A Review of Fabrication Strategies and Applications of Porous Ceramics Prepared by Freeze-Casting Method

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Review paper
A review of fabrication strategies and applications of porous ceramics

prepared by freeze-casting method
Ruiping Liua,n, Tingting Xub, Chang-an Wangb,nn
b
a
Department of Materials Science and Engineering, China University of Mining & Technology (Beijing), Beijing 100083, China
School of Materials Science and Engineering, State Key Laboratory of New Ceramics and Fine Processing, Tsinghua University, Beijing 100084, China
Received 1 October 2015; accepted 27 October 2015
Abstract
Freeze casting is a promising technique to fabricate porous materials with complex pore shapes and component geometries. Of particular
interest are the unique structure and properties exhibited by porous freeze-casted ceramics, which opened new opportunities in various
applications. In this review, we aim to elaborate the fundamental principles of the porous microstructure evolution and summarize the latest
achievements and strategies for the freeze casting process as well as the applications of porous ceramics prepared by this method. The effects of
additives, freezing conditions, suspension solids loading and particle size on pore structure of the porous ceramics and its applications are
discussed. We also outlook the existing issues and challenges in the fabrication porous ceramics by freeze a casting method.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: A. Sintering; B. Microstructure-nal; E. Batteries; E. Insulators
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Fabrication strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Principles of the freeze-casting method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Freezing parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.4. Solids loading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.5. Particle size. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1. Energy storage and conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2. Insulators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3. Filters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.4. Biomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.5. Ceramicmetal composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Outlook. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Corresponding author. Tel.: 86 10 6233 9175; fax: 86 10 6233 9081.

Corresponding author. Tel./fax: 86 10 6278 5488.
E-mail addresses: bjlrp165@126.com (R. Liu), wangca@tsinghua.edu.cn (C.-a. Wang).
nn
http://dx.doi.org/10.1016/j.ceramint.2015.10.148
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Please cite this article as: R. Liu, et al., A review of fabrication strategies and applications of porous ceramics prepared by freeze-casting method, Ceramics
International (2015), http://dx.doi.org/10.1016/j.ceramint.2015.10.148
R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]
Acknowledgments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1. Introduction
Porous ceramic as a technological important material
possess a wide range of applications, such as separation
materials [1], catalyst supports [2,3], and implantable bioceramics [46], etc. Parameters relating to the pore structure, such
as pore size, shape, distribution, and connectivity all play into
the resulting functionality of the porous ceramics. Various
methods for the manufacturing of such materials have been
developed in the past years, such as direct foaming method,
sacricial template method and gel-casting method [712].
Each of these methods has its own merits and drawbacks.
Among them, the freeze casting technique, or freeze drying, as
a novel method, is one of the most innovative techniques
which provide highly porous ceramics with a well-controlled
structure [1321].
Numerous research works on porous ceramics prepared by
freeze drying process have been published during the last
decade, and different types of porous materials such as aligned
porous materials and hybrid porous materials, have been
successfully prepared by freeze drying [2224]. The technique
consists of freezing a liquid suspension (aqueous or not),
followed by sublimation of the solidied phase from the solid
to the gas state under reduced pressure, and subsequent
sintering to consolidate and densify the walls. This method
has several advantages, including simple sintering process
without materials to be burnt out, a wide range of porosity
(3099%) controllable by the suspension concentration, applicability to various types of materials, and cost-effective
production with simple equipment requirement. Furthermore,
when removing the solvent, the freeze casting process does not
bring impurities into the samples and a further purifying
process is therefore not necessary. More importantly, by
changing the freezing parameters, it is possible to prepare
materials with a wealth of pore morphologies and nanostructures. To date, water [25,26], camphene [27,28], tert-butyl
alcohol (TBA) [29], naphthalenecamphor [30] and terpene
acrylate photopolymerizable [31] have been successfully used
as freezing vehicles. Unique or complex porous structures can
be obtained by adjusting the freezing vehicles, starting
materials and processing conditions. The tailorability of the

freeze casting technique makes it capable of fabricating
materials with dense, cellular, lamellar, unidirectional and
complex microstructures. Based on the special pore structure,
freeze-cast porous ceramics are also promising for various
applications including thermal and acoustic insulators, lters,
gas distributors, active substance delivery, piezoelectric elements, catalysts and catalyst supports due to high permeability,
high specic strength, large surface area, excellent adsorption
ability, and good chemical and thermal resistances [3241].
The objective of this paper is to provide a review of the
results obtained up to date and to offer insights on the
perspectives of the technique. The current understanding and
control over the processing route and the potential applications
are described and discussed. The review is organized as follows.
First, the processing principles of freeze-casting are briey
described, and the fabrication strategies and key factors of
freeze-casting processed to date are summarized in details.
Second, the potential applications of the porous ceramics
prepared by the freeze casting method are introduced extensively. Finally, we outline the actual limitations of the technique
and perspectives for the future of freeze-casting method.
2. Fabrication strategies
2.1. Principles of the freeze-casting method
As shown in Fig. 1, the freeze casting method consists of
preparing a stable colloidal suspension (aqueous or otherwise),
pouring the suspension into a mould, freezing a liquid
suspension, followed by sublimation of the frozen phase and
subsequent sintering, leading to a porous structure with
unidirectional channels in the case of unidirectional freezing,
in which pores are a replica of the ice crystals. Among them,
solidication of a prepared suspension is the most critical stage
during freeze casting, since the crystal morphology determines
the resulting porous microstructure and the volume change
associated with the phase transformation greatly inuences the
integrity. Different freezing conditions including the freezing
temperature, freezing time, freezing rate, solids loading,
Fig. 1. Schematic of freeze casting method [42] (Reprinted with permission from Ref. [42], Copyright 2012: Maney publisher Ltd.).
Fig. 2. The relationship between the aqueous suspension states and the
processing steps [25] (Reprinted with permission from Ref. [25], Copyright
2008: Wiley).
particle size, solvent type, and freezing direction can have a

