T. Ohji and M. Fukushima Macroporous Ceramics Processing and Properties PDF

Macro-porous ceramics: processing and
properties
T. Ohji* and M. Fukushima
Porous ceramics are now expected to be used for a wide variety of industrial applications from
filtration, absorption, catalysts and catalyst supports to lightweight structural components. During
the last decade, tremendous efforts have been devoted for the researches on innovative
processing technologies of porous ceramics, resulting in better control of the porous structures
and substantial improvements of the properties. This article intends to review these recent
progresses of porous ceramics. Because of a vast amount of research works reported in this field
these days, the review mainly focuses on macro-porous ceramics whose pore size is larger than
50 nm. Followed by giving a general classification of porous ceramics, a number of innovative
processing routes developed for critical control of pores are described, along with some
important properties. The processes are divided into four categories including (i) partial sintering,
(ii) sacrificial fugitives, (iii) replica templates and (iv) direct foaming. The partial sintering, the most
conventional technique for making porous ceramics, has been substantially sophisticated in
recent years. Very homogeneous porous ceramics with extremely narrow size distribution have
been successfully prepared through sintering combined with in situ chemical synthesis. Carefully
tailored micro-structure (size, morphology and orientation of grains and pores, etc.) of porous
ceramics has led to unique mechanical properties, which cannot be attained even in the dense
materials. Various types of the sacrificial fugitives have been examined for obtaining well-tuned
shape and size of pores. The freeze-drying techniques using water or liquid as fugitive materials
have been most frequently studied in recent years. Controlling growth of ice during freezing has
led to unique porous structures and excellent performances of porous ceramics, e.g. excellent
mechanical behaviour for highly porous lamellar hydroxyl-apatite scaffolds. Numerous
approaches on the replica templates have been developed in order to produce highly porous
ceramics having interconnected large pores and sufficiently strong struts without cracks. Natural
template approaches using wood, for example, as positive replica, have been intensively studied
in these years and have realised highly oriented porous open-porous structure with a wide range
of porosity. As for the direct foaming technique, a variety of novel techniques which stabilise the
bubbles in ceramic suspension have been developed to suppress large pore formation, e.g.
evaporation of emulsified alkane droplets and use of surface-modified particles. We also briefly
review porous ceramics with hierarchical porosity (incorporation of macro-, meso- and micro-
pores), which have attracted much attention in both academic and industrial fields. Finally the
article gives the summary and discusses the issues to be solved for further activating the potential
of porous ceramics and for expanding their applicability.
Keywords: Ceramics, Pores, Processing, Properties, Permeability, Mechanical property, Foam, Review
Introduction
For structural applications of brittle ceramic materials,
pores are generally what to be eliminated because they
act as fracture defects and degrade the structural
reliability, and therefore, ceramic engineers tried to
sinter ceramics to full density to attain high mechanical
National Institute of Advanced Industrial Science and Technology (AIST),
Anagahora 2266-98, Shimo-shidami, Moriyama-ku, Nagoya 463-8560,
Japan
*Corresponding author, email t-ohji@aist.go.jp
2012 Institute of Materials, Minerals and Mining and ASM International
Published by Maney for the Institute and ASM International
DOI 10.1179/1743280411Y.0000000006 International Materials Reviews 2012 VOL 57 NO 2 115
strength. On the other hand, there have been various
industrial applications where pores are taken advantage
of positively, from ltration, absorption, catalysts and
catalyst supports to lightweight structural components
and thermal insulator.
1,2
In these decades, a great deal of
research efforts have been devoted for tailoring deliber-
ately sizes, amounts, shapes, locations and connectivity
of distributed pores, which have brought improved or
unique properties and functions of porous ceramics.
312
The merits in using porous ceramics for these applica-
tions are generally combination of intrinsic properties of
ceramics themselves and advantages of dispersing pores
into them. The former include heat and corrosion
resistances, wear and erosion resistance, unique electro-
nic properties, good bioafnity, low density, and high
specic strength, and the latter are low density, low
thermal conductivity, controlled permeability, high sur-
face area, low dielectric constant, and improved piezo-
electric properties.
13,14
This article intends to review these recent progresses of
porous ceramics. Porous materials are classied into three
grades depending on the pore diameter d: macro-porous
(d.50 nm), meso-porous (50 nm.d.2 nm) and micro-
porous (d,2 nm), according to the nomenclature of
IUPAC (International Union of Pure and Applied
Chemistry). Figure 1 shows this classication along with
typical applications and fabrication processes specic to
the pore diameters. One of the most representative
applications of porous materials is ltration or separation
of matters in uids. Filtration is roughly classied into
several grades depending on pore diameter d and mole-
cular weight cut-off of the matters (MWCO); ltra-
tion (typically d.10 mm), micro-ltration (10 mm.d.100
nm), ultra ltration (100 nm.d.1 nm, MWCO510
3
10
6
),
nano-ltration (d<12 nm, MWCO520010
3
), and reverse
osmosis (d,1 nm, MWCO<100). When the pore size is
large like ltration and micro-ltration, the separation is
principally made by sieving effect where matters whose size
is larger than the pore size is trapped. In ultra ltration,
nano-ltration, and reverse osmosis where pore size is small,
uid permeability depends on the afnity of solute and
solvent with the porous materials as well.
Because of a vast amount of research works reported in
this eld these days, the review mainly focuses on macro-
porous ceramics; micro- and meso-porous ceramics
whose pore size is below 50 nm are not included here.
Representative applications of macro-porous ceramics
are briey described. Ceramic lters are now widely
loaded in diesel engines to trap particulate matters in the
exhaust gas stream, so called, diesel particulate lters
(DPFs). Since the high combustion efciency and low
carbon dioxide emission of diesel engines, the demand of
DPF is also expected to further increase over the
world.
1517
Ceramic water purication lters are used
for eliminating bacillus coli and suspension from waste
water, because of their higher ux capability, sharper
pore size distribution, better durability and higher
damage tolerance than those of organic hollow bres.
18
Ceramic foam lters have been used for removing
metallic inclusions from molten metals such as cast iron,
steel, aluminium, as well as rectifying ow of the molten
metals.
19
Since the metallic inclusions result in defects in
cast metals, this ltration process substantially improves
the performance of the products. Porous ceramics with
high specic surface area are employed for absorptive and
catalytic applications, where large area is required for
contacts with reactants, particularly in high-temperature
or corrosive atmospheres. Bioreactors are devices or
systems that provide a biologically active environment,
where micro-organisms and enzymes are immobilised and
biochemical reactions are performed in porous beds, and
porous ceramics are often used as such bio-reactor beds
due to chemical stability of ceramics and accommodative
function of porous structure.
20
Recently, porous biocera-
mics with open pore structures have attracted great
attention for bio-implant applications including of bone
regeneration.
21
Bone cells are impregnated through the
open pores and grow on their biocompatible walls
resulting in bone in-growth. Many electrodes used in
electro-chemical devices including gas puriers, gas
sensors, fuel cells, and chemical analysers are porous
ceramics.
22
Some porous electrodes require two mode
distributions of pore sizes; small pores are for the
electrochemical reactions while large pores are for ow
paths of reactants. Properties of electro-ceramics also
depend substantially on the porosity content and
morphology and therefore porous ceramics are also
applied or expected to be used in various electro-devices.
For example, porous piezoelectric ceramics have im-
proved piezoelectric property and are good candidates
for ultrasonic transducers, etc.
23
A variety of porous
ceramics have been applied as materials for refractory
bricks of kilns and furnaces in various industrial elds,
due to their low thermal conductivity and high thermal
shock damage resistance (against thermal spalling).
