Received: 18 August 2017

| Accepted: 24 September 2017

DOI: 10.1111/jace.15265

RAPID COMMUNICATION

Extrusion of highly porous silicon nitride ceramics with bimodal

pore structure and improved gas permeability

Guang-Peng Jiang1,2 | Jian-Feng Yang2

1
School of Chemistry and Materials
Engineering, Fuyang Normal College, Abstract
Fuyang, Anhui, China Highly porous Si3N4 ceramics with bimodal pore structure were prepared by
the extrusion processing with petroleum coke of 30 lm as pore-maker. The
2
State Key Laboratory for Mechanical
Behavior of Materials, Xi’an Jiaotong
microstructure, mechanical strength, and gas permeability were investigated. The
University, Xi’an, Shaanxi, China
microstructure with petroleum coke contained not only numerous fine pores by
Correspondence interlocking the high aspect ratio b-Si3N4 grains, but also some large pores of 15-
Jian-Feng Yang, State Key Laboratory for
Mechanical Behavior of Materials, Xi’an 25 lm left by the burnout of petroleum coke. The resultant samples obtained an
Jiaotong University, Xi’an, Shaanxi, improved gas permeability of 1.2 9 10
12 m2, which is approximately two times
China.
that of samples without petroleum coke addition. Furthermore, the mechanical
Email: yang155@mail.xjtu.edu.cn
strength is still superior even at a porosity of 67% in comparison with the other
porous ceramics used in the current diesel particulate filter.

KEYWORDS
extrusion, microstructure, permeability, porous materials, silicon nitride

1 | INTRODUCTION viewed from a shaping perspective, these routes are still

Porous silicon nitride (Si3N4) ceramics are gaining increas-
ing attention due to their superior mechanical properties
and thermal shock resistance in comparison with other
types of porous ceramics.1-6 They can be promising candi-
date as diesel particulate filter (DPF) in replacement of the
current cordierite and SiC ceramics. When used as DPF,
porous Si3N4 should be designed to possess as high as
porosity, while maintaining enough mechanical strength
and filtration efficiency, because high porosity can improve
exhaust permeability and lower the pressure loss of DPF,
thus improving fuel economy.7,8
To date, highly porous Si3N4 ceramics have been fabri-
cated by various processing routes including addition of
fugitive inclusions,9 replica,10 direct foaming,11 and ice-
templating method.1,12 Indeed, different routes have their
respective advantages. For example, replica and direct
foaming can readily obtain a high porosity of up to nearly
90%, while ice-templating can bring about a unique lamel-
lar structure with aligned pore channels. Nevertheless,
difficult to obtain articles with complex honeycomb struc-
ture, which are widely used in current DPF applications.
Actually, extrusion, a common shaping technique in
ceramics production, can be used to solve this problem.
In previous study, we have already prepared porous Si3N4
ceramics by extrusion using different binders.13 However,
it is still difficult to achieve porosity higher than 60%,
only by controlled sintering by changing sintering condi-
tions or sintering aids. More importantly, the most
obtained pore size is relatively small (around 1 lm),
which is disadvantageous in further improving gas perme-
ability.9,10,14,15
In this study, using petroleum coke with appropriate size
as pore-maker, highly porous Si3N4 ceramics with bimodal
pore structure were prepared via extrusion. For comparison,
porous Si3N4 ceramics without petroleum coke also were
prepared via the same processing. The microstructure,
mechanical strength, and gas permeability were investigated
and the feasibility of this processing route for producing
high-performance Si3N4 DPF is evaluated.

J Am Ceram Soc. 2017;1–5. wileyonlinelibrary.com/journal/jace © 2017 The American Ceramic Society | 1