great impact on the resulting pore structure of the materials.
The relationship between the aqueous suspension states and
the processing steps is shown by Deville et al. (Fig. 2) [25].
In freeze casting, the formation of porous microstructures
using freeze casting relies on the rejection of the particles by
the moving solidication front, the breakdown of the solidication front to a non-planar morphology, and the concentration and entrapment of the particles in between the solidied
crystals, all of which are determined by the interaction between
the solidication front and the particles. The detailed principle
of this technique using water as a vehicle is illustrated
schematically in Fig. 3.
While the ceramic slurry is freezing, the growing ice crystals
expel the ceramic particles, creating a lamellar microstructure
oriented in a direction parallel to the movement of the freezing
front. For highly concentrated slurries, the interaction between
particles becomes critical, and a small fraction of particles are
entrapped within the ice crystals by tip-splitting and subsequent healing, leading to the formation of inorganic arms
between adjacent walls. The control of the size and morphology of the pores is often the critical factor with regards to the
nal properties and different applications of porous ceramics.
Since the porosity of the sintered porous ceramics is a replica
of the original ice structure, the nal pore structure of the
porous ceramics can be tuned by varying the fabrication
parameters. The porosity can be tuned by varying the solid
particle content within the slurry, the size of pores is affected
by the freezing kinetics, and the pore morphology can be
controlled by choosing the different solvents and adding
different additives in the slurry.
2.2. Additives
Additives are used to modify the freeze casting parameters
since they are able to change the solvent phase diagram, the
anisotropy of the solid/liquid interfacial energy, the interparticle forces, the degree of undercooling, the solvent viscosity,
Fig. 3. Schematic diagram of the basic principle for freeze casting [21]
(Reprinted with permission from Ref. [21], Copyright 2006: American
Association for the Advancement of Science).
the suspension freezing point and the volume expansion of the

system.
Glycerol is one of the most commonly used additives. It is
non-toxic, highly soluble in water, inexpensive and has a low
freezing point and a low vapor pressure [43]. The addition of
glycerol changes the freezing behavior of water, and the
volumetric expansion of water will decrease from 9% to
7.4% by volume at 10 wt% glycerol in water [44]. A water
solidication modier, glycerol, was utilized to eliminate the
defects associated with the expansion and ceramic particle
rejection of water during freezing [17]. Zhang et al. [45]
investigated the effects of glycerol on the freeze casting
process and thereby on the microstructure and mechanical
properties of porous ceramics, and found that the addition of
glycerol into aqueous alumina slurries will increase their
viscosity and decrease their volume expansion. Interaction
between glycerol and other components in the slurries promotes a good connection between lamellae and thus improving
the mechanical properties of porous ceramics (Fig. 4).
Polyethylene glycol (PEG) is a another common additive for
water-based directional freeze casting systems, which acts as a
binder and affects the microstructure of freeze cast alumina
[46]. PEG added in the slurry decreases the local equilibrium
solidication temperature, and the liquid ahead of the solidication interface becomes supercooled, which thereby
Fig. 4. SEM micrographs of porous alumina ceramics, which are prepared by using: (a) 20 vol% slurry without glycerol, (b) 20 vol% slurry with glycerol,
(c) 30 vol% slurry without glycerol and (d) 30 vol% slurry with glycerol. The direction of fracture is parallel to the ice front [45]. (Reprinted with permission from
Ref. [45], Copyright 2010: Elsevier Ltd.).
stabilizing the growth of the tips of dendrites out into the melt.
This would lead to further breakdown of the solidication
interface and renement of the structure. PEG addition also
inuences the lamellar size of the freeze cast alumina, either by
poisoning the preferred growth direction or affecting the
diffusivity of water molecules [46]. Furthermore, the molecular
weight of PEG additives has great inuence on the microstructure of directionally frozen alumina ceramics. An increase
in molecular weight would cause the viscosity of the solution
to become greater and decrease the diffusivity of PEG in the
solution. Increasing the molecular weight was shown to reduce
the measured pore size from 10 m to 5.5 m [47].
Polyvinyl alcohol (PVA) is the third additive used to adjust the
pore morphology in directional freeze casting [19,34,48]. The
concentration of PVA additive has great effects on the process of
PVA gelation and manners of ice crystals growth, resulting in
different morphologies and pore sizes (Fig. 5). Without PVA,
solid particles are more likely to be repelled from the ice crystal
moving fronts and the accumulated particles are more likely to
hinder the growth of ice crystals. This leads to the formation of
lamellar porous microstructures. While with the addition of PVA,
the solution can experience a gelation process at a relatively high
temperature and the viscosity of the suspension increases