24,25
On the other hand, some porous materials of conductive
ceramics like zirconia and silicon carbide have been
utilised in heat exchangers and heaters.
13
As is known from Fig. 1, the representative processes
for making macro-porous ceramics are (i) partial
sintering, (ii) sacricial fugitives, (iii) replica templates,
1 Classication of porous materials by pore size and corre-
sponding typical applications and fabrication processes
Ohji and Fukushima Macro-porous ceramics: processing and properties
116 International Materials Reviews 2012 VOL 57 NO 2
and (iv) direct foaming. While the recent review articles
on porous ceramics
9,11,12
have placed emphasis on che-
mical approaches related to the latter three, this article
intends to overview the macro-porous ceramics fabri-
cated through each of these four routes in below sections
(Partial sintering, Sacricial fugitives, Replica tem-
plates and Direct foaming). A number of innovative
techniques which have been developed recently for critical
control of pores are introduced, divided into these four
categories, together with some important properties of
porous ceramics obtained in these processes. It should be
noted however, that a lot of new approaches for macro-
porous ceramics such as phase separations
2630
have been
developed other than the processes shown here. Figure 2
shows schematic illustrations of these processes, each of
which will be interpreted in its section. We then discuss
gas permeability of these porous ceramics in with
different pore sizes and structures in the section on Gas
permeability, and briey review porous ceramics with
hierarchical porosity (incorporation of macro-, meso-
and micro-pores) in the section on Hierarchically porous
ceramics, which have attracted much attention in both
academic and industrial elds. Finally the article gives
summary and discusses the issues to be solved for further
realising the potential of porous ceramics and for
expanding their applicability.
Partial sintering
Partial sintering of powder compact is the most
conventional and frequently employed approaches
to fabricate porous ceramic materials. Particles of
powder compact are bonded due to surface diffusion
or evaporationcondensation processes enhanced by
heat treatments, and a homogeneous porous structure
forms when sintering is terminated before fully densied
(see Fig. 2a). Pore size and porosity are controlled by
the size of starting powders and degree of partial
sintering respectively. Generally, in order to provide
the desired pore size, the size of raw powder should be
geometrically in the range two to ve times larger than
that of pore. Porosity decreases with increased forming
pressure, sintering temperature and time. In addition,
processing factors such as the type and amount of
additives, green densities, and sintering conditions
(temperature, atmosphere, pressure, etc.) also greatly
affect the micro-structures of porous ceramics.
31
The
mechanical properties depend largely on degree of neck
growth between grains, as well as porosity and pore
size. Green and coworkers
32,33
found that before any
densication occurs, the formation of necks between
touching particles by surface diffusion can increase
the elastic modulus to 10% of the fully dense value. The
porosities of porous materials obtained by partial sin-
tering are usually below 50%. In industry, this method
has been utilised for various applications including mol-
ten metal lters, aeration lters (gas bubble generation
in wastewater treatment plants),
13
and water purication
membranes.
18
Several processing approaches have been developed to
enhance grain bonding and improve strength of porous
ceramics. Oh et al.,
34
Jayaseelan et al.
35
and Yang et al.
36
fabricated porous Al
2
O
3
and Al
2
O
3
based composites by
the pulse electric current sintering (PECS) technique and
found that the strength was substantially improved due
to the formation of thick and strong necks. During
sintering the discharge is thought to take place between
the particles and to promote the bridging of particles by
neck growth in the initial stages of sintering. This strong
neck growth leads to substantially high strength com-
pared to those of the conventional porous materials. For
example, the exural strength of porous alumina-based
composites via PECS reached 250 and 177 MPa, with 30
and 42% porosity respectively, which are considerably
high compared to those of porous alumina fabricated by
conventional partial sintering, e.g. y100 MPa at 30%
porosity
35
(see Fig. 3). Using PECS, Akhtar et al.
37
also
fabricated porous ceramic monoliths from diatomite
powders, which are known as a cheap and renewable,
natural resource. The PECS which rapidly heats diato-
mite powder successfully bonds the particles together
into relatively strong porous bodies, without signi-
cantly destroying the internal pores of the diatomite
powder. The micro-structural features showed that
consolidation proceeds by the formation of necks at
temperatures around 700750uC, which is followed by
signicant melt phase formation around 850uC, resulting
in porous ceramics with a relatively high strength.
Deng et al.
38,39
tried to obtain strong grain bonding
through combination of partial sintering and powder
decomposition. A mixture of a-Al
2
O
3
and Al(OH)
3
was
used as the starting powder to make porous Al
2
O
3
ceramics, and because Al(OH)
3
experiences a 60%
volume contraction during decomposition and produces
ne Al
2
O
3
grains, the fracture strength of obtained
porous Al
2
O
3
was substantially higher than that of the
pure Al
2
O
3
sintered specimens because of strong grain
bonding that resulted from the ne Al
2
O
3
grains
produced by the decomposition of Al(OH)
3
. Similar
improvement of mechanical properties was also identi-
ed for ZrO
2
porous ceramics fabricated by adding
Zr(OH)
4
.
40
2 Representative fabrication processes of macro-porous
ceramics
International Materials Reviews 2012 VOL 57 NO 2 117
Partial sintering through reaction bonding techniques
have been frequently used for making porous ceramics,
where reaction products form or precipitate epitaxially
on grains, resulting in well-developed neck growth
between grains.
41,42
In combination with the reactive
sintering process, Suzuki et al.
43,44
synthesised a
CaZrO
3
/MgO porous ceramics with three-dimensional
grain net-work structure by using reactive sintering of
highly pure mixtures of natural dolomite [CaMg(CO
3
)
2
]
and synthesised zirconia powders. CaMg(CO
3
)
2
decom-
poses into CaCO
3
, MgO and CO
2
(g) at y500uC, and
CaCO
3
then reacts with ZrO
2
to form CaZrO
3
and CO
2
(g) at y700uC. Through liquid formation via LiF
doping, these reactions and liberated CO
2
gas result in
formation of a homogeneous open-pore structure with
strong grain bonding as shown in Fig. 4. The pore size
distribution is very narrow (with typical pore size:
y1 mm), and the porosity was controlled (about 30
60%) by changing the sintering temperature. The
relatively high exural strength (y40 MPa for 47%
porosity) was observed over the temperature range of
room temperature to 1300uC. The similar approach has
been applied other materials systems such as CaAl
4
O
7
/
CaZrO
3
and CaZrO
3
/MgAl
2
O
4
composite systems.
45,46
She et al.
47
used an oxidation-bonding process for the
low-temperature fabrication of porous SiC ceramics
with superior resistance against oxidation. In such a
process, the powder compacts are heated in air instead
of an inert atmosphere. Because of the occurrence of
surface oxidation at the heating stage, SiC particles are
bonded to each other by the oxidation-derived SiO
2
glass. The mechanical strength is strongly affected by
particle size; the exural strength attained as high as
185 MPa at a porosity of 31%, when using ne a-SiC
powder (0?6 mm), while it was 88 MPa at 27% porosity
for coarse powder (2?3 mm). The oxidation-bonding
technique has been applied to other materials including
silicon nitride,
48
SiC/mullite composites,
49
and SiC/
cordierite composites.
50
Partial sintering technique has been also applied for
making porous silicon nitride with brous grains of high
aspect ratios.
