added to the ink to generate micropores
in the printed filaments after thermal oxidation at high tem-
peratures. [8] Despite the demonstrated potential of these tech-
nologies, the chemical modifiers needed to stabilize emulsion-
and foam-based inks and the limited metal compositions lead-
ing to porosity by thermal oxidation may constrain the design
space for hierarchical porous ceramics produced via additive
manufacturing.
Hollow microspheres with inorganic shells offer a potential so-
lution to address the above limitations. Two examples of com-
mercially available sources of such microspheres are so-called
glass bubbles and cenospheres. Glass bubbles are 10–100 μm
hollow microspheres with a thin shell made out of mixtures of

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Figure 1. Workflow used to manufacture hierarchical porous ceramics by 3D printing suspensions of hollow microspheres. A) Mixing steps required for
the preparation of the suspensions employed as feedstock ink. B) Direct ink writing (DIW) of the suspension on a build platform for the creation of 3D
objects with complex shapes. C) Hierarchical structure within the printed filament, highlighting the hollow microspheres, the network of nano-bentonite
particles and the hydroxypropyl cellulose molecules. D) Migration of bentonite and cellulose to the contact points between microspheres to form bridges
within the filament during drying.
borosilicate and soda lime glass. Cenospheres feature a simi-
lar size range and hollow morphology but the shell material is
an aluminosilicate. Because they are formed in fly ash, a by-
product from coal-fired thermal power plants, cenospheres are
very abundant and affordable.[9] In contrast, glass bubbles have
been applied to more high-end applications that require better
control of morphology and chemical impurities. Both types of
hollow microspheres have been exploited for the fabrication of
thermal insulators, impact absorbers, as well as lightweight con-
crete and composite materials, also known as syntactic foams.[10]
Using such hollow microspheres as pore formers in conventional
manufacturing processes has enabled the fabrication of porous
ceramics[11] with enhanced thermal insulation properties[12] and
low dielectric constant.[13] Introducing such microspheres as
building blocks in colloidal inks for extrusion-based printing
could open new opportunities for the design and manufac-
turing of hierarchical ceramics with pores at multiple length
scales.
Here, we design suspensions of hollow microspheres and
use them as inks for the low-cost extrusion-based 3D printing
of hierarchical porous ceramics with enhanced mechanical ef-
ficiency. Rheological additives are incorporated in the ink for-
mulation to achieve the flow properties required for printing
via direct ink writing. We start by characterizing the morphol-
ogy, size distribution and chemical composition of selected sil-
ica and ash hollow microspheres, also known as cenospheres.
The effect of rheological modifiers on the colloidal stability,
viscoelastic behavior, and printability of suspensions is evalu-
ated to establish guidelines for the formulation of optimal inks.
Such inks are then utilized to 3D print grid-like architectures
with hierarchical porosity, which are mechanically characterized
and compared to conventional porous structures. Finally, we de-
velop an alternative ink formulation to enable light-assisted direct
ink writing of hierarchical porous ceramics with more complex
3D shapes.
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2. Results and Discussion
2.1. Formulation and Printability of Hollow Sphere-Based Ink
The manufacturing of hierarchical porous structures using pre-
formed hollow microspheres requires a series of simple process-
ing steps that include: i) the preparation of an ink with suitable
rheological properties, ii) the deposition of filaments into the de-
sired macroscopic architecture by direct ink writing (DIW) and,
finally, iii) the drying and sintering of the printed structure into a
mechanically robust 3D object (Figure 1). The inks investigated
in this work consisted of aqueous suspensions of hollow micro-
spheres containing 13–55 nm bentonite particles and hydrox-
ypropyl cellulose as rheological modifiers (Figure S1, Supporting
Information). The suspensions were prepared through the se-
quential addition of nano-bentonite particles and hollow spheres
into an aqueous solution with predissolved hydroxypropyl cellu-
lose (Figure 1A). After thorough mechanical mixing, the ink was
filled into the cartridge of a customized DIW printer and extruded
at room temperature in the form of a filament to create complex-
shaped macroscopic geometries (Figure 1B).