accordingly. During freezing, the gelled PVA combines with
solid particles and inhibits the growth of ice crystals, resulting in
a decrease of ice crystal sizes and providing rened pore sizes
and morphology [34,48]. For example, the morphologies of HAP
ceramics without PVA additive are composed of noninterconnected macroscopic lamellar pores and porous ceramic
walls. After adding PVA into HAP slurries, the pore morphologies change into smaller lamellar pores [48].
Gelatin is the fourth additive used to adjust the pore
morphology and microstructure of the porous ceramics
[49,50]. It is a hydrolyzed form of collagen, which comes from
animal's skin and bones. With the increment of gelatin
concentration, the viscosities of slurries increase. Gelatin addition is helpful to prevent from ice abnormally growing and
obtain the uniform microstructure of green body, resulting in the
small porosity and large linear shrinkage ratio. In addition, the
gelled gelatin formed a network, which binds the ceramic
particles together and prevents from their collapse in the green
body. Without gelatin addition, porous HAP ceramics are
composed of lamellar pores and ceramic walls. While with
gelatin addition, the microstructure of HAP ceramics was
Fig. 5. SEM images of porous TiO2 with cross-section parallel and perpendicular to the ice growth direction. (a) 3 wt% PVA, parallel; (b) 3 wt% PVA,
perpendicular; (c) 6 wt% PVA, parallel; and (d) 6 wt% PVA, perpendicular. [19] (Reprinted with permission from Ref. [19], Copyright 2009: Elsevier Ltd.).
Fig. 6. SEM micrographs of HAP ceramics with solids loading of 50 wt% and different gelatin concentrations of 0 wt% (a), 2 wt% (b) and 6 wt% (c) [50].
(Reprinted with permission from Ref. [50], Copyright 2009: Elsevier Ltd.).
Fig. 7. SEM images of porous structures of porous alumina samples prepared by the gelatin-gelationfreezing method with and without anti-freeze protein (AFP).
The sample with AFP shows uniform cell size throughout channels [49]. (Reprinted with permission from Ref. [49], Copyright 2014: Wiley).
changed remarkably. When 2 wt% gelatin was added to the

50 wt% HAP slurry, the pore morphology of HAP ceramics
shown in Fig. 6(b) was changed from the lamellar pore to the
homogeneous spherical pores. While the gelatin concentration
increased to 6 wt%, the pore morphology of HAP ceramics
shown in Fig. 6(c) became the reticulated pore [50].
Alcohol can also be used to modify the microstructures of
sintered porous ceramics since it changed the hydrogen
bonding of water. The hydrogen bonds between the hydroxyl
hydrogen and oxygen became strong with the increase of
alcohol concentration, resulting in the strong hydrogen bonding interactions between alcohol and water molecule, meanwhile water molecules in the mixtures were present around the
hydroxyl group of alcohols to form hydrogen bonds with the
hydroxyl groups [51], which may disrupt the crystallization of
ice and result in the differences in the microstructure of porous
ceramic. With the addition of ethanol or 1-propanol, the
viscosities of slurries increased and porosities of sintered
ceramics decreased. The compressive strengths of the sintered
porous alumina ceramics were improved due to a good
connectivity between lamellae with the addition of both types
of alcohols [52].
Besides, antifreeze glycoprotein (AFP) can bind to the prism
planes of embryo ice crystals generated in the supercooling
water, and inhibit its crystal growth [5358]. This inhibition

can lead to thermal hysteresis, when AFP is accumulated onto
the prism plane of ice crystal, numerous convex ice surfaces
can be formed from the limited open spaces among AFPs
bound on the ice. Thus, the further adsorption of water
molecules onto the convex ice surfaces and the growth of
ice along a-axis are inhibited by increasing the number of the
bound AFP [55,59]. As shown in Fig. 7, without AFP, the cell
size in the top region is substantially larger than that in the
bottom region, while the thorough channels of porous alumina
with AFP addition were homogeneous, ne and straight over
the whole body [49].
The incorporation of polyacrylamide (PAM) has strong
inuence on the pore structure, morphology of -Si3N4 grains
and mechanical properties of the obtained porous -Si3N4
composites. Increasing PAM content in the slurries changed
the pore structure from lamellar pores with dendrites to
columnar ones without dendrites, decreased the pore size and
increased the dense layer thickness [60].
2.3. Freezing parameters
Freezing conditions can modify the microstructure homogeneity and pore morphology by varying the solidication
Fig. 8. Microstructure of unidirectionally aligned pore channels in the porous YSZ ceramics at different locations from the cooled end of 15 mm (A1, B1 and C1),
9 mm (A2, B2 and C2), 3 mm (A3, B3 and C3) and under different freezing temperatures of 30 1C (A1, A2 and A3), 78 1C (B1, B2 and B3) and 196 1C
(C1, C2 and C3). FT: freezing temperature [62] (Reprinted with permission from Ref. [62], Copyright 2010: Elsevier Ltd.).
Fig. 9. Schematic of the experimental apparatus employed to directionally freeze the ceramic slurries while controlling the speed of the freezing front. The ceramic
slurry is poured into a Teon mold placed between two copper cold ngers whose temperature is controlled by liquid nitrogen baths and ring heaters [66] (Reprinted
with permission from Ref. [66], Copyright 2007: Elsevier Ltd.).
behaviors of dispersing media and the particle hindrance at the

solidication fronts. To our best knowledge, the current
activities in the study of freezing condition inuence on the
microstructure evolution are focused on freezing temperature,
freezing time and freezing rate. The pore channel size
decreased signicantly with decreasing freezing temperature,
as shown in Fig. 8. Freezing temperature affects the relative

dominance of ice nucleation and crystal growth. Under high
supercooling, namely, lower freezing temperature, nucleation
rate is higher than the crystal growth rate, so ice nucleation is
more favorable than crystal growth. At such freezing temperatures, a large number of small ice crystals form. In contrast, if
the freezing temperature is higher (supercooling is low), a

small number of large ice crystals form during freeze casting,
and the larger pores form after the ice sublimation [6164].
With increasing freezing time, the small dendrites merge into
large ones and the number of the resulting small pores inside
the walls decreases, while the number of the macrosized pores
increases [65].
The speed of the solidication front, i.e., the freezing rate
also has a great inuence on the thickness of the ice crystals.
Deville [66] has developed an apparatus to control the freezing
conditions precisely, as illustrated in Fig. 9. For low freezing
rates, only the bottom cold nger was used. To reach higher
freezing rates, a constant macroscopic temperature gradient
was established using the two cold ngers cooled at the same
rate. The average ice front velocity was estimated by measuring the time of freezing and dividing by the length of the
frozen sample.
For aqueous system, faster freezing velocities result in larger
supercooling in front of the growing crystals that will inuence
the crystal thickness (structure wavelength). In addition, as
faster growth is imposed in the direction of the temperature
gradient, lateral growth along the c-axis is increasingly limited,
resulting in thinner lamellae. As shown in Fig. 10, when the
freezing rate is increased, i.e. the solidication front speed
increases, the width of the channels and of the lamellae is
drastically affected. The faster the freezing rate, the ner the
microstructure.
The relationship between ice front velocity and structure
wavelength is extremely complex to describe via a simple
analytical model. The investigated system is a multicomponent