2
| JIANG AND YANG

4lL
2 | EXPERIMENTAL PROCEDURE DP ¼ Q (1)
pKD2
2.1 | Preparation of Samples where MP is the pressure drop from entrance to exit of the
sample, K the Darcy’s permeability, l the dynamic viscos-
Commercially available Si3N4 powder (a-Si3N4 ratio:
ity of the fluid, D the diameter of the sample, L the thick-
>95%; mean particle size: 1.2 lm; Shanghai Junyu,
ness of the sample, and Q the flow rate. The gas
Shanghai, China) was selected for use in this study.
permeability tests were carried out by a homemade appara-
Y2O3 (99.9% purity; Shin-etsu Chemical, Tokyo, Japan)
tus, whose schematic diagram can be found in the litera-
and hydroxypropyl methylcellulose (HPMC; Ruitai cellu-
ture.14 The samples cut into 1-2 mm in thickness were
lose, Taian, China) were used as sintering aid and bin-
fixed in the center of an epoxy resin mold. The gas perme-
der, respectively. The petroleum coke (carbon content:
ability is calculated from the slope of the line fitted using
90%; Shaanxi Chemical, Xi’an, China) with average par-
Equation (1). The fluid used is air, and its dynamic viscos-
ticle diameter of 30 lm was used as pore-maker. Firstly,
ity l is 1.8 9 10
5 Pas.10
powder mixture composed of Si3N4, 5 wt% Y2O3,
10 wt% HPMC, and 50 wt% petroleum coke (all based
on the weight of Si3N4 powder) was dry mixed in a 3 | RESULTS AND DISCUSSION
planetary mixer for 30 minutes. After 24 wt% distilled
water, 5 wt% glycerol, and 5 wt% castor oil (all based 3.1 | Porosity, Phase Composition, and
on the total weight of Si3N4 and petroleum coke) were Microstructure
added, the obtained mixture was kneaded in an alumina
After sintering, the porosities of the samples without and
mortar with a pestle for 20 minutes, providing a high-
with 50 wt% petroleum coke were 55% and 67%, respec-
shear mixing to break up agglomerates and to obtain
tively. It suggests that 50 wt% addition of petroleum coke
homogeneous paste. The resulting paste was extruded to
can bring about 12% increase in porosity. However, it is
form the rods 8.8 mm in diameter through a homemade
understandable in that the added amount of petroleum coke
piston-type extruder (barrel diameter: 25 mm, length of
was based on the weight of Si3N4 powder, and the resultant
die land: 12 mm) at room temperature. The extruded
volume fraction of petroleum coke in the paste was only
rods were subsequently cut into about 40 mm in length
about 20%. Moreover, shrinkage in different processing
and dried at 40°C for 10 hours. The dried rods were
stages can further contribute to the decrease in porosity.
then thermally debinded at 750°C with a heating rate of
For example, the measured linear shrinkage after sintering
30°C/h to remove HPMC, lubricant, and petroleum coke.
is 1.3% in this experiment, which can lead to about 4%
Finally, the samples were placed in a BN-coated graphite
decrease in porosity. Although porosity was increased by
crucible and sintered in a furnace (High multi-5000; Fiji-
only 12%, the current porous Si3N4 ceramics already pos-
dempa, Osaka, Japan) at 1700°C under 0.3 MPa nitrogen
sessed markedly higher porosity than other porous ceramics
atmosphere for 2 hours with a heating rate of 15°C/min;
used as DPF, whose porosity is usually between 45% and
no powder bed was covered on the samples during sin-
60%.
tering.
The XRD analysis of samples is shown in Figure 1.
In order to evaluate the effect of pore-maker, porous
After sintering, as expected, a- Si3N4 in the different sam-
Si3N4 ceramics without petroleum coke also were prepared
ples was transformed into b-Si3N4, regardless of the differ-
for comparison. The main difference in processing is that
ent starting paste formulation, indicating that petroleum
the formulation for control samples contained no petroleum
coke has no effect on the phase transformation. The reason
coke. However, in order to still obtain satisfactory plasticity
is that petroleum coke was already completely removed
of paste, the added amount of liquid need some minor
during debinding at 750°C, thus imposing no effect on
adjustment. The added distilled water, glycerol, and castor
sintering.
oil were 25%, 5%, and 10% (all on Si3N4 powder weight
Low-magnification SEM micrographs of samples are
basis), respectively.
presented in Figure 2. It can be seen from Figure 2A that a
number of large pores are uniformly distributed on the frac-
2.2 | Characterization ture surfaces of samples with 50% petroleum coke and this
phenomenon is more obvious on its polished surfaces in