The resulting printed object can be designed to display hierar-
chical structural features at multiple length scales. The printing
path of the extruding nozzle defines the structure at the coarser
millimeter scale, whereas smaller features arise from the build-
ing blocks within the ink (Figure 1C). The hollow microspheres
generate pores ranging from 10 to 100 μm, depending on the
raw material source selected. A network of nano-bentonite parti-
cles and cellulose molecules is formed between the hollow micro-
spheres and provided sufficient strength to enable direct drying
of the object in air. During drying, capillary forces pull the nano-
bentonite particles and cellulose molecules toward the contact
point between the hollow microspheres (Figure 1D). Sintering
of the dried structures leads to strong objects while preserving
the complex geometry created by the printing process.
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To illustrate the proposed printing process, we use ash and sil-
ica particles as examples of hollow microspheres incorporated in
the initial ink (Figure 2). Hollow ash (HA) and hollow silica (HS)
microspheres with densities of 0.42 and 0.23 g cm−3 , respectively,
are formed as by-products of the combustion of coal in power
plants and are commercially available at large quantities and very
low cost. The hollow microspheres employed in this study dis-
play a fully closed morphology with a shell layer on the order of a
few micrometers (Figure 2A,B). The closed nature of the spheres
makes them readily float when added to water (Figure 2C). X-ray
diffraction and chemical characterization of the microspheres re-
veal that the HA particles contain the aluminosilicate crystalline
phase mullite and 4% impurities, whereas the HS particles are
glassy silica spheres with about 14.0 wt% CaO and 4.4 wt% Na2 O
(Figure 2D and Table S2, Supporting Information). The HA and
HS microspheres exhibit a relatively broad size range, which can
be described by a lognormal distribution with median sizes of 61
and 37 μm, and standard deviations of 0.42 and 0.45, respectively
(Figure 2E,F).
The hollow nature and the large sizes of the microspheres
make the preparation of homogeneous inks a challenging task.
On the one hand, the low specific gravity of the hollow spheres re-
sults in undesired buoyant forces in water. On the other hand, the
large sphere size may lead to nozzle clogging issues and phase
separation phenomena. In order to design formulations that cir-
cumvent these potential issues and are suitable for direct ink writ-
ing, we first performed extensive exploratory experiments with
hollow sphere suspensions containing distinct rheology modi-
fiers. Rheological additives in the form of either nanoparticles or
molecular species were tested, including fumed silica particles,
bentonite nanoparticles, poly(vinyl alcohol), agar, 𝜅-carrageenan,
and hydroxypropyl cellulose (see Table S4, Supporting Informa-
tion).
Our experiments revealed that the combination of bentonite
nanoparticles with hydroxypropyl cellulose molecules is the most
promising to generate homogeneous printable inks (Figure 3 and
Figure S2, Supporting Information). Bentonite nanoparticles
are expected to form a strong percolating network between the
hollow spheres due to the negative and positive electric charges
developed on the faces and edges of the disc-shaped particles,
respectively (Figure 3A). The negative charges arise from the
dissolution of alkali and alkaline earth ions from the faces of the
particle into the aqueous phase, whereas the protonation of hy-
droxyl groups at slightly acidic pHs leads to the positive charges
at the particle’s edges. Chemical analysis by X-ray fluorescence
confirmed the presence of alkali and alkaline earth ions in the
bentonite nanoparticles (Table S3, Supporting Information).
The formation of a strong percolating network is manifested
by the high yield stress of aqueous suspensions containing ben-
tonite and hollow spheres. We experimentally found that the ad-
dition of hydroxypropyl cellulose to these suspensions allows us
to controllably reduce the strength of the percolating network and
thus obtain homogenous printable inks (Figure S3, Supporting
Information). This plasticizing effect of hydroxypropyl cellulose
is probably associated with the formation of hydrogen bonds with
the hydroxyl groups on the bentonite particle surface and the re-
sulting softening of interparticle bonds.
Tuning the concentrations of hollow spheres and of bentonite
nanoparticles in the aqueous suspension was found to be crucial
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to formulate inks with the required rheological properties (Fig-
ure 3 and Figures S4–S6, Supporting Information). To explore
the design space of our formulations, we conducted printing ex-
periments with systematically varied concentrations of hollow
spheres and bentonite nanoparticles, while keeping the content
of hydroxypropyl cellulose approximately constant at 2 wt% (Fig-
ure 3B).