one, combining the effect of the particle/ice front interactions
and solute segregation. The structure wavelength (or ice crystal
radius) will therefore depend on a large number of factors,
including the freezing rate (or ice front velocity); the interfacial
free energy between the particles, the water and the ice front;
the particles size, distribution and content, the interactions of
the particles with themselves, the anisotropic effects of the
surface tension of ice, the buoyancy forces acting on the
particles, the viscosity of the slurry, the diffusion of the solute
away from the interface, the latent heat diffusion, and so on.
Nevertheless, some trends, are summarized in Fig. 11.
Very fast cooling rates, region Fig. 11(a), will result in the
ice front trapping the particles and the formation of a dense
material. When the velocity is decreased below the critical
value for particle entrapment, the particles are expelled from
the growing ice but if the speeds are fast enough the ice will
grow with a columnar microstructure, region Fig. 11(b).
Slower velocities will result in the formation of lamellar ice.
However, if the velocity is still fast or, equivalently, the
gradient in temperature is small enough, the balance between
the preferential growth direction and the gradient direction will
result in the growth of lamellae tilted with respect to the later,
region Fig. 11(c). As the velocity decreases (or the gradient
increases), the lamellae will align with the direction of the
temperature gradient, region Fig. 11(d).
2.4. Solids loading
Solids loading is another factor that affects the characteristics of the freeze cast samples [14,17,61,67,68]. Higher solids
loading suspensions possess lower solvent content and thus
produce lower porosity and higher density freeze cast samples.
The main inuence of variation in solid loading is nevertheless
Fig. 10. Variation of structure wavelength vs. ice front velocity, for samples
with 64% total porosity. The samples were frozen using only the bottom cold
nger whose temperature was decreased at a constant rate (ranging between
0.1 and 10 1C/min). The only exception is the sample with 2 m lamellae
thickness where both the top and bottom cold ngers were cooled at 2 1C/min
in order to maintain a constant temperature gradient of 1 1C/min. A SEM
micrograph of the sample with the smallest lamellae thickness achieved in this
study is shown in the inset (a), cross-section parallel to the ice front [66]
Fig. 11. Strategies and limitations for controlling the structure: schematic plot
of wavelength vs. ice front velocity. The exponent n of the empirical law is
dependent on the particle size d, though the function n f (d) is not monotonic;
an optimum value of d is encountered where the exponent n is maximum. [66]
Fig. 12. Porosity vs. solid loading for freeze-cast porous ceramic materials [25] (Reprinted with permission from Ref. [25], Copyright 2008: Wiley).
and obviously found in the total porosity variations (Fig. 12)

[25]. Furthermore, the suspension solids loading can also
inuence the homogeneity of the resulting microstructure.
The rejection of solid particles at the solidication fronts is
so effective that pore channels appear in the sample during
freeze casting when the solids loading is relatively low, with
the increasing of solids loading, the walls of pore channels
become thicker and meanwhile, the pore channel size
decreases. However, for higher solids loading samples, the
rejection of solid particles is hindered by the crowded particles
and the formation of pore channel is inhibited, and furthermore, additional solid particles also provide numerous heterogeneous nucleation sites for freezing of ice, nally results in
homogeneous pore structure [61]. For gradient titanium
dioxide porous sheets, the pores evolve from dendritic into
three-dimensional reticular shapes with increasing suspension
solids loading [14]. For highly porous Si3N4 ceramics,
increasing the solid content of the slurries from 30 vol% to
50 vol% would change the pore structure from the aligned
channels with dendrites to the round pores with decreasing
pore size. Meanwhile, the increased solid content inhibited
--Si3N4 phase transformation [68].
2.5. Particle size
Particle size also inuences the freeze cast microstructure
[25,42,61, 69,70]. Since ice nucleation mostly experiences a
heterogeneous process, the nucleation of ice crystals is
controlled by the particle size, the surface of the particles
acting as nucleation sites. Apparently, smaller particles provide
a larger surface area and high surface curvatures, which lead to
increased nucleation sites and numerous small pores. Smaller
particle size leads to a lower degree of supercooling because
nucleation and growth can proceed at a higher temperature
than that of larger particles. In contrast, large particles produce
a smaller number of large pores. Large particles also provide
higher supercooling compared to small particles since fewer
nucleation sites allow the suspension to reach a lower
nucleation temperature. Thus, larger structural gradient occurs