The bulk density, porosity, three-point bending strength,
Figure 2B. According to Figure 2B, the size of large pores
X-ray diffraction (XRD) analysis, and the microstructure
is mainly between approximately 15 and 25 lm, which
were characterized according to previous methods.13 The
also can be seen from Figure 3A. By contrast, similar large
gas permeability of the porous ceramics was evaluated
pores are hardly seen on the polished surfaces of the
using Equation (1):
JIANG AND YANG
F I G U R E 1 X-ray diffraction results for samples with different
starting raw materials: (A) with 50% petroleum coke and (B) without
50% petroleum coke
control samples, even at a higher magnification in Fig-
ure 2C than in Figure 2B. The reason for the obvious dif-
ference is that petroleum coke was removed by burn-out,
leaving large pores, which remained through sintering.
Figure 3 shows high-magnification SEM micrographs
on fracture surfaces of samples. As seen from Figure 3A,
bimodal pore structure can be clearly revealed in the sam-
ples with petroleum coke. Besides the large pores, numer-
ous fine pores with a size of about 1 lm exist in the
microstructure, which originated from the interlocking of
the rod-like grains. The formation of numerous rod-like
grains were believed to result from the anisotropic growth
of the hexagonal b-Si3N4 grains to maximize the area of
the low energy (100) prismatic planes, thus further substan-
tiating the successful phase transformation from a- Si3N4
into b-Si3N4. These rod-like grains have a high aspect ratio
and a mean diameter of 0.5 lm, which can be seen in Fig-
ure 3B. In addition, by comparing Figure 3A,C, it is found
that the grain aspect ratio of samples with petroleum coke,
especially in the vicinity of the large pores, is considerably
(A) (B)
F I G U R E 2 Low-magnification SEM micrographs of samples: (A) on fracture surface with 50% petroleum coke, (B) on polished surfaces
with 50% petroleum coke, and (C) on polished surfaces without 50% petroleum coke
| 3
higher than that without petroleum coke addition. One rea-
son may be connected with the metallic element impurity
(Ca, Mg, Al, etc.) in petroleum coke, which exist in the
form of metal oxide sintering aids after thermal debinding.
It is well known that different sintering aids can have dif-
ferent impacts on the anisotropic growth of Si3N4 grains.
For example, it is reported that 0.5 wt% CaO addition to
the Y2O3:MgO sintering system can to some extent
increase the grain aspect ratio in porous Si3N4 ceramics.4
Another reason for the higher aspect ratio should be that
these large pores left by petroleum coke facilitate the free
growth of numerous elongated b-Si3N4 grains toward these
large pores, thus avoiding steric hindrance considerably.13
Accordingly, because of the free growth toward large
pores, the size of these large pores (15-25 lm) is smaller
than the supposed size (average particles size of petroleum
coke: 30 lm).
3.2 | Gas permeability
The gas permeability for the samples with and without pet-
roleum coke addition is 1.2 9 10
12 and 5.6 9 10
13 m2,
respectively. The permeability is improved by approxi-
mately one time with the use of pore-maker, while the
porosity is increased by only 12%. The dramatic improve-
ment of permeability can be explained through the follow-
ing Carman–Cozeny equation:9
pd2
K¼ (2)
16fCK s2
where K is Darcy’s permeability, p the efficient porosity
contributing to the permeability, d the average pore diame-
ter, fCK Carman–Kozeny coefficient, and s the tortuosity of
pore channels defined by the ratio between the mean length
actually traveled by the fluid passing through the porous
medium and the thickness of the porous medium in the
macroscopic direction of the flow. This equation indicates
that Darcy’s permeability is in direct proportion to the effi-
cient porosity and the square of the average pore diameter
but in inverse proportion to the square of the tortuosity. As
(C)
4
| JIANG
(A) (B)
F I G U R E 3 High-magnification SEM micrographs on fracture surfaces of samples: (A) with 50% petroleum coke, (B) with 50% petroleum
coke at higher magnification, and (C) without 50% petroleum coke
analyzed above, the numerous fine pores in the present
samples were formed by the interlocking of the high aspect
ratio, rod-like grains, which is intrinsically advantageous in
contributing to permeability. Therefore, in the present
highly porous ceramics, the efficient porosity can be