51
Compared with oxide ceramics, the
densication of silicon nitride ceramics is difcult
because of strong covalent bonding between silicon
and nitrogen atoms. This difculty of sintering silicon
nitride ceramics is benecial for controlling density or
porosity through adjusting the additives and the
sintering process. In order to suppress densication,
oxides with high melting point and high viscosity such as
Yb
2
O
3
are frequently used as sintering additives. The
addition of Yb
2
O
3
also is known to accelerate the
brous grain growth of b-Si
3
N
4
.
52
Figure 5 shows
micro-structure and mechanical properties of porous
silicon nitrides sintered at different temperatures by
using a-Si
3
N
4
and 5 wt-% Yb
2
O
3
.
52,53
The fracture
strength and fracture toughness were determined by
three-point exure and chevron-notched beam tests
respectively. While the porous structure sintered at
1600uC consists of equiaxed a-grains, those are trans-
formed from equiaxed to brous when increasing the
temperature to 1700uC. Further increase in sintering
temperature gives rise to micro-structural change from
ne to coarse grains, while maintaining the porosity
around 4045%. The brous micro-structure is advanta-
geous for the strengthening effects of grain bridging and
pullout. In actuality, both the fracture strength and
fracture toughness of the materials sintered at 1700uC
or higher are markedly improved, compared to those
at 1600uC. For examples, the strength for the sample
of equiaxed micro-structure sintered at 1600uC is
y40 MPa, while that at 1700uC is y380 MPa with
4 Micro-structure of porous CaZrO
3
/MgO composite fabri-
cated via in-situ reaction synthesis, exhibiting three-
dimensional network structure with strong grain necking
43
(Reproduced with permission of John Wiley and Sons)
3 Flexural strength as a function of porosity for alumina/
3 vol.-% zirconia (AZ) fabricated via PECS and conven-
tionally sintered alumina (top) and micro-structure of
AZ (bottom).
35
Strong neck growth of the AZ results in
substantially high strength compared to those of con-
ventional porous materials (Reproduced with permis-
sion of John Wiley and Sons)
the brous grain formation. As the sintering tempera-
ture further increases, the micro-structure becomes
coarser and the strength decreases with increasing
fracture toughness (though the toughness values are
still below 4 MPa m
1/2
). Porous b-Si
3
N
4
ceramics were
also fabricated by carbothermal reaction between silica
and carbon.
54
Micro-structure is controlled by varying
particle size of the carbon in this case. Tuyen et al.
55
fabricated porous reaction-bonded silicon nitride by
nitridation process at 1350uC and post-sintering at
15501850uC, which provides similar brous micro-
structure and high porosity. The duration time for
sintering had a signicant effect on the micro-structure
and grain morphology. The fabrication process is
advantageous due to the low cost of Si raw powder.
One of the unique processing routes for porous
ceramics with anisotropic micro-structure is tape-casting
brous seed crystals or whiskers. For porous silicon
nitrides, b-Si
3
N
4
seed crystals were mixed with sintering
additives as starting powders, and the green sheets
formed by tape casting were stacked and bonded under
pressure.
56
Sintering was performed at 1850uC under a
nitrogen pressure of 1 MPa. The texture of porous
silicon nitride with porosity of 14% is shown in Fig. 6.
The brous grains of silicon nitride are well aligned
toward the casting direction, and the pores, whose
shapes are mostly plate-like along the same direction,
exist among the grains. The anisotropic (brous grain-
aligned) porous silicon nitrides showed excellent
mechanical behaviour, when a stress is applied in the
alignment direction.
53,57
Figure 7 shows the fracture
strength and fracture toughness of the anisotropic
porous silicon nitrides as a function of porosity,
53,57
in
comparison with those of the isotropic porous silicon
nitrides that were sintered at 1800uC by using a-Si
3
N
4
and 5 wt-%Yb
2
O
3
.
53,58
The anisotropic materials exhib-
ited very high strength above 1?5 GPa, and very high
fracture toughness above 17 MPa m
1/2
in the porosity
range below 5%. It should be noted that the toughness of
the porous materials with porosities below 10% is
somewhat higher than that of the dense one (0%
porosity). These excellent mechanical properties were
due to enhanced crack shielding effects (bridging and
pull-out) of aligned brous grains. Debonding was
5 Micro-structures and mechanical properties (exural strength and fracture toughness) of porous silicon nitrides sintered
with 5 wt-%Yb
2
O
3
at 1600, 1700, 1800 and 1850uC. P denotes porosity
52
(Reproduced with permission of Elsevier)
promoted by the existence of pores, and aligned grains
bridging the crack or interlocking each other were
elastically deformed or drawn apart without breaking,
leading to the above crack shielding. It has been also
revealed that the anisotropic porous silicon nitrides are
much superior even to the dense materials, for both the
thermal shock fracture and damage resistances, which
are known to be in antagonistic relation.
53
Sacrificial fugitives
Porous ceramics can be obtained by mixing appropriate
amounts of sacricial fugitives as pore forming agents
with ceramic raw powder and evaporating or burning
out them before or during sintering to create pores (see
Fig. 2b). Frequently used pore forming agents include
polymer beads, organic bres, potato starch, graphite,
charcoal, salicylic acid, carbonyl, coal and liquid para-
fn. The pore forming agents are generally classied into
synthetic organic matters (polymer beads, organic bres,
etc.),
5989
natural organic matters (potato starch, cellulose,
cotton, etc.),
67,68,90105
metallic and inorganic matters
(nickel, carbon, y ash, glass particles, etc.),
49,106115
and
liquid (water, gel, emulsions, etc.).
116156
Porosity is
controlled by the amount of the agents, and pore shape
and size are also affected by the shape and size of the
agents respectively when their sizes are large in compar-
ison with those of starting powders or matrix grains. This
approach is useful particularly for obtaining high open
porosity. The agents, however, need to be mixed with
ceramic raw powder homogeneously for obtaining uni-
formand regular distribution of pores. Solid fugitives such
as organic materials are usually removed through
pyrolysis, which requires long-term heat treatment and
generates a great deal of vaporised, sometimes harmful,
byproducts.
Polymethylmethacrylate (PMMA) beads and micro-
beads have been frequently employed for sacricial
fugitives.
8,5964,77,79,8285
For example, Colombo and his
co-workers
8,5961
fabricated SiOC ceramic foam as
shown in Fig. 8, by dry mixing the silicon resin powder
with a sacricial template constituted by PMMA micro-
beads, and subsequent heat treatments. Cruz et al.
62
used
a colloidal processing technique with PMMA sacricial
templates, to fabricate macro-porous yttria-stabilised
zirconia ceramics. Descamps et al.
63,64
produced macro-
porous b-tricalcium phosphate (TCP) ceramics by using
PMMA. An organic skeleton, which was formed by inter-
connecting the PMMA balls through a chemical super-
cial dissolution, was impregnated by the TCP slurry.
The PMMA was eliminated by a thermal treatment at
low temperature, and sintering was carried out to obtain
nal porous structure. This process allows a total control
of the porous architecture; the porous volume can vary
from 70 to 80% and the interconnection size from 0?2 to
0?6 times the average macro-pore size.
