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Ceramics International 44 (2018) 1187–1192

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Short communication

Fabrication of porous ceramics with double-pore structure by stepwise T


freeze casting using water/diphenyl methane emulsion

Yufei Tang, Mengchen Mao, Sha Qiu, Kang Zhao
Department of Materials Science and Engineering, Xi’an University of Technology, Xi’an, Shaanxi 710048, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Porous alumina with double-pore structure was fabricated by stepwise freeze casting using water/diphenyl
Freeze casting methane (DPM) emulsion as freezing medium. The effects of DPM content in the alumina slurry on the pore
Water-diphenyl methane emulsion structure, mechanical properties, and specific surface area of porous ceramics were investigated. The porosity of
Alumina porous ceramics was not significantly affected by DPM content in the alumina slurry due to their same solid
Specific surface area
contents. The lamellar pore size decreased, and the spherical pore size increased in porous alumina with in-
Interception rate
creasing DPM content in the slurry. Closed spherical pores were formed in lamellar pore walls when the DPM
content was 10 vol%. The compressive strength slightly increased, and the specific surface area decreased in the
samples with DPM compared with those in porous ceramics with pure water as freezing medium. The specific
surface area of porous alumina was 0.566 m2/g, and the interception rate for titan yellow was 44.16% when the
DPM content reached 25 vol% because the large spherical pore was connected to the outside. Hence, the fab-
ricated porous alumina with DPM exhibited potential as adsorption and filtration materials.

1. Introduction immiscible solvents are mixed to form an emulsion, which is used as


freezing medium to prepare ceramic slurry, the resulting crystalline
Porous ceramics have gained increasing attention in the fields of morphology and ultimate pore structure are completely different due to
filter materials, bone implant scaffolds, and solid oxide fuel cells be- the different physical properties of the two solvents during freezing
cause of their high porosity and specific surface area [1–3]. The prop- [22–24]. These studies reported that dispersed oil phases in the emul-
erties of porous ceramics mainly depend on the pore structure (pore sion were used as spherical pore-forming agents after solidification;
shape, pore distribution, pore number, porosity, and pore size) and on spherical porous materials were obtained due to shaping and drying in
the nature of ceramic materials [4–6]. Porous ceramics with con- the freeze-drying process. Qian et al. [25] used cyclohexane to prepare
trollable pore structure and excellent mechanical properties can be emulsion and fabricate porous materials with lamellar and spherical
prepared by freeze casting [7]. When the solvent in ceramic slurries is pores by directional freeze casting in liquid nitrogen. The density of
frozen at low temperatures, crystallization occurs, leading to the for- cyclohexane was 0.78 g/cm3. Various additives were used to stabilize
mation of pores after sublimation at low pressure [8,9]. Water, tert- the emulsion. Moreover, if adding ceramic particles in the emulsion to
butyl alcohol, and camphene are the main solvents (freezing medium) form emulsion ceramic slurry, then the ceramic particles will con-
used to prepare porous ceramics through freeze casting; this method siderably affect the stability of the emulsion and the resulting pore
also produces frozen crystals with lamellar, six square, and dendritic structure; this limitation must be further explored in future studies.
structures [10–12]. The pore structure of the final porous ceramic is In this study, we mixed diphenyl methane (DPM) with distilled
determined by the shape, size, and distribution of crystals [13–15]. water; DPM possesses similar density (1.006 g/cm3) to that of water
Porous ceramics with regular crystal distribution can be obtained by and a melting point of 24.5 °C. The mixture was emulsified by stirring
introducing multiple cooling sources or electromagnetic fields to con- and ultrasonic pulverization. The emulsion was used as freezing
trol the growth of ice crystals [16,17]. Addition of soluble NaCl crystals medium in preparing ceramic slurry and frozen stepwise at 10 °C and −
or glycerin in water can also affect the shape of ice crystals [18,19]. 30 °C. The mixture was dried and sintered to obtain porous ceramics.
Scholars used two kinds of miscible solvents as freezing medium, which The purpose of adding DPM is to increase the specific surface area of the
forms eutectics when frozen [20]. Therefore, a pore morphology that pore walls of porous ceramics with lamellar pore channels while
differs from that of single solvent can be obtained [21]. When two maintain their mechanical properties. The emulsion crystallization


Corresponding author.
E-mail address: kzhao@xaut.edu.cn (K. Zhao).

http://dx.doi.org/10.1016/j.ceramint.2017.09.233
Received 23 June 2017; Received in revised form 28 September 2017; Accepted 29 September 2017
Available online 29 September 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Y. Tang et al. Ceramics International 44 (2018) 1187–1192