Too low bentonite concentrations resulted in gravity-induced
phase separation of the ink or to the phenomenon of liquid phase
migration during extrusion (gray and blue areas in Figure 3B,C).
Gravity-induced phase separation results from the buoyant forces
on the hollow spheres and can be prevented through the forma-
tion of a strong percolating network of bentonite nanoparticles
around the spheres. Liquid-phase migration is a well-known ef-
fect that occurs when the pressure exerted upon extrusion leads
to compaction of the particle network within the ink and thereby
the displacement of the liquid phase relative to the solid phase.[14]
Our experiments show that concentrations of bentonite
nanoparticles above 3–4 wt% are necessary to create a particle
network that is strong enough to withstand buoyant forces and
to prevent the compaction of the microspheres along with the rel-
ative displacement of the aqueous phase (Figure S7, Supporting
Information). It is important to note that the fraction of hollow
spheres in the ink also has to be tuned within a relatively nar-
row range in order to prepare homogenous inks for direct ink
writing (green area, Figure 3B,D). Too low microsphere contents
lead to distortion of the printed objects due to the insufficient
yield stress of the ink, whereas too high concentrations of hollow
spheres result in nozzle clogging combined with liquid phase mi-
gration (pink and orange areas in Figure 3B, respectively). Such
qualitative results provide useful guidelines for the formulation
of printable inks with ash and silica hollow spheres (Figure 3B
and Figure S6, Supporting Information).
2.2. Rheological Behavior of Hollow Sphere-Based Ink
To better characterize the inks that were identified as homoge-
neous and printable in the first qualitative assessment, we mea-
sured the rheological properties of selected ink formulations un-
der steady-shear and oscillatory conditions (Figure 4 and Figure
S4, Supporting Information). Our experiments indicate that the
presence of bentonite nanoparticles at concentrations above 3
wt% in the ink is essential to achieve the rheological properties
suitable for 3D printing via DIW. Previous work has shown that
inks suitable for DIW should exhibit a viscoelastic behavior with
storage modulus (G′) and yield stress (𝜏 y ) on the order of at least
105 and 102 Pa, respectively, in order to prevent capillary-induced
shape distortion and gravity-driven sagging effects.[15] The exact
storage modulus and yield stress values required for printing de-
pends on the several ink- and object-specific parameters, such
as the surface tension, printing resolution, specific gravity of the
ink, and length of free-spanning filaments.[3a,16]
Oscillatory shear measurements reveal that inks with ben-
tonite concentrations of 3.5 and 7.0 wt% feature a well-defined
viscoelastic response (Figure 4A), which is characterized by a stor-
age modulus (G′) that is higher than the loss modulus (G″) for
all applied stresses below the yield point of the ink (𝜏 y ). The stor-
age modulus of the ink was found to increase from 7.6 × 10−3
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Figure 2. Hollow ash (HA) and hollow silica (HS) microspheres investigated in this study. Scanning electron microscopy (SEM) images of A) HA and
B) HS microspheres used for the preparation of printable inks. C) Pictures of HA and HS microspheres floating in water. D) X-ray diffraction pattern of
as-received HA and HS particles. Particle size distributions of the investigated E) HA and F) HS microspheres.

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Figure 3. Expected microstructure and printability of suspensions containing hollow spheres, bentonite nanoparticles, and hydroxypropyl cellulose. A)
Schematics illustrating the molecular interactions expected to occur within the percolating network of bentonite nanoparticles and between bentonite
surfaces and hydroxypropyl cellulose molecules. B) Diagram displaying the concentrations of bentonite nanoparticles and HA microspheres required
to obtain printable inks with good shape retention (green area) and the printability issues encountered outside the optimum ranges. C) Representative
ink that undergoes liquid phase migration during printing. Liquid migration leads to a lower water content in the ink inside the syringe compared to the
printed filaments. D) Example of grid-type structure manufactured using a homogenous printable ink [green area in (B)].