Andersson and Bergstro m
82
used expandable micro-
spheres as a sacricial template to produce macro-
porous ceramic materials by a gel-casting process. The
micro-spheres consist of a co-polymer shell and are lled
with a blowing agent (isobutane), which allows rapid
and facile burn-out. By controlling the amount and size
of the expandable micro-spheres, it is possible to tune
the porosity up to 86% and the pore size distribution
from 15 to 150 mm. As low amounts as 12 wt-% of the
micro-spheres are required to create a nal porosity
above 80 vol.-%. Expandable micro-spheres as sacricial
templates, rather than other templates such as PMMA
micro-beads, are advantageous because of lower levels
of gaseous byproducts generated during pyrolysis, and
7 Porosity dependence of fracture strength and fracture
toughness, K
IC
of anisotropic and isotropic porous sili-
con nitrides. Stress is applied parallel to alignment
direction for anisotropic material
8 SiOC ceramic foam using a sacricial template consti-
tuted by PMMA micro-beads
8
(Reproduced with permis-
sion of Elsevier)
6 Micro-structures of anisotropic porous silicon nitride
prepared by tape-casting brous seed crystals (poros-
ity: 14%)
56
(Reproduced with permission of John Wiley
and Sons)
lower cost of the overall materials. Kim and his
co-workers
83,84
used hollow micro-spheres as sacricial
templates to make porous silicon carbide ceramics
synthesised from carbon-lled polysiloxane and others.
Using preceramic polymer and organic micro-spheres
for fabricating porous ceramics allows use of the low-
cost and/or near-net shaped processing techniques like
extrusion and direct casting. They reported relatively
high exural strength for porous SiC ceramics (e.g. 60
and 45 MPa at 40 and 50% porosity, respectively) and
very low thermal conductivity (2 W m
21
K
21
, at y70%
porosity).
84
Song et al.
85
produced micro-cellular silicon carbide
ceramics with a duplex pore structure by using expand-
able micro-spheres and PMMA spheres; which resulted
in the large pores and the small windows in the strut
area respectively. This porous ceramics showed excel-
lent air permeability as shown in the section on Gas
permeability.
Diaz et al.
93,94
fabricated porous silicon nitride
ceramics by using a fugitive additive, corn starch
(particle size: 518 mm). In order to obtain homoge-
neous dispersion of the fugitives, the mixture slurry was
kept in agitation by using a magnetic stirrer for a while,
and then was frozen and dried under vacuum for sieving.
Kim et al.
95
mixed various amounts of corn starch to
(Ba, Sr) TiO
3
powder to obtain (Ba, Sr) TiO
3
porous
ceramics. They found that depending on the porosity,
the PTCR effect was 12 orders of magnitude improved
in comparison with the dense reference.
Chen et al.
66
developed porous silicon nitride of
equiaxed a-grains by using phosphoric acid (H
3
PO
4
) as
the pore-forming agent and pressureless sintering of
relatively low temperatures techniques (10001200uC).
On the other hand, Li et al.
80
fabricated porous silicon
nitride with brous b-grain structure, using naphthalene
powder as the pore-forming agent and gas-pressure
sintering of high temperatures above 1700uC. The
bending strength of the former materials was 50
120 MPa in porosity range of 4263%, while that of
the latter was 160220 MPa in porosity of 5054%. This
substantial difference in strength is most likely due to
the micro-structural difference (equiaxed versus brous),
which was similar to what we observed in Fig. 5.
Ding et al.
49
used graphite as the pore-former to
fabricate mullite-bonded porous silicon carbide ceramics
in air from SiC and a-Al
2
O
3
through in situ reaction
bonding technique. Graphite is burned out to produce
pores and the surface of SiC is oxidised at high
temperatures to SiO
2
, which, at further increased
temperatures, reacts with a-Al
2
O
3
to form mullite
(3Al
2
O
3
.2SiO
2
). SiC particles are bonded by the mullite
and oxidation-derived SiO
2
.
Long bres such as cotton thread,
96
natural tropical
bre
97
and metal wires
109
are often used as pore forming
agents for obtaining porous ceramics of through
channels. Zhang et al.
96
produced porous alumina
ceramics with unidirectionally aligned continuous pores
(diameter: y160 mm) via the slurry coating of mer-
cerised cotton threads. The pore size can be adjusted by
using cotton threads of different diameters, and the
porosity can be controlled by changing the solids
concentration of the slurry. In this case excellent
permeability can be achieved for porous ceramics with
unidirectional through channel pores, because gas can
ow directly through the pores. However, the prepara-
tion of such ceramics is complex because handling long
bres such as thin wire or cotton thread is difcult.
Using short bres or whiskers as the pore-forming agent
is an alternative that combines the advantages of
partially sintered porous ceramic and those of unidirec-
tional pores. Yang et al.
65
demonstrated formation of
rod-shaped pores in silicon nitride ceramics, using slip
casting of aqueous slurries of silicon nitride powder and
sintering additives with 060 vol.-% fugitive organic
whiskers. Rheological properties of slurries were opti-
mised to achieve a high degree of dispersion with a high
solid-volume fraction. Samples were heated at 800uC in
air to remove the whiskers and sintered at 1850uC in
nitrogen atmosphere to consolidate the matrix. Porosity
was adjusted in 045% by changing the whisker content
in 060 vol.-%. The obtained porous silicon nitride
contained uniform rod-shaped pores with random
directions, exhibiting relatively high gas permeability
in comparison with porous silicon nitride containing
equiaxed pores.
157
Isobe et al.
81,110
and Okada et al.
86,87
used carbon bres (14 mm diameter and 600 mm length)
or Nylon 66 bres (9?543 mm diameter and 800 mm
length) for pore-forming agent, and tried to align them
by extrusion technique to produce porous alumina
81,110
and mullite
86,87
ceramics with unidirectionally-oriented
pores. They showed that the pore sizes and porosities
can be controlled by varying the bre diameter and bre
content. The obtained samples showed better air
permeability than the conventional porous materials
used for lter applications.
110
This technique can allow
the production of highly oriented porous ceramics by
industrially favoured extrusion method.
Liquid phases such as water and oil, which are readily
sublimated or evaporated, are often used as pore
forming agents.
116157
One of the most frequently
studied approaches in recent years is freeze-drying the
water or liquid-based slurry to produce porous ceramics
of unique structure.
119155
Figure 9 shows a schematic
illustration of the procedures which was employed by
Fukasawa et al.
119121
, and a porous silicon nitride body
obtained thereby. When the bottom part of the slurry is
frozen, ice grows macro-scopically in the vertical
direction, and pores are generated subsequently by
sublimation of the ice. Through sintering this green
body, a porous ceramics with unidirectionally aligned
channels can be obtained; these channels contain smaller
pores in the internal walls (Al
2
O
3
)
119,120
or brous grains
protruding from them (Si
3
N
4
).
121
This method has
several advantages, including simple sintering process
without materials to be burnt out, a wide range of
porosity (30 to 99%) controlled by the slurry concentra-
tion, applicability to various types of ceramics and
environmental friendliness without emitting harmful
products. In particular, porous scaffolds with ice-
designed channel-like porosity have been intensively
studied for a wide variety of applications including
biomedical implants and catalysis supports.
The porosity of the porous materials obtained by using
this technique is a replica of the original ice structure. The
porous channels run from the bottom to the top of the
samples, and the pores most frequently exhibit an
anisotropic morphology in the solidication plane.
Deville et al.
128131
investigated freeze casting of ceramic
slurries, and particularly the relationships between the
freezing conditions and the nal porous structures, for
moderate to highly concentrated suspensions. It has been
claried that the morphology of the porous structures,
i.e. the content, dimensions, shape and orientation of
porosity, was adjusted by varying the initial slurry
compositions and the freezing conditions. For highly
concentrated solutions, the particleparticle interactions
presumably lead to the formation of ceramic bridges
between two adjacent lamellae. They used the freeze-
drying technique to make sophisticated porous and
layered-hybrid materials. The nacre-like structure with
lamellar dendrites was obtained with a lamellar template
assembled by ice crystals, as shown in Fig. 10. Proper
control of the freezing conditions resulted in a porous
multilayered ceramics with compressive strengths up to
four times higher than those of materials currently used
for implantation. Munch et al.