Table 1 electron microscopy (SEM, JSM 6390A; JEOL, Tokyo, Japan). The pore
Composition of 100 mL of emulsion ceramic slurries. sizes of porous alumina were determined by measuring the cross-sec-
tion of the samples in the SEM images with SmileView (Software, JEOL,
Emulsion ceramic slurries (100 mL)
Japan). The lamellar pore size is the distance between the adjacent pore
DPM/H2O emulsion I (50 mL) Alumina suspension II (50 mL) walls, and the spherical pore size is a nominal radius. One hundred
pores were tested to obtain the average value. The porosity of the
DPM Emulsifier /g Dispersant /g Alumina Dispersant /g Binder /g scaffolds was evaluated using mercury porosimetry (Poremaster33,
content/ content /g
mL
Quantachrome Instruments Trading, Co., Ltd., USA). Compressive
strength of porous ceramics was determined using cylindrical samples
0 0 0 51.9 0.519 0.519 of Φ 7 mm × 11 mm on a computer servo that controlled the material
8.5 0.51 0.085 51.9 0.519 0.519 testing machine (HT-2402-100 kN, Hungta, Taiwan) at 0.5 mm min−1.
21.25 1.275 0.213 51.9 0.519 0.519
Ten samples were tested to obtain the average value. The specific sur-
face area of porous ceramics was measured by BET surface area mea-
behavior of the ceramic slurry at low temperatures was investigated, surement (Gemini VII2390, Micromeritics Instrument Ltd., USA).
and the pore structures and mechanical properties of porous ceramics Meanwhile, the specific surface area of porous ceramics was measured
were characterized. The adsorption performance of the porous alumina using mercury intrusion porosimetry (Poremaster33, Quantachrome
was also tested. Instruments Trading Co. Ltd. Shanghai). Three samples were tested
using two methods to obtain the average value. The isoelectric point of
alumina ceramics is approximately 8.8 [26], and their surface has a
2. Experimental procedure positive charge under neutral and acidic conditions. With its porous
structure, alumina ceramics can absorb and separate titan yellow with
Alumina powder, with a median size of 1 µm (GW-1; Dengfeng two negative charges on its surface. A 10 mL titan yellow solution
Smelting Materials Co., Ltd., Zhengzhou, China), was used as starting (10 mg/L) was filtered using the porous alumina (Φ 7 mm × 16 mm) at
material. DPM (C13H12) and distilled water were used as freezing pH 2. The absorbance of the original and filtered solutions was de-
media. Sodium dodecyl benzene sulfonate (SDBS, Tianjin Tianli termined using 7600 MC UV–Vis spectrophotometer (BILON). Inter-
Chemical Reagent Co., Ltd., Tianjin, China) was used as emulsifier. ception rate was calculated using Eq. (1).
Carboxymethylcellulose (AR, Fuchen Chemical Regent, Tianjin, China)
was used as binder. Polyacrylate sodium (AR, Sinopharm Chemical A
R = ⎛1 − 1 ⎞ × 100%
⎜ ⎟

Reagent Co., Ltd., Shanghai, China) was used as dispersant to stabilize ⎝ A2 ⎠ (1)
the slurries.
where R is the interception rate, A1 is the absorbance of the filtered
The composition of 100 mL of emulsion ceramic slurries is shown in
titan yellow solution, and A2 is the absorbance of the original titan
Table 1. The emulsifier and dispersant were dissolved in distilled water
yellow solution.
and added with DPM at 50 °C. The mixture was placed on BILON-65OY-
type ultrasonic dispersion device for 30 min to obtain DPM/H2O (O/W
type) emulsion I. The dispersant and binder were dissolved in distilled 3. Results and discussion
water. The solution was added with alumina powders and balled milled
for 24 h to obtain alumina suspension II. The DPM/H2O (O/W type) DPM solidifies at 24.5 °C, possesses density close to that of water,
emulsion I was slowly added to the alumina suspension II and stirred and is insoluble in water [27]. DPM and water can form emulsion with
for 10 min to obtain emulsion ceramic slurry (solid content of 15 vol%; the emulsifier SDBS. SDBS is a non-ionic surfactant that contains two
and DPM contents of 0%, 10%, and 25% in liquid medium). The functional groups, namely, hydrophilic and lipophilic groups [28]. The
emulsion slurries were injected into the mold with bottom sealing and hydrophilic group attracts the water layer, and the lipophilic group
placed on a precooled plate at 10 °C and − 30 °C successively in a surrounds the reservoir. SDBS accumulates at the water/oil interface
freeze drier (Freezone 2.5 L Triad; Labconco, Kansas, USA). The sam- and reduces the interfacial tension and the energy for emulsion for-
ples were frozen for 3 h and dried for 24 h to remove the DPM and ice mation, resulting in the formation of a uniform and stable emulsion.
after complete solidification. The samples were sintered at 1600 °C in Fig. 1 shows that one end of SDBS is surrounded by DPM droplets in the
air for 2 h. The furnace was cooled to room temperature to obtain emulsion, and the other end is in contact with water. This structure
porous alumina. allows uniform mixing of water with DPM. Water is used as continuous
The microstructure of the solidified DPM/H2O (O/W type) emulsion phase, and DPM is used as dispersed phase to form a dispersed system.
crystals was observed through optical microscopy (SZ61, OLYMPUS, During freezing, water and DPM in the emulsion slurry were frozen.
Tokyo, Japan) by dropping the emulsion onto a glass slide and freezing. Initially, the DPM liquid beads were distributed in water. After freezing
The morphology of the porous alumina was observed by scanning at 10 °C, the liquid beads solidified into spherical solid beads, and the

