Feature article
State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, PR China
University of Chinese Academy of Sciences, Beijing 100049, PR China
a r t i c l e
i n f o
Article history:
Received 9 January 2015
Received in revised form 11 June 2015
Accepted 14 June 2015
Available online 26 June 2015
Keywords:
Porous ceramics
SiO2 spheres
Dense packing
Uniform pore
Three dimension
a b s t r a c t
Porous silica ceramics with uniform and fully interconnected pores in three dimensions are fabricated via
sintering of randomly dense packed SiO2 spheres. The pores which origin from the space existed between
stacked spheres are well reserved and the necks between spheres are formed during heat treatment.
Due to the inactive surface of raw spheres, the uneven shrinkage is well restrained and the interconnected uniform pores are obtained. The pore size has linear relationship with sphere size as equivalent
to D50 = 0.320 d50 1.6. The neck strength can be enhanced by increasing sintering temperature in
the range of 10901230 C with negligible effect on pore structures. The permeable performance shows
that the synthesized porous ceramic with D50 of 8.13 m has an enhanced nitrogen permeance of about
4.4 106 L/(m2 h) under 150 KPa and its rejection coefcient of oil\water mixtures is up to 99% meanwhile
the ux can reach 3.0 105 L/(m2 h).
2015 Elsevier Ltd. All rights reserved.
1. Introduction
Porous ceramics, by virtue of their high specic surface area, low
thermal-expansion coefcient, excellent mechanical and chemical stability at elevated temperatures, have been expected to be
used for a wide variety of industrial applications from ltration,
absorption and catalyst supports to lightweight structural components [14]. The characterization of pores is the key factor for
their functional and structural applications [5]. The uniformity and
connectivity of pores have positive correlation with the ltration
performance of porous ceramics when they are applied as ceramic
lters [6]. The nonuniform pores which contain defects usually
suffer dissatised clearance for the smaller sized particle impurity, hence the desired ltration efciency cannot been achieved.
Except for larger ux, the fully interconnected pores can provide
more paths for uids which result in the enhanced sustainability
of lter. In addition, reduced stress concentration is promised and
the mechanical stability of porous ceramics is improved when uids ow through the interconnected uniform pores [5]. Hence, the
preparation of porous ceramics with uniform and interconnected
pores in three dimensions is of great signicance to industrial applications [5].
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stacked SSPs and the pores are reserved after sintered necks appear.
The spherical shape of the powders ensures the pores existed
between compact particles, which favors the formation of interconnected channels in ceramics. Dense packing can not only increase
the number of sintered necks to enhance ceramic strength, but
also reduce the probability of pores surrounded by numerous particles and thus results in a narrower pore size distribution. At last,
PSC with interconnected uniform pores and ne micro-morphology
was successfully fabricated, and its performance in nitrogen permeation and oil/water separation was veried.
2. Experimental procedure
2.1. Materials
SSPs were prepared via a two-step method combining
spray drying and DC thermal plasma sintering, and the
process conditions were shown in our earlier publication
[16]. In gelcasting process, acrylamide (AM, C2 H3 CONH2 ) and
N,N -methylenebisacrylamide (MBAM, (C2 H3 CONH)2 (CH2 )) were
used as monomers for polymerization. Ammonium persulfate
((NH4 )2 S2 O4 ) was added as an initiator and tetramethylethylenediamine (TEMED, (CH3 )2 NCH2 CH2 N(CH3 )2 ) was used as a catalyst.
All of these reagents were analytical pure.
2.2. Preparation of the porous silica ceramics
The preparation procedure is illustrated in Fig. 1. To begin of all,
AM and MBAM (mass ratio 30:1) were completely dissolved in a
certain amount of deionized water by mechanical stirring, and a
10 wt.% (for AM) premix solution was obtained, which served as
a dispersing media for the ceramic spheres. Secondly, the SSPs,
moderate TEMED and ammonium persulfate were added into
appropriate amount of premix solution successively. The slurry
was stirred evenly and the upper turbid liquid which contained
lots of superne debris was poured out after gravity sedimentation
Fig. 2. The characterization of synthesized spherical SiO2 particles: (a,b) SEM image of morphology, (c) cross-section image, and (d) XRD pattern.
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Table 1
Chemical composition of synthesized spheres.
Composition
SiO2
Na2 O
CaO
Al2 O3
Others
Content (wt.%)
97.734
0.907
0.403
0.293
0.234
0.429
Fig. 3. The size distributions of four groups (Pt.14) of synthesized SiO2 spheres.
Fig. 4. (a) SEM image of typical fracture surface of porous silica ceramics, (b) the size distribution of SiO2 spheres in Sp.2 and Pt.2, (c) the cross-section image of pores and
(d) pore size distribution of porous silica ceramics.
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Table 2
Effect of particle size on porous silica ceramics.
Sample mark
Density (g/cm3 )
Sp.1
Sp.2
Sp.3
Sp.4
30.75
41.73
56.20
63.85
8.13
11.75
16.04
19.52
1.33
1.20
1.13
0.87
29.35
34.15
38.94
41.34
29.8
17.1
8.5
4.7
Cp
Co
100
(1)
Fig. 4(a) is the SEM image of the typical fracture surface of PSCs
sintered at 1230 C for 2 h, exhibiting that densely arranged particles still have good sphericity and smoothness after sintered.
