Microstructure control in ceramic foams via mixed

cationic/anionic surfactant
Min Wang, Haiyan Du
n
, Anran Guo, Ruihua Hao, Zhenguang Hou
School of Materials Science and Engineering of Tianjin University, Key Lab of Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin 300072, PR China
a r t i c l e i n f o
Article history:
Received 13 June 2012
Accepted 7 August 2012
Available online 17 August 2012
Keywords:
Silica
Ceramic foams
Microstructure
Mixed surfactant
a b s t r a c t
Silica ceramic foams with controllable microstructure were produced by direct foaming method. The
silica foams were prepared through three different systems: individual cationic surfactant stabilized
system, individual anionic surfactant stabilized system, and the mixed cationic/anionic surfactant
stabilized system. The foaming ability and foam stability of the three systems were investigated and the
related mechanisms were discussed. The results showed that the mixed system had both long-term
stability and good foaming ability compared with the others. In addition, the role of the anionic
surfactant (SDS) on microstructure of the ceramic foams was studied. The results showed that the foam
structure changed from closed pores to open pores with the increasing concentration of SDS.
& 2012 Elsevier B.V. All rights reserved.
1. Introduction
Ceramic foams have been widely used in a range of elds, such
as lters, catalysts supports, bone scaffolds and refractories, due
to their characteristics of high permeability, high porosity, high
specic surface area, and good thermal stability [14]. In these
extensive applications, microstructural features of ceramic foams,
such as the morphology, porosity, and pore size, are crucial
factors that dominate the functional properties of the nal
product [5]. Direct foaming method offers a simple, low-cost
and effective way to fabricate ceramic foams by incorporation of
air bubbles into a suspension of powders and it can effectively
control the pore structure by articially controlling the foaming
ability [2]. However, the thermodynamic instability of wet foams
often leads to the coarsening of bubble, ultimately affecting the
structure of the nal product. Therefore, the stabilization of the
incorporated bubbles is the most critical step to prepare suitable
ceramic foams. Surfactants [6] and surface modied particles are
always used to stabilize foam. Binks et al. [7] prepared the
completely stable foams by controlling the hydrophobicity of
silanized silica nanoparticles. Gonzenbach et al. [8,9] also
reported that the foam stability could be drastically improved
by using partially hydrophobic particles as foam stabilizers.
Using mixed cationic/anionic surfactants in aqueous foam
systems have been of interest for several years because they
could provide good foam stability [10]. Though the mixed
surfactants used in pure aqueous foam are investigated
intensively, there are few studies about the mixed surfactants
used in the slurry foam system. The aim of this work is to
investigate the stabilization of foams with the mixed SDS/CTAB
in silica slurry system and develop a method for fabricating
ceramic foams with tailored microstructure. Besides, the foams
stabilized by the mixed and individual surfactants were compared
in terms of foaming ability and stability, and the related mechan-
ism was discussed. Furthermore, the effect of the concentration of
SDS on the microstructure was also studied.
2. Experimental procedure
The raw materials used in the study include spherical silica
powder (d
50
2 mm, Zhejiang Tongda Weipeng Electric Co., Ltd.,
China) with a specic surface area of 0.483 m
2
/g, cetyl trimethyl
ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS)
(98% pure, CR grade, Tianjin Kewei Chemical Reagent Co., Ltd.,
China). Besides, carboxymethyl cellulose (CMC, LR grade, Tianjin
Kemiou Chemical Reagent Co., Ltd., China) was used as binder to
avoid cracks during drying process.
The suspension was prepared by adding 35 wt% silica powder
to an aqueous solution containing CMC (1 wt% to silica), followed
by ball-milling with zirconia balls (5 mm diameter, ratio balls:
powder 2:1) in a 250 mL nylon milling pot for 20 h. Then,
different amounts of CTAB and SDS were added to 50 ml slurry
to obtain different slurry systems (A: CTAB 0.2 g/L, B: CTAB
0.2 g/LSDS 0.04 g/L, C: CTAB 0.2 g/LSDS 0.1 g/L, D: CTAB
0.2 g/LSDS 0.3 g/L, E: SDS 0.3 g/L). Afterwards, the slurries were
agitated with a household mixer at a rate of 1000 rpm for 5 min to
produce the foamed slurries. Finally, the green bodies were dried
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Materials Letters
0167-577X/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
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n
Corresponding author. Tel.: 86 1350 2052161; fax: 86 022 27892251.
E-mail address: [email protected] (H. Du).
Materials Letters 88 (2012) 97100
at 40 1C for 48 h, and the dried samples were sintered at 1050 1C
for 2 h. The heating and cooling rates were set to 2 and 4 1C/min,
respectively.
The foaming ability and foam stability in different systems
were characterized by measuring the height of slurries after
agitation and different idle times, respectively. The microstruc-
tures of sintered samples were observed by scanning electron
microscopy (XL30, Philips, Netherlands). The densities and por-
osities of the sintered samples were measured by Archimedes
principle.