Fig. 1. Schematic of diphenyl methane (DPM) in water.

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Y. Tang et al. Ceramics International 44 (2018) 1187–1192

Fig. 2. Distribution of DPM beads in slurries when


freezing: (a) schematic diagram; and (b) stereoscopic
photograph.

Fig. 3. Morphologies of porous alumina with different DPM contents in the emulsion: (a) 0%, (b) 10%, and (c) 25%. The inset images show the longitudinal section morphologies of
porous alumina.

solid content of the slurry increased. When the slurry continued to cool structure, but the lamellar spacing is reduced; numerous small pores are
to − 30 °C, ice crystals grew directionally to form parallel lamellar ice also distributed on lamellar pore walls. When the DPM content in-
crystals from the bottom to up (Fig. 2a). The crystal shapes of the DPM/ creases to 25%, the size of spherical pores on the pore wall of porous
H2O (O/W type) emulsion were observed at low temperatures (Fig. 2b). alumina increases, and numerous spherical pores are present in the
The coagulated DPM beads were distributed between the lamellar ice porous ceramics (insert image in Fig. 3c). The spherical pores are more
crystals. Spherical DPM beads were pushed to both sides of the ice evident in Fig. 3c than in Fig. 3b. Some small droplets collide and ag-
crystals due to their directional growth. The lamellar ice crystals and gregate into large droplets due to the large number of DPM droplets in
DPM beads were sublimated to form pores with double-pore structures. the emulsion. Large spherical pores were formed on the pore walls after
Porous ceramics with lamellar channels and spherical pores were ob- freeze drying. When using DPM/H2O emulsion as freezing medium, the
tained after sintering. water in the emulsion was frozen directionally to form lamellar crystals.
Fig. 1 shows the cross-section morphologies of porous alumina with DPM was set in situ to form spherical crystals. Finally, porous alumina
different DPM contents in the emulsion, and the inset shows the long- with lamellar and spherical pores was obtained after drying and sin-
itudinal section morphologies. When the DPM content is 0%, the pore tering.
shape of porous alumina is typical lamellar pore channels. No bridge The morphology of the spherical pores on the pore walls of porous
exists between the pore walls, which are compact. When the DPM alumina (with DPM content of 25%) was observed before and after
content is 10%, the pores of porous alumina retain the lamellar sintering to clarify the formation process of the spherical pores (Fig. 4).

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Y. Tang et al. Ceramics International 44 (2018) 1187–1192

Fig. 4. Morphologies of porous alumina with 25% DPM/75% water emulsion as solvents: (a) and (b) before sintering; (c) and (d) after sintering; (b) and (d) are enlarged images of the
black rectangle regions of (a) and (c), respectively.