to 660 and 830 kPa as the bentonite concentration was changed
from 0 to 3.5 and 7.0 wt%, respectively (Figure 4B). Such stiffen-
ing effect was accompanied by an increase in yield stress from
2 to 694 and 1491 Pa for the same increasing bentonite concen-
trations, respectively. These observations reflect the formation of
a percolating network of nanoparticles between the large hollow
spheres, which becomes stronger as the bentonite content is in-
creased. Fixing the bentonite content at 7.0 wt% and varying the
concentration of hollow ash spheres between 35 and 41 wt% also
results in viscoelastic inks with G′ and 𝜏 y values within the ranges
270–2600 kPa and 607–2200 Pa, respectively (Figure 4C,D). These
storage moduli and yield stress values are higher than the typical
thresholds required for DIW, thus supporting the findings of our
qualitative printing experiments (Figure 3B) and providing quan-
titative rheological criteria for the design of inks containing large
hollow particles.
Besides the storage modulus and yield stress, another rheo-
logical property that is relevant for DIW printing is the shear-
thinning behavior of the ink. Shear thinning is desired because
it reduces the pressure that needs to be applied to extrude the ink
through the printing nozzle. Steady-state rheological analysis of
our inks reveal that all formulations considered to be printable
in the qualitative experiments also exhibit strong shear-thinning
response (Figure 4E,F, and Figure S5A,B, Supporting Informa-
tion). Such a fluidizing behavior reduces the apparent viscosity of
the ink by five orders of magnitude when the shear rate is ramped
up to 1000 s−1 . Importantly, we found that the initial apparent vis-
cosity on the order of 107 Pa s is fully recovered when the ink is
allowed to rest (Figure S5C, Supporting Information). Such re-
covery is essential to minimize shape distortion of the filaments
after extrusion through the printing nozzle. Our results indicate
that the percolating network of bentonite nanoparticles is able to
completely re-assemble after the applied shear stresses cease.
2.3. 3D Printing Hollow Sphere-Based Ink into Complex-Shaped
Structures
Ink formulations identified as homogeneous and printable can
be employed to create complex-shaped 3D objects, such as grid-
like structures, profiled cellular architectures, or any other ge-
ometry accessible by the direct ink writing technique. The op-
timum rheological behavior of the inks ensures high fidelity
and minimum shape distortion of the manufactured objects
(Figure 5A,B; Figures S7–S10 and Videos S1–S5, Supporting In-
formation). Because of the network of bentonite nanoparticles
formed between the hollow spheres, no aging effect was observed
and the ink remained printable for as much as two weeks after
preparation (Figure S9 and Video S3, Supporting Information).
To better understand the microstructure of the printed ink at dif-

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Figure 4. Rheological behavior of suspensions containing hollow spheres and bentonite nanoparticles. Viscoelastic properties of selected inks mea-
sured by oscillatory rheology, illustrating the effect of A) bentonite nanoparticles at a fixed total solid content of 45 wt% (bentonite + HA) and C) HA
microspheres in suspensions containing 7 wt% bentonite. Storage modulus measured at shear stress of 10 Pa (G′) and yield stress (𝜏 y ) data obtained
from the oscillatory measurements as a function of the concentration of B) bentonite nanoparticles and D) HA microspheres. E) Apparent viscosity as a
function of the applied shear rate for inks containing distinct concentrations of HA microspheres while keeping the bentonite content constant at 7 wt%.
F) Schematics illustrating the rupture and re-assembly of the network of bentonite nanoparticles when subjected to shear and rest periods, respectively.
All compositions represented in this figure contain 2 wt% hydroxypropyl cellulose.

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Figure 5. Complex-shaped hierarchical structures obtained by direct ink writing of suspensions with hollow spheres, bentonite nanoparticles and hydrox-
ypropyl cellulose. A) Photographs of a grid-like structure along the printing, drying and sintering steps of the fabrication process. The optical microscopy
image shown in the far left depicts the homogeneous distribution of hollow spheres in the ink. B) Printing of profiled cellular architectures, highlighting
the porosity within the printed filaments after sintering. C) SEM images of a filament that was frozen in liquid nitrogen, freeze-dried and fractured for
microstructural analysis. SEM cross sections of two separate filaments after D) drying and E) sintering at 1300 °C. The above structures were obtained
using inks containing 41.5 wt% HA microspheres, 6.8 wt% bentonite, and 2.0 wt% hydroxypropyl cellulose.

ferent stages of the process, we SEM-imaged printed samples
after freeze drying (Figure 5C), after drying in air (Figure 5D),
and after drying in air followed by sintering (Figure 5E). SEM
images of ink filaments that were frozen in liquid nitrogen and
later freeze-dried show that the network of bentonite nanoparti-
cles forms a homogeneous continuous phase around the larger
hollow spheres (Figure 5C and Figure S11, Supporting Informa-
tion).