132
emulated natures
toughening mechanisms in aluminium oxide and poly-
methyl methacrylate composites by using porous ceramic
structure fabricated by freeze-drying techniques, and
succeeded in obtaining toughness more than 300 times (in
energy terms) that of their constituents.
In order to avoid the freezing process under the
extremely cold temperature, Araki and Halloran
133135
used camphene, C
10
H
16
, as a vehicle for producing
porous ceramics via freeze-drying process. Slurries
containing ceramic powder in the molten camphene,
which were prepared at 55uC, were quickly solidied
(frozen) when they were poured into polyurethane
moulds at room temperature. The obtained porous
ceramic bodies have interconnected pore channels of
nearly circular cross-sections, unlike ellipsoidal ones in
conventional aqueous freeze casting. The channels are rep-
licas of entangled dendrites of frozen camphene. Employ-
ing a similar camphene-based freeze-casting approach, Koh
and his co-workers fabricated highly porous Al
2
O
3
,
136138
SiC,
139,140
PZT-based ceramics,
141,142
hydroxyapatite,
143,144
glass ceramics,
145
and ZrO
2
,
146,147
etc., having intercon-
nected pore without noticeable defects.
Combining freeze-drying process and gelcasting techni-
que has been also most frequently employed approaches to
make porous ceramics with rened micro-structure.
148156
These studies show the use of organic polymer in freeze
casting route affects the pore size and morphology by
controlling ice crystal growth during freezing. Chen
et al.
148,149
used alumina slurries containing tert-butyl
alcohol (TBA) and acrylamide (AM) for the freeze-drying
process. TBA, which freezes below 25uC and volatilises
rapidly above 30uC, acts as the freezing vehicle and
template for forming pores. Polymerised in the slurry as
the gelation agent, AM strengthens the green bodies
substantially. The sintered porous ceramics have good
mechanical strength (compression strength of 150 MPa at
porosity of y60%) because the pore channels formed by
the TBA template are surrounded by almost fully dense
walls without any noticeable defects. Ding et al.
150
also
used a gel freeze-drying process to fabricate porous mullite
ceramics with porosity up to 93%. Alumina gel mixed with
ultrane silica was frozen (isotropically), followed by
sublimation of ice crystals. Porous mullite ceramics were
prepared in air at 14001600uC due to the mullitisa-
tion between Al
2
O
3
and SiO
2
. Porous yttria-stabilised
ziroconia
151
and porous alumina
152
were fabricated by
freeze-drying process with addition of polyvinyl alcohol,
which prevents ice crystal growth and reduces the pore
sizes substantially. Porous alumina with oriented pore
structures has been also prepared by freeze casting
technique with a water-soluble polymer such as poly-
ethylene glycolon.
153
Using precursor silica hydrogels,
Nishihara et al.
154
fabricated ordered macro-porous silica
(silica gel micro-honeycomb), by freeze-drying methods
where micrometre-sized ice crystals are used as a template.
The pore sizes can be controlled by changing the
immersion rate into a cold bath and the freezing
temperature. For example, the average pore size can be
reduced to as small as 4?7 mmwith the rate of 20 cm h
21
at
77 K. It was also reported that the thickness of the
9 Schematic illustration of freeze-drying process for
macro-porous ceramics and a porous silicon nitride
body obtained thereby
121
(Reproduced with permission
of John Wiley and Sons)
10 Multilayered porous alumina structures a with dendri-
tic-like features b (detail) produced via freeze-drying
process
129
(Reproduced with permission of Elsevier)
honeycomb walls was affected by the SiO
2
concentration
and the pore size.
Using a gel-freezing method, Fukushima et al.
155,156
fabricated porous cordierite or silicon carbide ceramics
with porosity from 80 to 95%, where unidirectionally
oriented cylindrical channels are uniformly distributed
over relatively large bulk samples (typically several
centimetre). They used gelatin as the gelation agent,
which was mixed with water for the freezing vehicle
and rawpowder. The gel was frozen at 210 to 270uC and
was dried under vacuum, followed by degreasing and
sintering. The cell size and cell wall thickness both
decreased with decreasing the freezing temperature, rang-
ing from 20 to 200 mm and from 3 to 20 mm respectively.
The numbers of cells, for example, for the cordierite
sample frozen at 250uC and sintered at 1400uC was
1500 cells mm
22
in the cross-section, which is a markedly
large number in comparison with those of samples
obtained by extrusion method (12 cells mm
22
). Micro-
structural observation revealed dense cell walls as shown
in Fig. 11, which leads to relatively high compressive
strength, for example 17 MPa for 86% porosity sample of
silicon carbide.
Replica templates
Macro-porous ceramics having interconnected large
pores, or channels, of high volume porosity and open
cell walls have been frequently fabricated by the replica
techniques (Fig. 2c). The rst step of a typical template
process is impregnation of a porous or cellular struc-
ture with ceramic suspension, precursor solution, etc.
Various synthetic and natural cellular structures can be
used as templates. The templates need to have adequate
exibility, shape recovery ability and homogeneous open
cell structure.
The most frequently used synthetic template is porous
polymeric sponge such as polyurethane. They are soaked
into a ceramic slurry or precursor solution to impregnate
the templates with them, and the surplus is drained and
removed by centrifugation, roller compression, etc. In
this process, the appropriate viscosity and uidity
depending on the cell size, etc. are required so that
uniform ceramic layer forms over the sponge walls. The
ceramic-impregnated templates are dried and then heat-
treated to decompose the organic sponges. Following
the pyrolysis, the ceramic layers are sintered at higher
temperatures to densify. Porosity higher than 90% can
be obtained with cell sizes ranging from a few hundred
micrometres to several millimetres. The open cells are
interconnected, which allows uid to pass through the
foams with a relatively low pressure drop. However, due
to cracking the struts during the pyrolysis, the mechan-
ical properties of ceramic reticulated foams are generally
poor.
158
In order to avoid the strut crack formation, a
variety of approaches have been developed. In order to
increase the struts thickness and heal the strut cracks,
Zhu et al.
159
recoated repeatedly a reticulate porous
ceramic body with thinner slurry of the same composi-
tion, after the green body coated with thicker slurry
was preheated to burn out the sponge. In addition, Vogt
et al.
160
attempted the vacuum inltration of ceramic
slurry to ll up the struts in the pre-sintered foam.
The hollow struts caused by burnout of the polyur-
ethane template could be completely lled up, which
resulted in a considerable increase in compressive
strength. Luyten et al.
161
used a reaction bonded,
modied replica technique to produce strong struts
of ceramic foam. Jun et al.
162,163
produced hydroxya-
patite scaffolds coated with bioactive glassceramics
using the polymer foam replication method, to enhance
their mechanical properties and bioactivities. Plesch
et al.
164
fabricated a reticulated macro-cellular alumina
foam coated with TiO
2
for photocatalytic applications.
They showed that the photocatalytic activity can be
affected by the pore size of the host foam due to the
accessibility of UV light. This study implies that the
surface of macro-porous ceramic can play a role to
provide the additional functionalities for a component.
Highly porous ceramics can be derived also from
preceramic polymers after pyrolysis above 800uC in
inert atmosphere.
8
One of the typical methods is
dissolving the silicone resin preceramic polymer into a
suitable solvent and adding appropriate surfactants and
catalysts, followed by the pyrolysis. The advantages
include a very wide range of pore (cell) sizes (typically
1 mm to 2 mm), well-dened open-cell structures and
macro-defect-free struts.