in a system with larger particles as a result of the corresponding faster moving solidication front [70].
Morphological features of the crystals cannot be well
replicated into the nal structure if the size of the particle is
in the range of order of that of the interdendritic spaces. Hence,
the particle size must be kept below the wavelength of the
desired structure. Micron-sized particles can obviously not be
used to create nanometer-sized structure (Fig. 13). To ensure a
homogeneous and well dened structure, powders with submicronic mean particle size seem to be desirable. Distribution
of the particle size should also be taken into account for the
same reasons, and the presence of large particle or particles
agglomerates is detrimental to the homogeneity of the nal
structure.
A critical velocity for a certain particle size exists in the
process of freeze casting, above which the particle cannot be
ejected by the moving solidication front and engulfment
occurs. Meanwhile, the particle size and viscosity of slurries
have signicant effect on the critical velocity during freezing.
Furthermore, the particle size also has an important effect on
the nal mechanical properties because the powders with
smaller particle size improve the densication of ceramics or
composites and lead to lower porosity.
3. Applications
3.1. Energy storage and conversion
The electrode should work as a structural support and gas
transport passage, as well as an electrochemical reaction site.
Electrochemical activity of an electrode is generally proportional to the amount of triple-phase boundary, which indicates
the interface of pore, electrode and electrolyte (pore/electrode/
electrolyte). Therefore, the support must be processed to yield
high surface area with ne microstructure [71]. Electrode
topology control such as spatially ordered macroporous
structures [72,73] and multimodal/hierarchical pore size
10
Fig. 13. Inuence of particle size on pores morphology. Details of the crystals are well replicated in the case of small particles (a) whereas such details are lost with
large particles (b) [25] (Reprinted with permission from Ref. [25], Copyright 2008: Wiley).
distributions [7476] has been demonstrated to provide higher

power, and now there is increasing attention to the impact on
energy density as well [7779]. There persists a need for
scalable electrode designs and fabrication methods that maximize energy density while meeting C-rates relevant to broad
classes of application. Conventional porous supports have
required gas phase to travel a long tortuous path to reach a
triple phase boundary, whereas the parallel pore conguration
reduces this path length. The incorporation of straight and
parallel pores may reduce the effective path length necessary
for gas phase diffusion. Moreover, the ne pores may provide
sufcient amount of electrochemical reaction sites. The freeze
casting method is one of the environmentally friendly tools to
control the morphology of electrode for rechargeable battery
because the low concentration of additives is needed. Thus,
this method opens up a new route to develop electrodes with
controlled morphologies.
Bae et al. [80] have identied theoretically and experimentally an ordered, dual-scale porosity distribution that maximizes power at a given pore fraction and thickness by
minimizing electrode tortuosity (Fig. 14). Compared with
optimized conventional Li-ion electrodes [81], approximately
threefold higher capacity per unit area is achieved at relevant
12 C discharge rates. Hamamoto et al. [82] prepared
LiFePO4/carbon composite cathodes for lithium ion batteries
with ultra-high porosity around 88% through a novel gelation
freezing method using gelatin solution as a gelation agent.
Film shapes of carbons that originate in the gelatin were found
inside the wall. The carbon lms and LiFePO4 particles were
formed a lamella structure. The LiFePO4/carbon composite
shows a good discharge capacity at a low current density
though there is low carbon content ( o 3.71 wt%). The

discharge capacities can be regulated by changing the freezing
temperature, particle size distribution, the carbon content, and
the total density of porous cathodes.
The freeze casting method is also an effective way to
prepare supports and cathode used for solid oxide fuel cells
(SOFC). Moon et al. [83] reported an approach to fabricate a
tubular type NiOYSZ support with radially aligned pore
channels, which is considered to be ideal for constructing
SOFC (Fig. 15). This may reduce the effective path length
necessary for gas phase diffusion. Anisotropic, and hierarchically porous composites for potential applications as solid
oxide fuel cell (SOFC) cathodes were prepared by the freeze
casting and partially sintered method with aqueous codispersions of Lanthanum Strontium Manganite (LSM) and
Yttria-Stabilized Zirconia (YSZ) [84]. Chen et al. [85] have
fabricated high performance low temperature SOFCs with
hierarchically porous nano-cathode network by vacuum-free
inltration and subsequent freeze-drying combustion. The
unique structure facilitates mass transport while the nanocathode catalyst promotes the electrochemical reactions (Fig.
16). The cell with straight open electrodes and hierarchically
porous cathode network demonstrates a maximum power
density of 0.65 W/cm2 at 500 1C and impressive stability for
more than 500 h at 400 1C using H2 as fuel and ambient air as
oxidant.
Piezoelectric materials that transfer electric energy to
mechanical energy or in reverse are widely used in modern
engineering applications such as electromechanical transducers
and actuators. The freeze casting method has been thought to
be an effective way to prepare 3-1 type porous ceramics
11
Fig. 14. Periodic channel array threading across a porous matrix of sintered active particles. (A) Decomposition into hexagonal unit cells, further approximated as
cylindrical cells of same volume. (B) Contour plot of effective electrode tortuosity, based on electrolyte concentration drop across the electrode during discharge
under a steady-state assumption. The case for 36% overall porosity is shown. The darker background colors correspond to lower tortuosities. (C) Improved power
performance is guaranteed for o o T (experimentally corresponding to our sample Gen 3), likely for T (Gen 2). For 4 T (Gen 1), 1D transport inside the
porous matrix, parallel to the channels, dominates, yielding higher effective tortuosity than in a homogenous monolith of the same overall porosity [80] (Reprinted
with permission from Ref. [80], Copyright 2012: Wiley). (For interpretation of the references to color in this gure legend, the reader is referred to the web version
of this article.)
Fig. 15. YSZ-coated NiOYSZ tube prepared in this study showing radially
aligned pore channels extended from the inside toward outside (solid loading
of the slurry; 30 vol%, sintered at 1400 1C for 5 h) [83] (Reprinted with
permission from Ref. [83], Copyright 2003: Elsevier Ltd.).
[8691]. Generally, porous piezoelectric ceramics usually

show decreased piezoelectric properties compared to the dense
ones. Interestingly, however, the 3-1 type porous lead zirconate titanate (PZT) ceramics with one dimensional pore
channel structure, which were fabricated by a tert-butyl alcohol