Drying of the printed structures in air preserves the macro-
scopic geometry of the object and is accompanied by a linear
shrinkage as low as 0.5% (Figure S12, Supporting Informa-
tion). The capillary forces developed during drying leads to the
accumulation of bentonite nanoparticles at the contact points
between the hollow spheres (Figure 5D). The formation of
such bentonite bridges increases significantly the mechanical
strength of the dried structures. Indeed, HA (HS) samples with
porosity of 87.7% (88.9%) show a high compressive strength
of 1.82 MPa (2.65 MPa) after drying (see Table S5, Supporting
Information). This strength is sufficiently high to allow for ma-
chining of the structure into objects with smooth surfaces and
precise end dimensions. Considering its excellent strength and
the low cost of the raw material, the HA ink can be potentially

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utilized to produce affordable lightweight blocks for structural
and insulating applications. In this case, a proper surface coating
is required to endow water resistance to the final structure.
Sintering of the dried structures leads to the densification and
reaction of the bentonite nanoparticles, thus strengthening the
interconnections between the hollow spheres (Figure 5E). This
enhances the mechanical strength of the object and makes it
fully water resistant. The low concentration of cellulose present
in the dried structure minimizes the amount of organic matter
that needs to be removed during heat treatment, avoiding the in-
troduction of defects in the sintered object. Sintering tempera-
tures in the ranges 800–850 and 1250–1350 °C were found to be
adequate to densify and strengthen the printed structures made
out of HS and HA microspheres, respectively (Figure S13, Sup-
porting Information).
The densification process associated with sintering results in
a total linear shrinkage in the range of 7.0%–8.0% and 16%–18%
for the HA and HS ceramics, respectively. The stronger shrink-
age observed for HS-containing samples results from the change
in shape of the HS particles from spheres to polygons during the
sintering process (Figure S13, Supporting Information). Overall,
these shrinkage levels are much lower than those observed after
drying and sintering of ceramic foams prepared via colloidal pro-
cessing routes, which typically shrink between 20% and 30%.[17]
In contrast to colloidal approaches, the use of hollow spheres
with dense shells does not require the sintering of particle as-
semblies to form dense pore walls upon heat treatment. Instead,
sintering and densification occurs predominantly within the ben-
tonite nanoparticles that form interconnections between the hol-
low spheres, thus reducing the overall shrinkage of the porous
material.
The level of densification of the bentonite nanoparticles deter-
mines the strength of the sphere interconnections. For HA ce-
ramics, a low sintering temperature of 1250 °C results in weak
interconnections that are easily broken upon mechanical load-
ing. By increasing the sintering temperature above 1300 °C,
stronger interconnections with larger contact area are formed.
This changes the crack path from intergranular (along spheres)
to intragranular (through spheres) during fracture of the struc-
tures (Figure S14, Supporting Information). At these temper-
atures the ash and bentonite nanoparticles transform into the
crystalline phase mullite (Figure S15A, Supporting Information),
which forms needle-like morphologies that reinforce the inter-
connections between hollow spheres (Figure 5E). The presence
of high contents of SiO2 and Al2 O3 in the HA microspheres is
crucial for mullite formation at high temperatures. Because it
lacks Al2 O3 in its chemical composition, the initially amorphous
HS microspheres form predominantly cristobalite after sintering
(Figure S15B, Supporting Information).