3. Results and discussion
The foaming ability and foam stability in the mixed and
individual surfactant systems and the corresponding stages are
shown in Fig. 1. The stage 1 shows the foaming ability which was
characterized by the increased height of the foamed slurries after
5 min agitation. The stage 2 shows the variation of the foam
height as a function of the idle time after foaming process. The
instable foam will lead to collapse, which would ultimately cause
the dramatically decrease of the foam height. It was observed that
the height of the individual SDS stabilized foam was the highest
after 5 min agitation, but the height decreased by around 52%
after 240 min (Fig. 1E). In contrast, the height of the individual
CTAB stabilized foam after agitation was low, but the height only
decreased by about 5.6% after 1440 min (Fig. 1A). The analysis of
these phenomenon revealed that the individual SDS system had
short-time foam stability in spite of excellent foaming ability,
while the individual CTAB system had long-term stability but
poor foaming ability. However, both the excellent stability and
well foaming ability are required to control the microstructure. To
achieve this goal, we choose to add different amounts of SDS to
the individual CTAB system to obtain the mixed SDS/CTAB
systems. The results shown in Fig. 1BD demonstrate that the
mixed systems had both well foaming ability and long-time
stability compared with the individual system, and the foaming
ability increased with the increasing concentration of SDS.
Fig. 2 shows the variation in porosities and densities of the
sintered bodies with the increase of the concentration of SDS. The
concentration of CTAB used in these experiments was xed at
0.2 g/L. The results indicated that the porosity increased with the
increasing concentration of SDS. More specically, when the
concentration of SDS was 0.04 g/L, the open porosity was
obviously less than the total porosity, revealing that the structure
of sintered foam was mainly composed of closed pores. With the
increasing concentration of SDS, the open porosity increased
dramatically compared with the total porosity, indicating that
the closed pores gradually transform into the open pores. When
the SDS concentration reached 0.3 g/L, the open porosity was
practically equal to the total porosity, demonstrating an open
pore structure was obtained.
Fig. 3A shows the photograph of sintered foams made from
CTAB/SDS stabilized system. The sintered ceramic foam had a
diameter of 65 mm and a thickness of 40 mm. The SEM micro-
graphs of the ceramic foams with different systems were pre-
sented in Fig. 3BF. The foam structure of the individual CTAB
stabilized system was a small number of well-developed closed
pores due to the excellent stability but poor foaming ability of the
individual CTAB system (Fig. 3B). When a small amount of SDS
was added to the individual CTAB system, the foaming ability was
obviously improved, consequently obtaining more pores after
sintering (Fig. 3C). Moreover, it could be clearly seen that these
pores were mostly closed, which was attributed to the well
stability of mixed system. As the SDS concentration increased,
the mean pores size became to increase and the space between
the pores (cell wall thickness) began to decrease (Fig. 3CE).
When the SDS concentration reached 0.3 g/L, the well-developed
open-pores, which interconnected through windows in many
directions, were obtained (Fig. 3E). However, when the foam
was stabilized by individual SDS surfactant, the foam was not
stable, and consequently the pores were coarse and large coales-
cence after sintering (Fig. 3F).
The schematic foam stabilization mechanism for the three
different stabilization systems is given in Fig. 4. In the individual
SDS stabilized system, the SDS molecules would adsorb at the
interface of the bubbles to decrease the surface tension and the
decrease of surface tension would in favor of the foam stabiliza-
tion, as presented in Fig. 4A. However, these molecules could not
completely avoid bubble growth and coalescence because of their
low adsorption energy [11]. Consequently, individual SDS system
had great foaming ability but poor stability. While in the indivi-
dual CTAB stabilized system, positively charged CTAB molecules
can strongly adsorb onto the negatively charged silica particle
surface, because of the electrostatic interactions. The adsorption
of CTAB molecules result in a partially hydrophobic particle
surface. Then these modication particles can attach to
Fig. 1. The height variation of different stabilized system during agitation and
idle time.
Fig. 2. Bulk density and porosity of sintered ceramics varies with the concentra-
tion of SDS.
M. Wang et al. / Materials Letters 88 (2012) 97100 98
gas-liquid interfaces to stabilize bubbles (Fig. 4B), and this gives
rise to long-term stable foam in comparison with only adsorption
by surfactant molecules [12].
Compared with the individual stabilized system, the SDS/CTAB
mixed system had a synergy effect in foam stabilization, as
presented in Fig. 4C. First, CTAB molecules in the slurry can
attach to the silica particles obtaining partially hydrophobic
particles, which can signicantly improve the stability of bubbles.
Besides, surfactant mixtures could create a mixed surfactant layer
at gas/liquid interfaces. When two bubbles are approaching each
other to form a thin liquid lm, this mixed surfactant layer can
confer disjoining pressures to hinder this approaching. The
increasing SDS concentration allows more air bubbles to be
introduced into the suspensions. Based on the outstanding foam
stability resulted from the synergy effect, the microstructure
of samples was mainly closed pores, at low SDS concentration.
While at high SDS concentration, it will obtained well-developed
open pores.
Fig. 3. Photograph and SEM micrographs of sintered foam in different stabilized systems.
Fig. 4. Mechanism of bubbles stabilization in the different stabilized systems.
M. Wang et al. / Materials Letters 88 (2012) 97100 99
4. Conclusion
The preparation of silica ceramic foams with controllable micro-
structure fromSDS/CTAB mixed stabilized systemwas accomplished
by direct foaming method. In the foaming process, three different
systems (individual CTAB stabilized system, individual SDS stabi-
lized system, and the mixed SDS/CTAB stabilized system) were used
to stabilize the foam. The results showed that the mixed system had
long-term stability as well as good foaming ability compared with
the others. In this study, we tailored the structure of silica foams by
changing the SDS concentration in the mixed system. The SDS
concentration signicantly inuenced the structure of ceramic
foams, and the structure changed from closed pores to open pores
with the increasing concentration of SDS.
Acknowledgements.
This work is supported by National Natural Science Founda-
tion of China (Project No. 51172156).
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