(TBA)-based freeze-casting process, were found to possess
excellent piezoelectric properties with high porosity [86].
Especially, for some of them with a lower porosity level, the
piezoelectric voltage coefcient (d33) could even be larger than
that of dense PZT ceramics [87]. Porous lead zirconate
titanatelead zinc niobate (PZTPZN) piezoelectric ceramics
with interconnected pore channels and high hydrostatic gures
of merit were also fabricated using the camphene-based freezecasting method by Lee et al. [88]. It was concluded that the
oriented growth of grain in 3-1 type porous PZT ceramics and
002 crystalline direction along the pore channel can contribute to the high piezoelectric properties. Moreover, compared with the dense PZT ceramics, the pore wall of PZT
ceramics with unidirectional pore structure has smaller domain
size, which is benecial to deection of domain and enhancement of piezoelectric coefcient [89].
Besides, the novel composite based on the porous PZT
prepared by the freeze casting method with super physical
properties can also be prepared. Xu et al. [90] reported a novel
3-1 type PZT/epoxy composites fabricated using a freeze-casting
12
Fig. 16. 3D X-ray microscopic image (a) for the cell consisting of anode (bottom layer), electrolyte (middle layer) and cathode (top layer) (a1) and cross-sectional
view of X-ray microscopic image showing internal gas diffusion channel (a2). Reconstructed 3D image for single cell (b), SEM images for the cross-section of the
cell (c), the cathode (d,e), and high resolution TEM (HRTEM) image for the surface of SSCGDC cathode after electrochemical measurement (f) [85] (Reprinted
with permission from Ref. [85], Copyright 2014: Elsevier Ltd.).
and impregnation method, and found that the special structure of

one dimensional epoxy phase and connected PZT phase is
benecial for not only the acoustic impedance but also the
hydrostatic properties. Liu et al. [91] also employed the freeze
casting technique to fabricate ceramicepoxy composites, and the
composites exhibited modest piezoelectric constant d33
(r56 pC/N), the dielectric constant was 1 order of magnitude
higher than that of conventional composites with randomly
distributed ceramic particles. Furthermore, three-phase magnetoelectric (ME) composites of lead zirconate titanate (PZT)/cobalt
ferrite CoFe2O4 (CFO)/epoxy were also synthesized in sequence

by a tert-butyl alcohol (TBA)-based freeze-casting technique, a
chemical solution deposition method, and an impregnation
process. The composites showed not only stable and excellent
dielectric behavior in a wide frequency range, but also good
ferroelectricity and ferromagneticity at the same time [92].
A recent report of porous mullite/Na2SO4 composites with
both novel structure and improved heat storage properties can
also be found [93]. The composites were prepared by inltration of the molten Na2SO4 into the porous mullite matrix,
which is fabricated by the TBA-based freeze casting method.

This novel composites with unique structure are advantageous
for the improvement of the heat storage properties, and could
nd applications as high performance thermal storage
materials.
3.2. Insulators
A freeze casting technique appears to be the most effective
method for processing porous ceramics intended for thermal
insulation applications in terms of high porosity and low
thermal conductivity [62]. For highly porous ceramics, the
relatively high mechanical strength attainable by this method
and relatively well established control over microstructure
enables this processing method to meet the functional requirements for enhanced effective insulation.
A common feature of the microstructure of the porous
ceramics prepared by the freeze casting is the dendritic
structure. The presence of dendrites promotes interconnectivity
between the pore channels, promoting cross-ow convection
current between the channels. Thus dendritic structures could
lower the insulation effectiveness of porous ceramics [94].
Therefore porous ceramics intended for thermal insulation
should be free of dendrites, or the primary dendrite arm
spacing should be wide enough to avoid overlapping of
dendrite arms, to prevent convection currents. Fukushima et
al. [95] fabricated SiC foam by empolying the gelatin as a
gelation agent and the dendritic structure was absent. They
suggested that gelatin in the slurry strongly prevented the
growth of dendritic ice crystal during ice formation. Li and Li
[96] fabricated porous Y2SiO5 ceramics without dendritic
morphology by using tert-butyl-alcohol (TBA) as the solvent.
Highly porous silica thermal insulators were produced by
gelation of a gelatin solution with dispersed silica particles,
followed by freeze-drying and heating at 800 1C, as shown in
Fig. 17 [97]. The porosity and thermal conductivity of the
insulators ranged from 88 to 98 vol% and from 0.168 to
0.054 W/(m K), respectively, both of which could be controlled by changing the silica content in the gel stage.
Gelationfreezing route was proved to be a feasible and
promising route for the production of very highly porous and
machinable insulators. Porous YSZ ceramics prepared by
TBA-based freeze casting was reported, and it was found that
Fig. 17. Photograph of the S1 insulator and sliced thin-section specimens [97]
(Reprinted with permission from Ref. [97], Copyright 2014: Wiley).
13
the unidirectionally aligned pore channels produced by this

method offered distinct applications of porous YSZ ceramics
in thermal insulators: one end with high porosity along the
channel direction was promising in thermal insulation, and the
other end which was much denser provided high strength for
load bearing [62] (Fig. 18). Haixia Yang A novel silica
aerogel/porous Si3N4 composite with low thermal conductivity
(0.043 W/(m K)), low dielectric constant ( 1.6) and loss
tangent ( 0.0018) has been prepared by the freeze casting
and solgel impregnation, and the composite is expected to be
suitable for use in thermal insulation and wave-transparent
functional integration material [98].
3.3. Filters
Porous ceramics for ltration applications may require
mechanical strength, material and environmental compatibility,
thermal shock resistance and other properties relevant and
peculiar to specic uses. High ow-rate and high permeability
are two important factors to evaluate the effectiveness and
efciency of a lter. It is known to all that the unidirectional
pores aligned parallel to the ow direction are more effective
for uid ow properties than pores running perpendicular or
otherwise. Freeze casting technique has been used by various
researchers for preparing unidirectionally aligned porous
ceramics, and signicant control has been exercised over the
pore size and porosity. The pore structures would enhance ow
rate and permeability of porous ceramics lters.
Since the uid ow properties can be improved by the
connectivity of the pores and gradient structure, the dendritic
structures formed along the aligned channels prepared by using
camphene or water as the freezing vehicle are very essential
features in ltration applications. Also, the hierarchical pore
structure and variation in channel size along the height of the
channels formed during the freezing process would endow the
porous ceramics prepared by the freeze casting method with
the capability of ltering a wide range of particle sizes, thereby
enhancing the effectiveness and efciency of freeze casting
ceramics [62]. We have tested the nitrogen ux and pure water
Fig. 18. Variation of room-temperature thermal conductivity with distance