2.4. Mechanical Strength of Printed Hierarchical Porous
Ceramics
Inks containing HA and HS microspheres can be printed into
hierarchical structures featuring intrinsically porous filaments
with pore sizes of 30–110 and 15–70 μm, respectively. This pore
size range directly reflects the size distribution of the micro-
spheres used as macropore generators. Together with the large
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open channels of the printed grid-like architecture (coarser pores)
and the interstices between the microspheres (finer pores), these
intermediately sized macropores eventually lead to a unique hi-
erarchical architecture displaying three classes of pores at dif-
ferent length scales (Figure 6A). The hierarchical porous struc-
ture is mechanically reinforced by the dense bentonite intercon-
nections formed between the microspheres after sintering. To
quantify the mechanical properties of such hierarchical struc-
ture, we compare the compressive strength of HA and HS grid-
like samples with literature data for mullite- and silica-based ce-
ramics with monomodal porosity and similar chemical composi-
tion (Figure 6B,C). Porous ceramics with high mechanical prop-
erties are essential for several possible functional applications of
our printed objects, including thermal insulation, catalysis, and
filtration.[1c,18]
The hierarchical porous structures obtained by printing and
sintering microspheres show enhanced mechanical efficiency
compared to state-of-the-art ceramics containing monomodal
porosity. This is evidenced by depicting the measured compres-
sive strength data as a function of the relative density of the sam-
ples (Figure 6B,C). Our experimental results indicate that the
compressive strength of structures with multiscale pores is about
one order of magnitude higher than that of reference samples
at comparable low relative densities. This places the hierarchi-
cal porous architecture in an unpopulated region of the strength
plot, which is assigned to structures with high mechanical effi-
ciency. The elastic modulus of the printed ceramics was observed
to follow a similar trend with respect to the apparent porosity (Fig-
ure S16, Supporting Information). Such findings are in agree-
ment with recent studies on the mechanical properties of hier-
archical porous materials obtained by 3D printing.[3] In partic-
ular, grid-like HA porous ceramics with porosity of 87.6% and
HS porous ceramics with porosity of 92.3% show a high strength
of 4.1 and 2.4 MPa, respectively. Analogous to the hierarchical
design principles found in bamboo and other natural materials,
printing of such hierarchical porous architectures enables the re-
moval of material from less stressed regions of the structure, re-
ducing its weight without a major drop in mechanical properties.
This is expected to occur when the load-bearing elements of the
porous structure are subjected to bending stresses during me-
chanical loading.[3b]
In contrast to previous pore templating approaches,[3b] the
use of hollow spheres to create macroporosity within printed
filaments enables the manufacturing of hierarchical porous
structures without the surface modification procedures typically
needed to stabilize pore-forming foam and emulsion templates.
This feature provides flexibility to the ink formulation, which can
be designed to fulfill other processing requirements or accom-
modate additional functionalities. We illustrate this flexibility by
formulating photo-curable inks that can be printed into com-
plex geometries using a light-assisted direct ink writing approach
(Figure 7).
To make the ink light-curable, we either add photo-
polymerizable monomers into the aqueous ink of hollow
microspheres or replace the liquid phase altogether by a
light-reactive monomer mixture. Using acrylamide (AM)
and bis-acrylamide as water-soluble mono- and bifunctional
monomers, it was possible to print a porous structure with 3D
spring geometry using this light-assisted extrusion approach
© 2023 The Authors. Advanced Materials Technologies published by Wiley-VCH GmbH

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Figure 6. Mechanical properties of hierarchical porous ceramics obtained via DIW printing followed by sintering. A) Schematics showing the hierarchical
architecture of the grid-like porous structure. Compressive strength as a function of relative density for structures prepared with B) HA and C) HS
microspheres in comparison with literature data for mullite (B)[19] and silica-based (C)[20] porous samples of similar chemical composition.
(Figure 7). During the direct ink writing process, the extruded
filament is locally exposed to UV light to immediately consol-
idate the structure on the fly. The presence of bentonite and
hydroxypropyl cellulose in the ink is important to maintain
the extruded shape before light-induced polymerization of the
filament. The dried filament obtained by this light-assisted DIW
process shows a continuous polyacrylamide network between
the hollow microspheres. Similar 3D spring-like structures
have also been printed using a light-reactive monomer mixture
as liquid phase of the microsphere suspension (Figure S17,
Supporting Information). During calcination and sintering, the
polymer phase is thermally decomposed, leaving only the inor-
ganic constituents in the printed object. Because the fractions
of bentonite and hollow spheres in the light-curable ink remain
unchanged, the mechanical properties of the sintered objects are
expected to be comparable to those printed using conventional
DIW.[21] These examples indicate that light-curable inks provide
free-forming capabilities that significantly widen the design
space of the direct ink writing process, nicely complementing
other extrusion-based additive manufacturing technologies.