165168
Paper-based template
has been also proposed; Travitzk et al.
169
succeeded in
fabricating single-sheet, corrugated structures, and
multilayer ceramics by using various paper replica
templates. Unique micro-structures such as aligned
pores derived from bres in the paper, elongated
morphology and multilayer stacking were observed,
and they substantially affected the anisotropic mechan-
ical properties.
Natural resources of porous structures such as woods,
corals, sea sponge, etc. have been also used as replica
templates. The woods are transformed to carbonaceous
preforms by heat-treatment under inert atmosphere. They
are then inltrated with oxides and non-oxides that react
to form porous ceramics. The frequently used inltrations
include molten metals,
170180
gaseous metals,
175,181186
alkoxide solutions,
187189
and others.
190,191
The benets
are a wide variety of obtained porous structures (de-
pending on the type of wood selected), low-cost start-
ing materials, near-net and complex shape capabilities,
and relatively low temperature manufacturing process.
Examples of porous structures of the pyrolysed woods
and Si inltrated samples are shown in Fig. 12. Par-
ticularly, the oriented vessels of the woods provide unique
11 Micro-structures of porous silicon carbide prepared
by freeze-drying technique using gelatin as gelation
agent frozen at 210uC
156
of Elsevier)
anisotropic porous structure of aligned unidirectional
channels, which is suitable to the applications such as
ltration and catalysis supports. Porous biomimetic
silicon carbide produced through this approach has been
also studied for the use as a medical implant material.
192
Biomorphic porous silicon nitride was produced from
natural sea sponge via replication method. The sponges
were impregnated with silicon-containing slurry via dip-
coating, and were heat-treated to delete the bio-
polymers, leading to a Si-skeleton. Subsequent thermal
treatment under owing nitrogen promoted the nitrida-
tion of the silicon, porous a/b-silicon nitride with a
porosity of 88% and the original morphology of the sea
sponge.
193
Direct foaming
In direct foaming techniques, ceramics suspension which
is foamed by incorporating air or gas is stabilised and
dried, and subsequently is sintered to obtain consoli-
dated structure (Fig. 2d). This technique allows low-
cost and easy production of highly porous ceramic
materials, up to more than 95% porosity. Porous
ceramics with unidirectional channels have been also
developed recently by using continuous bubble forma-
tion in ceramic slurry
194,195
However, due to the thermodynamic instability, the
gas bubbles are likely to coalesce in order to reduce the
total Gibbs free energy of the system, resulting in large
pores in the nal porous bodies. It is, therefore, critically
required to stabilise the air or gas bubbles in ceramic
suspension. One of the most frequently approaches for
the stabilisation is to use surfactants which reduce the
interfacial energy of the gasliquid boundaries. The pore
size of the produced porous body ranges from below
50 mm up to the mm scale,
196201
depending on how
effectively and rapidly the used surfactants work.
Surfactants used for the stabilisation are classied into
several types including non-ionic, anionic, cationic and
protein. A variety of effective surfactants have been
developed for the direct foaming of porous ceramics,
and representative approaches have been reviewed by
Studart et al.
9
and Sepulveda.
202
Barg et al.
199,200
developed a novel direct foaming
process with emulsifying a homogeneously dispersed
alkane or airalkane phase in the stabilised aqueous
powder suspension. In contrast to the conventional direct
foaming methods, foaming is made here by evaporation
of the emulsied alkane droplet, leading to a time-
dependent expansion of the emerging foam in a mould. It
was possible to realise interconnected structures with cell
sizes from 0?5 to 3 mm and porosities up to 97?5%. This
autonomous foaming process also allows high exibility
in the production of ceramic parts with gradient
structures and complex shaping. Foaming proceeds as a
consequence of the evaporation of the alkane phase
resulting in the growth of the stabilised alkane bubbles
and in a volume increase in the foam. The resulting
foamed green body possesses a tight cylindrical form with
a cross-section corresponding to the mould. Figure 13
shows typical three stages of the foaming process of an
emulsied alumina powder suspension (using 5?5 vol.-%
heptane and 0?83 vol.-% anionic surfactant):
(i) alkane emulsion in the powder suspension
(ii) transition of emulsion to wet foam
(iii) formation of a polyhedral structure (transition to
stable foam). While alkane droplets in the top
region evaporate and grow, new droplets are
simultaneously starting the foaming process in
the lower parts until the whole volume of the
emulsion is converted into stable foam.
Similarly to replica template approach, preceramic
polymer solution has been used instead of ceramic
suspension for direct foaming. Colombo and Modesti
203
fabricated porous ceramics by dissolving preceramic
polymers (silicone resins) into a suitable solvent and
adding blowing agent, surfactant, catalyst, etc., followed
by pyrolysis at 10001200uC in inert atmosphere.
12 Micro-structures of a different types of natural wood-
derived carbon performs
172
and of b biomorphous porous
silicon carbides from pinus silvestris
186
(Reproduced with
permission of Elsevier)
a alkane emulsion in the powder suspension; b transi-
tion of emulsion to wet foam; c formation of polyhedral
structure (transition to stable foam)
13 Three stages of foaming process of emulsied cera-
mic powder suspension
199
(Reproduced with permis-
sion of John Wiley and Sons)
Expansion was achieved by high speed mixing (intro-
duction of bubbles in the solution) and heat treatment at
2540uC. Because of the limited amount of defects in the
struts, the obtained porous ceramics showed higher
strength in comparison to conventional reticulated
foams.
204
Kim et al.
205,206
developed porous ceramics with a ne
and uniformly distributed micro-cellular structure from
preceramic polymers using CO
2
as a blowing agent. A
mixture of polycarbosilane and polysiloxane was satu-
rated with gaseous CO
2
under a high pressure and then a
large number of bubbles were introduced using a
thermodynamic instability via a rapid pressure drop.
The micro-cellular ceramics were obtained through
pyrolysis and optional, subsequent sintering.
It has been shown that particles with tailored sur-
face chemistry can also be used efciently to stabilise
gas bubbles for producing stable wet foams.
207210
Gonzenbach et al.
211214
have developed a novel direct
foaming method that uses colloidal particles as foam
stabilisers in order to obtain macro-porous ceramics
with smaller cell sizes than those of the foams prepared
with long-chain surfactants. Owing to the adsorption of
partially hydrophobic particles to the air/water interface,
the method allows for the fabrication of ultra-stable wet
foams which show neither bubble coalescence nor
disproportionation over several days, as opposed to
several minutes typically required for the collapse of the
surfactant-based foams. The attachment of colloidal
particles at the air/water interface is promoted by
adjusting the wettability of the particle upon adsorption
of short-chain amphiphilic molecules on the surface.
Because of its remarkable stability, the particle-stabi-
lised foams can be dried directly in air without crack
formation. The macro-porous ceramics obtained after
sintering exhibit porosities from 45 to 95% and cell sizes
between 10 and 300 mm. The compressive strengths of
the sintered foams with closed cells (for example 16 MPa
at porosity of 88% in alumina foams) are substantially
higher than those of foams prepared with other
conventional techniques. The surface-modied particles
which originally cover the air bubble in wet foams
become a thin surface layer of single grains after
sintering. Macro-porous ceramics with open porosity
can be also prepared with this technique by simply
decreasing the concentration of stabilising particles.