from the cooled plate of porous YSZ ceramics with unidirectionally aligned
pore channels under different freezing temperatures of 30, 78 and
196 1C [62] (Reprinted with permission from Ref. [62], Copyright 2010:
Elsevier Ltd).
14
ux of the tubular porous mullite membrane supports prepared

by the TBA-based freeze casting method, and demonstrated
that the unidirectionally aligned pore structures with gradient
distribution along the freezing direction are potential for the
applications in ceramic membrane supports and microltration of ceramic membranes [61].
equilibrium, regardless of the processing used. As illustrated

in Fig. 19, a powerful design protocol of strategies for
researchers to nely tune the ice templated scaffolds structure
to their specic needs was presented.
3.4. Biomaterials
The fracture toughness of most ceramics is at or below

5 MPa m1/2 [113], which is not favorable for most industrial
applications, and one of the research area is toughening
ceramics via the incorporation of a secondary phase to
reinforce the matrix, thus forming ceramic matrix composites.
Among them, the ceramicmetal composites have attracted
much attention due to the super mechanical properties. One
of the main methods for preparing the ceramicmetal
composites includes the fabricating a porous ceramic preform
and then inltrating the preform with a metal melt [114119].
The pore structure of the porous ceramic performs will affect
the overall properties of the composite. It is therefore
imperative to have a well-designed and processed preform.
Obviously, the preforms must contain completely interconnected pores to facilitate the inltration of the molten metal,
and the distribution of the pores should also be highly
controllable because preforms with regular spacing between
pores will have higher reliability resulting from reduction in
local variation of properties.
Open porous ceramic bodies obtained by the freeze-casting
and subsequent drying of ceramic suspensions are attractive as
preforms for the fabrication of reinforced composites by
inltration of metallic melt [120,121]. Several experimental
studies have been carried out in the last few years to
investigate the mechanical properties of metal/ceramic composites fabricated by inltrating metal melts in freeze casting
ceramic preforms. Deville et al. [21,25] have produced
lamellar porous Al2O3 scaffolds by freeze-casting aqueous
Bio-scaffolds may be utilized for bone tissue engineering

applications in order to facilitate the repair of bone that has
been awed due to illness, injuries or deterioration [99101].
The scaffold must meet certain requirements with regard to its
structure and properties. They should provide a porous matrix
with interconnecting porosity and surface properties that
promote rapid tissue ingrowth, at the same time, they should
possess sufcient stiffness, strength and toughness to prevent
crushing under physiological loads until full integration and
healing are reached. It has been reported that an optimal pore
size exists for successful cell inltration and host tissue
ingrowth: 515 m for broblasts, 20125 m for adult
mammalian skin tissues and 100350 m for bone tissues
[102]. There is also some evidence that pore interconnectivity
is as important as porosity for bone in growth, particularly in
the early stages of bone regeneration and penetration in the
scaffold [103,104]. Among the numerous processing routes, as
a processing technique for the manufacture of biomaterials, the
freeze casting method permits to prepare complex, hybrid
materials through excellent control of structural and mechanical properties [6, 105107]. A wide variety of materials have
already been investigated, including chitin [108], gelatin [109],
collage [110], PLA, PDLLA, and PLGA [111], etc.
Pawelec et al. [112] proposed a universal principle to predict
the nal pore size of scaffolds prepared by the freeze casting,
which was the amount of time that the slurry spent at
3.5. Ceramicmetal composites
Fig. 19. A ow chart summarizing the key points to creating scaffold structure and ways in which to alter the processing to tailor the scaffold structure [112]
(Reprinted with permission from Ref. [112], Copyright 2014: The royal society publishing).
15
Fig. 20. SEM micrograph of (a) the AlSiMg/SiC composites with 30 vol% SiC and elemental maps: (b) Al; (c) Si; and (d) Mg [122] (Reprinted with permission
from Ref. [122], Copyright 2015: Elsevier Ltd.).
Fig. 21. Compressive stressstrain curves for (a) SiC scaffolds and (b) AlSiMg/SiC composites (L represents longitudinal direction and T represents transverse
direction) The inserted gure in (b) shows the compressive stressstrain curve for the as-cast AlSiMg alloy [122] (Reprinted with permission from Ref. [122],
Copyright 2015: Elsevier Ltd.).
alumina slurries and then fabricated shell-like composites by

inltrating an AlSi alloy or a polymer into the scaffolds. In
these composites, hard and ductile phases were alternately
arranged and both strength and toughness of the composites
were improved. Launey et al. [121] used an ice-templating
technique to create a ne layered microstructure with 10 mm
layer thicknesses. The laminates contained up to 40 vol%
ceramic. The porous ceramic was inltrated with an AlSi

alloy and the resulting composite displayed steady-state
fracture toughness of 40 MPa m1/2 [121]. Shaga et al. [122]
used freeze casting and pressureless inltration techniques to
prepare the AlSiMg/SiC composites with a lamellar interpenetrating structure, as shown in Fig. 20. The resultant
composites exhibit different compressive strengths but similar
16
Fig. 22. Variations in ultrasonic wave velocities (longitudinal CL and shear