3. Conclusions
Direct ink writing of suspensions of hollow microspheres
is a cost-effective additive manufacturing approach to create
lightweight ceramics combining hierarchical porosity and strong
mechanical properties. In these ceramics, millimeter-sized open
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channels are formed by the interfilament spacing produced by
printing grid-like or profiled architectures, whereas pores smaller
than 100 μm arise from the hollow morphology of the micro-
spheres and the interstices between them. Aqueous inks with
rheological properties suitable for extrusion-based printing re-
quire the addition of bentonite nanoparticles and hydroxypropyl
cellulose into a suspension of ash or silica hollow microspheres.
Upon drying and sintering, the bentonite nanoparticles form
dense interconnections between the hollow microspheres, signif-
icantly increasing their mechanical properties. The compressive
strength of the resulting hierarchical porous ceramic was found
to be about one order of magnitude higher than that of state-
of-the-art porous materials of similar chemical composition and
relative density. By re-designing the liquid phase of the suspen-
sion to contain photo-curable chemicals, we show that the DIW
approach can be combined with light-induced curing to enable
free-form printing of complex-shape objects with exquisite hier-
archical porosity. The additive manufacturing of inks with hol-
low microspheres opens the way for the affordable fabrication of
mechanically efficient ceramic structures for lightweight, impact
absorption, thermal insulation and acoustic applications.
4. Experimental Section
Materials and Chemicals: HA spheres were purchased from Lanke In-
sulation Materials Factory (China), whereas HS spheres were acquired
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Figure 7. Complex-shaped hierarchical porous ceramic obtained by direct ink writing of a light-curable ink of hollow microspheres. A) Schematics
depicting the freeform printing process based on the light-assisted DIW of a suspension of hollow microspheres containing photo-curable monomers.
B) Spring-like structure printed using the light-assisted DIW approach. The ink used in this example contained 37 wt% HS microspheres, 6 wt% bentonite,
2 wt% hydroxypropyl cellulose, and 55 wt% aqueous solution of photo-reactive monomer mixture. Photo-curing was induced by local exposure of the
extruded filament to 365 nm UV light.

from Forsman (China). Hydrophilic bentonite nanoparticles and hydrox-
ypropyl cellulose (average molar mass, Mw = 105 g mol−1 ) were ob-
tained from Sigma-Aldrich (USA, Figure S1, Supporting Information).
AM as the photosensitive monomer, N, N′-methylenebisacrylamide as
the crosslinking agent, and polyethylene glycol (PEG) were purchased
from Sinopharm Chemical Reagent Co., Ltd., China. The photosensi-
tive resins including polyurethane acrylate (PUA) and ethoxylated pen-
taerythritol tetra-acrylate (PPTTA), photoinitiators including 2-hydroxy-
2-methylpropiophenone (HMPP) and Irgacure 819 were obtained from
Shanghai Guangyi Chemical Co., Ltd., China.
Preparation of Inks: For the preparation of the standard inks, an aque-
ous suspension of bentonite nanoparticles was first ball-milled and then
mixed with an aqueous cellulose solution under continuous magnetic stir-
ring. This was followed by a sonication step to obtain a homogeneous col-
loidal suspension. Finally, the hollow microspheres were slowly added to
the suspension under mechanical stirring at a rotation speed in the range
of 300–700 rpm.
Light-curable inks with HS microspheres were prepared following two
strategies. In a first approach, the liquid phase of the ink consisted of an
aqueous solution containing AM as monomer, methylene bisacrylamide
(MBAM) as cross-linker, and HMPP as photoinitiator. The concentrations
of AM, MBAM, and HMPP were fixed at, respectively, 25, 0.8, and 0.8 wt%
based on the total mass of aqueous solution. The second strategy explored
a nonaqueous curable system as liquid phase of the ink. To this end, a
photosensitive resin commonly used for SLA 3D printing was employed.
The resin contained 30.0 wt% PUA, 68.5 wt% PPTTA, and 1.5 wt% Irgacure
819 for photoinitiation. PEG was also mixed into the photosensitive resin
at a mass ratio of PEG/photosensitive resin of 1:9.