Gas permeability
Gas permeability is one of the most important properties
of porous ceramics which are expected to be used for gas-
lters such as DPF, since large pressure drops cannot be
tolerated in such applications. Highly porous ceramics
with aligned unidirectionally through pore channels,
which were prepared by freeze-drying process, are
expected to provide excellent permeability. In this section,
we discuss Darcian permeability of porous ceramics
with different pore sizes and structures. Figure 14 shows
the Darcian permeability as a function of pore size
for porous ceramics fabricated by the freeze-drying
processes,
152,156
organic spherical fugitives,
61,85
extruded
organic brous fugitives,
81,87
direct foaming,
196,215
and
replica templates.
215,216
The pore structures are classied
into three categories of Spherical (Connected),
61,85,196,215
Cylindrical (Connected)
81,87
and Cylindrical,
152,156
as
schematically shown. The Darcian permeability K is
determined from pressure drop and owrate of air by the
Darcys law.
217
Based on the capillary model, K is
expressed by
K~wD
p
2
=C (1)
where w is the porosity, D
p
is the pore diameter and C is a
constant depending on the pore structure.
217,218
All the K
values of Fig. 14 are adjusted at the porosity of 0?85 by
using equation (1) for comparison. Note that the inertial
contribution (non-Darcian permeability) was considered
in addition to the viscous one (Darcian permeability) in
Refs. 61, 152, 215 and 216, which results in high values of
K, compared to the case of neglecting the inertial
effect
81,85,87,156,196
(the ratio of viscous contribution in
total is 6090%
152
). If the uid ows through the
unidirectional cylindrical pores penetrating in parallel,
C is 32 (Ref. 218), which is shown as the solid line
(w50?85) in the gure. The porous ceramics fabricated by
the freeze-drying processes,
152,156
which have cylindrical
through channels, showed the permeability very close to
this solid line, indicating the unidirectional alignment of
the cylindrical pores. The permeability required for a
commercially available DPF is 10
211
to 10
212
m
2
,
219
and
most of the freeze-dry-processed materials exceed this
criterion. The porous ceramics prepared with extruded
organic brous fugitives
81,87
showed lower permeability
values than those of the freeze-dry-processed ones, most
likely because of limited contact area among the short
bres. As for the porous ceramics with a duplex pore
structure,
85
the permeability increases with increasing the
amount of PMMA micro-beads and decreasing the
averaged pore size, since the number of the small
windows in the strut area increases.
14 Darcian permeability as a function of pore size for porous
ceramics fabricated by freeze-drying processes,
152,156
in comparison with those of other processes includ-
ing organic spherical fugitives,
61,85
extruded organic
brous fugitives,
81,87
direct foaming,
196,215
and replica
templates.
215,216
Solid line indicates theoretical perme-
ability K5wD
p
2
/32 (w50?85) for case of unidirectional
cylindrical pores penetrating in parallel
Hierarchically porous ceramics
Porous ceramics can be divided into three categories of
macro-, meso- and micro-porous, according to its pore
size, as described in the section on Introduction. Based
on very recent review article of Colombo et al.,
12
hierarchical porosity can be dened as incorporation
of two or three of these different porous structures,
which can be provided by various methods of templat-
ing, impregnation, emulsion, phase separation, coating
and etching. Porous ceramic components with such
hierarchical porosity have attracted a great deal of
attention, due to the synergy effects of different
advantages that each porous structure can provide.
A typical example is micro-porous hydrogen permse-
lective silica membrane coated on the surface of meso-
porous c-alumina or macro-porous a-alumina supports,
which is expected to be widely used in future for hydrogen
usage. In this case, thin micro-porous layer has a role of
permselective of hydrogen gas and macro-porous mem-
brane support provides a mechanical strength due to
neck among alumina particles and mass transfer due to
interconnected macro-pores.
220224
Generally, the macro-
porous supports are fabricated by extrusion route or slip
cast and following partial sintering, and then meso-
porous or micro-porous membranes are coated onto the
supports by dip coating of sol solution through hydrolysis
and condensation of silicon alkoxide, or chemical vapour
deposition. Meso-porous intermediate layers frequently
put between membranes and supports. Yoshino et al.
220
fabricated micro-porous silica membranes and membrane
modules and examined the gas permeation characteristics
and stability of substrate. Tubular type a-alumina
substrate with 0?7 mm was prepared by an extrusion
method, and c alumina intermediate layer with 60 nm
pore size was formed by dip-coating of boehmite sol over
the substrate, followed by another dip coating process of
silica sol to make silica membranes on the top. The
alumina tube showed good heat-cycle stability for
strength and permeation (,5% changes after 100 cycles
of room temperature773 K). Excellent hydrogen perme-
ability of 5610
28
to 5610
26
mol m
22
s
21
Pa
21
with
H
2
/N
2
selectivity of 30300 was obtained at 873 K
with the silica membranes. Gu et al.
221
reported that a
dual-element silica-alumina composite membrane was
deposited by chemical vapour deposition of tetraethy-
lorthosilicate and aluminium-tri-sec-butoxid, on a-alu-
mina macro-porous support with c-alumina meso-porous
intermediate layers, as shown in Fig. 15. The meso-
porous intermediate layers were formed by dip coating of
boehmite sols with different particle sizes, resulting in
multiple graded structures without cracks. The supported
composite silicaalumina membrane showed high hydro-
gen permeability in the order of 10
27
mol/m
22
s
21
Pa
21
and good stability against water vapour in comparison to
pure silica at 873 K. Besides gas separation membranes,
similar processing approaches have been applied for a
variety of ltrations, adsorptions and catalysts.
225229
In
addition biomorphous method,
230,231
etching method
232
and PECS method
233,234
can also provide hierarchically
porous ceramics.
The above fabrication processes comprise several
steps including forming, sintering, coating, etc. For the
more simplied and efcient processes, several attempts
for one-pot synthesis (single step pyrolysis) have been
made to realise hierarchically porous ceramics. The most
frequent approach for the one-pot synthesis is to use
preceramic polymers. Preceramic polymers, including
organic and inorganic polymer with continuous silicone
network and sol solution prepared by hydrolysis and
condensation of metallic alkoxide, can provide ceramic
materials as residue through its pyrolysis. During heat
treatment of preceramic polymer with silicone network,
organic groups can be decomposed and be transferred to
inorganic bonds such as SiO, SiC and SiN, and
usually under inert atmosphere to prevent an oxidation
of organic groups. When preceramic polymer is used as
raw material to fabricate hierarchically porous ceramic,
meso- or micro-porosity has been formed by varying the
pyrolysis temperature of preceramic polymer,
235,236
using the block copolymer,
237242
and the addition of
ller into the polymer.
236,243
Several macro-porous
processing approaches including sacricial fugitives,
replica templates and direct foaming have been utilised
in order to provide the macro-posority. Holland et al.
237
reported that porous titania, zirconia, and alumina
from the inltration of the corresponding alkoxides
into the latex spheres as the templates for macro-
pores and revealed the highly ordered micro-structures.
Kim et al.
238
fabricated hierarchically porous alumina
with meso- and macro-pores, where meso-porous struc-
ture was obtained using alkyl carboxylate as a chemical
template, and macro-pore structure was developed
through polystyrene beads or silica gels. Suzuki
et al.
239
prepared hierarchically porous silica and
alumina by dual templating method of surfactant and
polystyrene beads. They conrmed macro-pores around
200 nm from the polystyrene sphere, and ordered meso-
pores around 4 nm due to the triblock copolymer and
micro-pores of ,2 nm due to the tail of copolymer.
Dacquin et al.
241
prepared macro-porousmeso-porous
alumina by using 400 nm polystyrene beads for macro-
pores and triblock copolymer for meso-pores, as shown
in Fig. 16. The regular macro-porous skeleton obtained
from polystyrene template was observed (A, B) while
high resolution TEM study revealed the ordered,
hexagonally packed meso-pores resulting from self-
assembly of the block copolymer solution (C).