assumed to be equal to the obtained porosity. On the other
hand, the large pores introduced by petroleum coke not
only increase the mean pore diameter, but also decrease the
tortuosity during permeability tests. Since the decreased
tortuosity and the increased porosity and pore diameter can
be simultaneously achieved, it is understandable that a dra-
matic improvement in permeability is realized by the petro-
leum coke addition of 50%.
Hence, the reason for introducing large pores, rather
than small pores, to improve permeability is obvious. It is
because permeability is in direct proportion to the square
of the mean pore diameter, so permeability enhancement
by introducing large pores of 15-35 lm in this study is
more efficient. Actually, pore size of 10-25 lm is common
in DPF application. Furthermore, it is revealed that pressure
drop of DPF drastically increases when mean pore size is
less than 10 lm.
3.3 | Mechanical strength
Excellent mechanical strength is highly desirable in DPF
application because it determines the durability to a large
extent. The bending strength of samples with petroleum
coke addition is 35 MPa, nearly one-third of the strength
without petroleum coke (104 MPa). It is well known that
porosity and mechanical strength are always contradictory,
and a function can be used to express the relation between
strength and porosity.14,16
r ¼ r0 expð
bPÞ
where r0 is the strength at a porosity of 0, b the structural
factor, and P the porosity. The strength decreases exponen-
tially with the porosity. In view of the similar development
of b-Si3N4 grains, the b value for different samples can be
thought to be the same. Based on Equation (3) and the
AND YANG
(C)
obtained strength, it can be calculated that the current
structural factor is ~9, which is relatively large, considering
that the typical reported b value is 3-9.17 The high b means
a more dramatic degradation in strength with the increase
in porosity, which should originate from existence of the
large pores in the samples with petroleum coke. These
large pores are usually thought as serious flaws from a
mechanical strength perspective, which lead to stress con-
centration in the vicinity of the large pores.
The current strengths are compared with other sources
in the literature in the Figure 4. Recrystallized SiC, Si–SiC
(SiC bonded by Si) and cordierite are the three common
materials used as DPF, and their mean pore sizes are
between 10 and 20 lm,7,8 similar to the current samples
with petroleum coke. It is surprising that, in contrast with
Si–SiC material, the porosity and strength of the present
samples can be improved simultaneously and the present
samples exhibited an obviously higher mechanical strength
even with a porosity of 67%. The superior mechanical
property can be attributed to the interlocking of the well-
developed, high aspect ratio Si3N4 grains, which does not
(3)
F I G U R E 4 Comparison of the current strengths with other
porous ceramics used as DPF7,8
JIANG AND YANG
exist in other types of porous ceramics. In view of the high
permeability and mechanical properties obtained, the cur-
rent processing route is very promising for manufacturing
high-performance Si3N4 DPF.
4 | CONCLUSION
Highly porous Si3N4 ceramics with bimodal pore structure
were prepared by the extrusion processing with petroleum
coke of 30 lm as pore-maker. For comparison, porous
Si3N4 ceramics without petroleum coke also were prepared.
The microstructure, mechanical strength and gas permeabil-
ity were investigated. The microstructure with petroleum
coke contained not only fine pores by interlocking the high
aspect ratio b-Si3N4 grains, but also large pores left by the
burnout of petroleum coke. The resultant samples obtained
a high porosity of 67% and an improved gas permeability
of 1.2 9 10
12 m2. Furthermore, the mechanical strength
is still superior in comparison with the other porous ceram-
ics used in the current DPF.
ACKNOWLEDGMENTS
This work is financially supported by the National Natural
Science Foundation of China (51072157, 51302208) and
the Start-up Foundation for Doctor and Natural Science
Foundation (2017FSKJ15) of Fuyang Normal College of
China.
ORCID
Guang-Peng Jiang http://orcid.org/0000-0002-1347-
821X
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How to cite this article: Jiang G-P, Yang J-F.
Extrusion of highly porous silicon nitride ceramics
with bimodal pore structure and improved gas
permeability. J Am Ceram Soc. 2017;00:1–5.
https://doi.org/10.1111/jace.15265