CS) and elastic modulus of the composites with the initial SiC volume fraction
[122] (Reprinted with permission from Ref. [122], Copyright 2015:
Elsevier Ltd.).
elastic modulus in the longitudinal and transverse directions

(Fig. 21 and 22). Roy et al. [123127] studied the elastic
anisotropy, elasticplastic ow behavior, damage evolution
under external uniaxial compression and the mechanisms of
internal load transfer of the aluminum/alumina composites
prepared by the above methods systematically. The results
showed that the stiffness and compressive strength of the
composite are highly dependent on the lamellae orientation.
Along the freezing direction and along the lamellae in the
plane normal to the freezing direction, the composite displays
ceramic controlled behavior with high compressive strength
and limited or no ductility. While with increasing orientation
of the lamellae with respect to the loading direction, the
behavior becomes more metallically controlled, which displaying reduced strength and large plasticity.
However, for non-aqueous system, the research on the

freezing behavior, pore morphology evolution process and
critical factors, such as feasible additives, freezing parameters, is limited and needs to be further evaluated.
Further optimization of the pore structure will be welcome
by continuing to study the processing, structure, and
property relationships. Ideally, the optimized architecture
and geometry of pores will provide improved functionality
while still maintaining the required mechanical properties.
Further expanding the scope of applications of the porous
ceramics prepared by the freeze casting method, and
development of functional structures, either by development
of new materials and corresponding processing strategies,
or by a post-processing functionalization of the structures
are still to be fully required.
5. Summary
In this paper, a review of the freeze casting process for
preparing porous materials by either aqueous or non-aqueous
dispersing media is presented. The fundamental principles,
fabrication strategies and the applications are discussed extensively. The microstructures of porous ceramics can be effectively adjusted by controlling additives, freezing temperature,
freezing rate, freezing time, suspension solids loading and
particle size. Due to the unique controlled pore structure, the
porous ceramics with engineered porosity fabricated by the
freeze casting method are promising materials for a number of
functional and structural applications including energy storage
and conversion, thermal insulation, lters, bio-scaffolds for
tissue engineering, and preforms for ceramicmetal composites
fabrication.
Acknowledgments
4. Outlook
Owing to its versatility and exibility in the fabrication of
porous materials with controllable porous structures, the freeze
casting technique has a promising perspective in both scientic
studies and industrial applications. As mentioned above,
reports of many research investigations have appeared in the
last decades, and great developments have been made using
the freeze casting technique. However, those investigations are
mainly focused on the fabrication of the porous ceramics with
aqueous suspension and the evaluation of the mechanical
properties. Incremental developments can be expected in the
following four aspects:
The understanding of the relationships between the rheological properties of the initial suspension and the nal
characteristic of the porous structures, and corresponding
mechanisms in freezing process, is lacking and still at an
early stage, so further investigation involving those aspects
is urgently required.
Freeze casting of aqueous systems has been extensively
studied and the main issues as well as their effects on
porous microstructure evolution are well investigated.
The authors would like to thank the nancial support from

the National Natural Science Foundation of China (NSFCNo.
51172119 and 51202117) and the Fundamental Research
Funds for the Central Universities (No. 2014QJ02).
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A Review of Fabrication Strategies and Applications of Porous Ceramics Prepared by Freeze-Casting Method

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Available online at www.sciencedirect.

Ceramics International ] (]]]]) ]]]]]]

A review of fabrication strategies and applications of porous ceramics

Received 1 October 2015; accepted 27 October 2015

Keywords: A. Sintering; B. Microstructure-nal; E. Batteries; E. Insulators

Corresponding author. Tel.: 86 10 6233 9175; fax: 86 10 6233 9081.

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

materials and processing conditions. The tailorability of the

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

particle size, solvent type, and freezing direction can have a

the suspension freezing point and the volume expansion of the

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

temperature and the viscosity of the suspension increases

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

changed remarkably. When 2 wt% gelatin was added to the

water, and inhibit its crystal growth [5358]. This inhibition

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

behaviors of dispersing media and the particle hindrance at the

as shown in Fig. 8. Freezing temperature affects the relative

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

the freezing temperature is higher (supercooling is low), a

analytical model. The investigated system is a multicomponent

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

and obviously found in the total porosity variations (Fig. 12)

nucleation temperature. Thus, larger structural gradient occurs

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

distributions [7476] has been demonstrated to provide higher

though there is low carbon content ( o 3.71 wt%). The

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

[8691]. Generally, porous piezoelectric ceramics usually

channel structure, which were fabricated by a tert-butyl alcohol

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

and impregnation method, and found that the special structure of

ferrite CoFe2O4 (CFO)/epoxy were also synthesized in sequence

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

which is fabricated by the TBA-based freeze casting method.

the unidirectionally aligned pore channels produced by this

Fig. 18. Variation of room-temperature thermal conductivity with distance

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

ux of the tubular porous mullite membrane supports prepared

equilibrium, regardless of the processing used. As illustrated

The fracture toughness of most ceramics is at or below

Bio-scaffolds may be utilized for bone tissue engineering

3.5. Ceramicmetal composites

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

alumina slurries and then fabricated shell-like composites by

ceramic. The porous ceramic was inltrated with an AlSi

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

Fig. 22. Variations in ultrasonic wave velocities (longitudinal CL and shear

elastic modulus in the longitudinal and transverse directions

However, for non-aqueous system, the research on the

The authors would like to thank the nancial support from

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

[33] A.H. Lu, F. Schueth, Nanocasting: a versatile strategy for creating

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

[57] M.M. Harding, P.I. Anderberg, A.D. Haymet, Antifreeze' glycoproteins

R. Liu et al. / Ceramics International ] (]]]]) ]]]]]]

[116] F. Scherm, R. Volkl, A. Neubrand, F. Bosbach, U. Glatzel, Mechanical

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