15 Micro-structure of hierarchically porous ceramics com-
prising silica-alumina composite membrane, c-alumina
multi-intermediate meso-porous layers and alumina
macro-porous support
221
of Elsevier)
The growth of nano-structure on macro-porous substrate
can be also categorised as hierarchically porous ceramics.
The freeze-drying process is one of the routes which give us
such porous structures.
119121
As already stated, the macro-
scopic through channels obtained by this process contain
small pores in the internal walls and protruding whisker-like
grains, which results in pore size distribution with two or
three peaks corresponding to the respective pores. Another
approach is the chemical process via preceramic polymer.
As shown in Fig. 17, Vakifahmetoglu et al.
244,245
developed
a cellular SiOC ceramics with nano-wires using preceramic
polymer, foaming agent and metallic catalyst and showed
high specic surface area of 110 m
2
g
21
. They revealed the
much formation of long SiCor Si
3
N
4
nano-wires on the wall
of the cellular SiOC, and the effect of pyrolysis conditions
(atmosphere and temperature) on the formation of nano-
wires. SiC nano-wires on the macro-pores have been also
formed by conventional pressing,
246
replica templates
247
and camphene dendrites,
140
where preceramic polymer and
SiC powder as raw materials have been heated on the one-
pot synthesis. It was suggested that the formation of nano-
wires were due to iron impurities in the raw SiC powder.
Some other approaches have been also proposed;
Vanhaecke et al.
248
and Edouard et al.
249
fabricated SiC
nano-wires on the surface of SiC foam by the reaction
between carbon nano-bres and SiO gas, followed by the
oxidation removal of residual carbon. Jayaseelan et al.
prepared cordierite whiskers
250
and SiC nano-bres
251
on
the cordierite honeycombs via air sintering and carbother-
mal reduction respectively, using mixture of cheap raw
powder such as kaolin, talc, alumina, carbon and silica.
Summary and future prospective
During the last decade, tremendous efforts have been
devoted for the researches on innovative processing
technologies of porous ceramics, resulting in better
control of the porous structures and substantial
improvements of the properties. This article reviewed
these recent progresses of porous ceramics. Because of a
vast amount of research works reported in this eld
these days, the review mainly focused on macro-porous
ceramics whose pore size is larger than 50 nm. Followed
by giving a general classication of porous ceramics, a
number of innovative processing routes developed for
critical control of pores were described, along with some
important properties. They were divided into four
categories including (i) partial sintering, (ii) sacricial
fugitives, (iii) replica templates, and (iv) direct foaming.
The partial sintering, the most conventional technique
for making porous ceramics, has been substantially
sophisticated in recent years. Very homogeneous porous
ceramics with extremely narrow size distribution has
been successfully prepared through sintering combined
with in situ chemical synthesis. Porous silicon nitrides
with anisotropic micro-structure (aligned brous grains
and pores) produced via tape-casting and partial
sintering have exhibited excellent mechanical properties,
which are equivalent, or sometimes superior, to those of
the dense materials.
Advantage of the sacricial fugitives is that pore
shape and size are controlled by the shape and size of the
agents respectively. Various kinds of fugitive agents
have been used for obtaining desired porous structure.
The fugitives are most frequently removed through
pyrolysis, generating a great deal of vaporised, some-
times harmful, byproducts, and a lot of works have been
made to reduce or eliminate them. The freeze-drying
16 Micro-structures of macro-porousmeso-porous alumina
prepared by using polystyrene for macro-pores and tri-
block copolymer for meso-pores. (A) SEM and (B) TEM
observations for macro-porous skeleton, and (C) high-
resolution TEM for meso-pores
241
(Reproduced with per-
mission of American Chemical Society)
17 Micro-structure of SiOC foam (top), and SiC nano-wires
formed on its wall surface (bottom)
244
(Reproduced with
permission of John Wiley and Sons)
processes using water or liquid as fugitive materials are
advantageous in this viewpoint and have been very
intensively studied in recent years. Controlling growth of
ice during freezing leads to unique porous structures and
excellent performances of porous ceramics. For exam-
ple, the highly porous lamellar hydroxyl-apatite scaf-
folds via this approach are several times stronger than
materials currently used for implantation. Also the
freeze-dry-processed porous ceramics that have cylind-
rical through channels demonstrated the excellent
permeability.
The replica template techniques have been widely
used to fabricate porous ceramics with interconnected
large pores of high volume porosity. Porous polymeric
sponge such as polyurethane is the most typical
synthetic template used for this process. However, due
to cracking struts during pyrolysis of the sponge, the
mechanical reliability is substantially degraded; a variety
of approaches have been used to avoid the strut crack
formation. Natural template approaches using wood,
for example, as positive replica, have been frequently
used in these years and have realised highly oriented
porous open-porous structure with a wide range of
porosity.
The direct foaming technique offers low-cost and easy
production of highly porous ceramic materials. In order
to suppress coalescence of gas bubbles in ceramic
suspension that results in large pores in the nal porous
bodies, various methods which stabilise the bubbles have
been developed, including use of effective surfactants,
evaporation of emulsied alkane droplets, and use of
surface-modied particles. These novel processing routes
also lead to better mechanical properties. Then, the
article briey reviewed porous ceramics with hierarchical
porosity (incorporation of macro-, meso- and micro-
pores), which have attracted much attention in both
academic and industrial elds. Several attempts for one-
pot synthesis (single step pyrolysis) such as preceramic
polymer-derived approaches have been made to produce
hierarchically porous ceramics in more simplied and
efcient manner.
We now discuss several issues to be solved for further
activating the potential of macro-porous ceramics and
for expanding their applicability. As has been seen in
this review, a number of approaches have been already
used towards environmentally benign, resource-produc-
tive, and inexpensive fabrication processes. This ten-
dency will be of course enhanced in future, and a greater
amount of efforts will be devoted to the following
targets; fewer heat-treatments (pyrolysis, calcination,
sintering, etc.) of shorter time and lower temperature,
processing in air atmosphere and ambient pressure,
complete elimination of harmful byproduct generation,
use of abundant resources or recycled materials, near net
shape forming and sintering, etc.
Another important issue is further improved perme-
ability of porous ceramics even with smaller pore size,
which will be strongly demanded in many applications
of porous ceramics such as lters, membrane/catalysts
supports, and reactor beds. This will be potentially
attained by more precisely controlling pores themselves
(size and its distribution, shape, location, orientation,
etc.) and matix micro-structures (grains, whiskers, bres,
etc.) at different scale levels from nano to macro. For
example, the DPF of next generation will be desired to
lter smaller pollutants in the exhaust gases with less
pressure drop. We presume that one of the effective
solutions will be a hierarchically porous structure
incorporating well controlled macro-scaled cylindrical
pores and micro- or nano-scaled whiskers grown from
the internal walls, which enable the uid permeation and
pollutant capture respectively.
250,251
Finally, it should be remarked that porous ceramic
components are most frequently subjected to mechanical
loads and thermal shocks in their numerous applications
and that better structural reliability will be critically
needed to further expand their applicability in future
industries. Greater efforts will be made for ensuring the
mechanical reliability, such as enhancing neck growth
among matrix grains and avoiding crack formation
during fabrication. On the other hand, while pores are
generally believed to deteriorate the mechanical proper-
ties, this is not always true as seen in this review.
Carefully tailored porous micro-structures have a great
possibility to give rise to substantially improved or
unique properties that are not attained even in dense
materials.
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