The pores are mostly composed by the cell walls of three or
four SSPs, and the pore channels can be considered that they are
made up of countless of continuous similar triangle and rectangle
cross sections. The sintered necks between spheres can be easily
observed, and the broken pieces and particles indicate adequate
neck strength. The size distribution of 300 random spheres on the
fracture surface of Sp.2 is almost coincided with the raw spheres,
as shown in Fig. 4(b). The d50 of spheres on Sp.2 is about 41 m
and is nearly the same as that of Pt.2, which conrmed the spheres
were rarely affected by sintering process and the pore structures
Fig. 5. (a) Pore size distributions of Sp.1, Sp.2, Sp.3 and Sp.4, (b) the liner relation of pore size and open porosity of sintered porous silica ceramics with median particle size.
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Fig. 8. SEM images of fracture surface of porous silica ceramics heat-treated for 2 h at different temperatures: (a) 1090 C, (b) 1160 C, (c) 1230 C and (d) 1300 C.
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(2)
(3)
where D50, Po and d50 are pore size, open porosity and median particle size. The decreasing density of Pt.14 decreases the centrifugal
force during sedimentation, which brings the looser packing density and increased porosity. The tting equation brings us an
important guidance in practice for a targeted porous ceramic with
a certain pore size.
In addition to the inuence on pore size of synthesized PSCs, the
size of SSP can also affect the mechanical properties, and the results
are listed in Table 2. It is found that the strengths of PSCs drop gradually from 29.8 to 4.7 MPa with the SSP size increase from 30.75 to
63.85 m. The mechanical properties of PSC made by partial sintering depend largely on porosity, neck numbers, as well as neck
strength between grains [1]. It is a consensus from a scientic and
industrial viewpoint that the average neck strength between particles is equal after same heat treatment [20]. With the increase of
particle size, the number of necks per unit volume decreased and
porosity increased correspondingly. So, it was reasonable for the
decreasing strengths and densities of synthesized porous ceramics
when particle size increased [20].
3.4. Effects of sintering temperature on porous silica ceramics
In order to identify the appropriate sintering schedule, TGDSC
analysis (Fig. 6) on the green ceramics was applied with a heating
rate of 10 C/min. The DSC curve was divided into three stages for
a clear idea of analysis.
I) For temperatures ranging from 50 to 520 C, a slope on TG curve
is observed. The departure of the organics is responsible for the
mass variation (loss of 12%) and is correlated to the (A) and (B)
exothermic peak. In this temperature range, the decomposition
products are released through gaps of spheres.
II) Temperatures between 520 C and 1000 C can be classied as
stage two. In this stage, the baseline of DSC curve declines
notably illustrating a mild heat release process, and phase
changes may take place.
III) In stage three (10001300 C), an endothermic peak (noted (C))
around 1066.9 C is characteristic of glass transition, while the
higher reported value of Tg is 1200 C [21]. It could be explained
by the presence of mineralizing agent (Na2 O, etc., Table 1)
which could weaken the glass structure and reduce the viscosity by breaking the Si O Si bonds in the SiO4 network [22,23].
Then, a weak exothermic peak around 1165 C (Tn , noted (D))
was supposed to be bulk crystallite nucleation and the next
noticeable exothermic peak around 1242.3 C (Tc , noted(E)) is
denoted as bulk crystallization. Similar conclusions could also
be found in other literature reports [24,25].
Fig. 9. The compressive strength (a), open porosity (b), and density (c) of porous
silica ceramics sintered for 2 h at different temperatures.
The phase changes of SSPs heat-treated at different temperatures are shown in Fig. 7. After treatment at 700 C, quartz
and tridymite started to precipitate from the amorphous matrix
to reduce the internal energy of glass system, which was corresponded to the decline of DSC curve at stage two. Keeping
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Fig. 10. SEM images of cracks on sphere (a) and neck (b).
variation trends as function of sintering temperature are summarized in Fig. 9. When treated temperature increases from 1090 to
1230 C, the compressive strengths of all samples increase to different extent while the densities and porosities change slightly.
It illustrated that the neck strength could be enhanced through
increasing sintering temperature in a wide range while the pore
structures were rarely affected. However, when heat treatment is
above 1300 C which exceeds Tc , the strengths decrease signicantly. To nd the reason of this phenomenon, the cross-section
features of PSC sintered at 1300 C are studied and shown in
Fig. 10. It is clear to see that cracks on spheres (Fig. 10(a)) and
necks (Fig. 10(b)) extend randomly, which are negative to strength.
The formation of cracks was related to the bulk crystallization
of -cristobalite at high temperature. It is reported that the cristobalite, as a high temperature polymorph of silica, undergoes
phase transformation with a volume contraction of about
5 vol.% when it is cooled down to 200270 C [27,28], which results
in the formation of cracks in as obtained silica ceramics. Besides, the
amorphous silica crystallization into cristobalite could increase the
glass viscosity drastically and inhibit the kinetics of mass transfer
during sintering [26]. In order to obtain the maximum strength of
PSCs, the sintering temperature should be precisely controlled to
get a balance between mass transfer rate and crystallization degree
of cristobalite. After contrasting the performance trend as shown
in Fig. 9, 1230 C can be chosen as the optimal treatment temperature.
3.5. Application of synthesized porous ceramics in uid ux
To explore the benet of three-dimensional interconnected and
uniform pores packed by spherical powders, a lter tube with same
micro dimensions of Sp.1 was used in nitrogen permeation test and
Fig. 11. Picture of prepared lter tube (a), ux (b) and rejection (c) of oil/water separation as a function of ltration pressure.
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