DIW Printing: DIW was performed in a Ultimaker platform cus-
tomized for volumetrically controlled extrusion. Glass sheets were used to
support the printed samples. In order to demold the dried samples easily,
the glass sheet was coated with a layer of petroleum jelly before printing. To
prevent clogging induced by the large microspheres (120 μm) present in
the inks, printer nozzles with large diameter in the range of 1.29–2.10 mm
were utilized. The geometry of printed grid-like objects was determined by
the print toolpath and extrusion parameters. The final filament diameter
was determined by the nozzle diameter and the extrusion rate, whereas
the filament spacing was programmed by the toolpath to a fixed value that
varied in the range 4–8 mm. The printhead speed was tuned between 5
and 20 mm s−1 , depending on the targeted shape. For grid-like structures,
the printhead speed was set to 15 mm s−1 and the extrusion rate was ad-
justed to generate filaments with diameter 4.88% larger than the nozzle
diameter.
To qualitatively assess the printability of the inks with hollow micro-
spheres, if a free-spanning filament with length of 5 mm resisted gravity-
induced sagging was observed. In addition, simple extrusion experiments
using 25 mL syringes were carried out to evaluate the stability of inks
against shear-induced liquid phase migration. Inks were considered to be

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printable when they prevent sagging, resist liquid phase migration and can
be printed into a 14-layer grid-like structure without shape distortion.
As-printed samples were dried in a climate chamber with temperature
of 40 °C and humidity of 60%. For sintering, the dried structures were
heated up to the sintering temperature at a heating rate of 3 °C min−1 and
dwelling time of 2 h in an electrical furnace. The sintering temperature was
set to a fixed value within the ranges 1250–1350 and 750–850 °C for the
HA and HS samples, respectively.
Characterization: The chemical compositions of hollow microspheres
(HA and HS) and bentonite nanoparticles were determined by X-ray fluo-
rescence spectroscopy (XRF-1800, Shimadzu, Kyoto, Japan). For imaging
by transmission electron microscopy (TEM, S-5500, Hitachi, Japan), the
bentonite nanoparticles were subjected to ultrasonication in ethanol for
20 min before deposition on a copper grid. The microstructure of hollow
microspheres and printed samples was imaged by scanning electron mi-
croscopy (SEM, MERLIN VP Compact, Carl Zeiss, Jena, Germany) with an
acceleration voltage of 5 kV. The rheological behavior of inks was evalu-
ated using a stress-controlled rheometer (Gemini 200 Advanced Rheome-
ter, Bohlin Instruments). The porosity (P) of structures was calculated
from the bulk density of sample (Db ) and the theoretical density of the
dense ceramic (Dt ) using the equation: P = (1−Db /Dt ) × 100%. Using
the Archimedes methods, theoretical density values of 3.13 and 2.58 g
cm−3 for the samples with hollow ash and hollow silica spheres, respec-
tively, were measured. The relative density was taken as the ratio (Db /Dt )
× 100%. The phase compositions of samples containing HA and HS mi-
crospheres were analyzed by X-ray diffraction using Cu K𝛼 radiation (XRD,
D8 ADVANCE, Bruker, Karlsruhe, Germany).
The microstructure of the liquid phase of the inks was characterized by
electron microscopy on samples prepared using two methodologies. In a
first approach, the ink was frozen instantaneously in liquid nitrogen and
then freeze-dried to completely remove the amorphous ice. In a second
method, the microstructure was imaged directly by Cryo-SEM (FEI Helios
Nanolab 600i, with low temperature sample carrier Quaroum PP3000T).
During Cryo-SEM, the frozen inks were subjected to sublimation at −85 °C
for 20 min to remove a thin layer of amorphous ice and expose the par-
ticles present on the surface of the sample. The compressive strength of
printed samples was tested using a universal material testing machine
(AG-IC 20kN, Shimadzu, Japan) with loading speed of 1 mm min−1 . At
least three specimens were tested to obtain the average value.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
Acknowledgements
The authors thank the financial support of ETH Zürich, the Swiss National
Science Foundation under the grant BSCGIO_157696, and the National
Natural Science Foundation of China (Grant No. 52072202).
Open access funding provided by Eidgenossische Technische
Hochschule Zurich.
Conflict of Interest
Etienne Jeoffroy, Elena Tervoort and André R. Studart are cofounders of the
company FenX AG, which develops insulating mineral foams.
Data Availability Statement
The data that support the findings of this study are available from the cor-
responding author upon reasonable request.
Keywords
direct ink writing, hierarchical porosity, hollow spheres, mechanical
strength
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Received: January 16, 2023
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