Fig. 5 shows the pore sizes of porous alumina with different DPM
contents in the emulsion. The lamellar pore size of porous alumina is
the largest (102.7 µm) when the DPM content is 0% but gradually de-
creases to 64.9 µm with further increase in the DPM content. The DPM
droplets in the emulsion were solidified alone at 10 °C, thereby in-
creasing the solid content in the slurry and decreasing the size of the ice
crystals in subsequent freezing. In addition, the spherical pore size is
about 12.8 µm when the DPM content is 10% and increases to 35.8 µm
when the DPM content increases to 25%.
Some tiny DPM droplets moved close to each other or collided with
each other when suspension II was mixed with emulsion I, resulting in
the coalescence of the droplets [30]. In addition, the collision between
ceramic particles and DPM droplets caused demulsification in the
mixing process [31], resulting in the aggregation of emulsion droplets.
Moreover, some emulsifier molecules loosely settled on the interface,
producing weak interfacial tension; hence, the emulsion system became
Fig. 5. Pore sizes of porous alumina with different DPM contents in the emulsion. unstable and formed large spherical DPM droplets.
Fig. 6 shows the porosity of porous alumina with different DPM
contents in the emulsion. The porosity of the three groups of porous
Figs. 4b and 4d present the enlarged images of the rectangular regions
ceramics is almost the same. When the DPM content is 0%, the porosity
of Figs. 4a and 4c, respectively. After freeze drying of the emulsion
of porous alumina is approximately 71.93%. Some spherical closed
ceramic slurry, lamellar pores were formed by lamellar ice crystal
pores were formed in the ceramic wall. After adding 10% DPM in the
sublimation; moreover, the DPM beads leaved spherical pores on the
emulsion, the porosity decreases slightly to 70.22%. When the DPM
alumina walls after sublimation (Fig. 4a). In the magnified image
content is 25%, the number of spherical pores formed by DPM in-
(Fig. 4b), the ceramic wall possesses pores, and the ceramic particles
creases, and the pore size is large. The pores are distributed on the edge
are loose because they were squeezed out in the pore walls by ice so-
of the ceramic wall and combine with the lamellar pores.
lidification before sintering. After sintering, the double-pore structure
The compressive strength of porous alumina with different DPM
of porous alumina remains (Fig. 4c), but the pore wall density increases
contents in the emulsion was also tested (Fig. 7). When the DPM con-
(Fig. 4d). The alumina powders grow and remain close, forming a
tent is 10%, the lamellar spacing between the ceramic walls is shor-
connection; thus, gaspores between alumina particles are constantly
tened, thereby increasing the compressive strength. Most of pores in the
removed, and the ceramic walls become dense [29].
ceramic walls are spherical closed pores. The bearing area of the

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Y. Tang et al. Ceramics International 44 (2018) 1187–1192

distributed on the edge of ceramic wall when the DPM content increases
to 25%. The positions of such large spherical pores are easy to crack,
causing fracture at the intersection point. However, the compressive
strength data were discrete because the compressive strength of porous
ceramics is sensitive to their surface states (pore distribution, number,
etc.). The compressive strength of porous alumina with different DPM
contents in the emulsion had no evident difference; hence, the forma-
tion of spherical pores in the lamellar pore walls does not reduce their
compression strength.
Fig. 8 shows the specific surface area of porous alumina with dif-
ferent DPM contents in the emulsion. When the DPM content is 10%,
the partial spherical pores in the ceramic walls are closed pores.
Moreover, the water proportion in the emulsion slurry is low, leading to
decreased volume of the lamellar pores. As such, the specific surface
area of the porous alumina is lower than that of the sample without
DPM. However, the partial spherical pore sizes increase and become
connected with the lamellar pore channels when the DPM content in-
Fig. 6. Porosity of porous alumina with different DPM contents in the emulsion.
creases, resulting in specific surface area of 0.566 m2/g. The specific
surface area of porous ceramics was measured through mercury por-
osimetry, and its variation trend is consistent with that obtained
through BET method. Spherical pores on the lamellar pore walls not
successful to increase the specific surface area due to some closed pores.
Fig. 9 shows the interception rates of porous alumina at pH 2. The
titan yellow interception rate of the samples prepared with the regular
freezing casting method was 34.67%. The interception rate of porous
ceramics with double-pore structure fabricated through stepwise freeze
casting with water/diphenyl methane emulsion was increased to
44.16% when the DPM content was 25%. The interception rate of
porous alumina is related to its specific surface area. The spherical pore
increases the specific surface area of the lamellar pore walls, thereby
improving the adsorption performance. However, large size of lamellar
pore channels of porous alumina cannot absorb the titan yellow dye. In
water treatment, the fiber material is usually filled in the lamellar pore
channels to obtain high adsorption and filtration performance. The role
of lamellar pore walls with spherical pores will be highlighted in the
Fig. 7. Compressive strength of porous alumina with different DPM contents in the application.
emulsion.

4. Summary

DPM, which possesses density similar to that of water and insoluble


properties, was added to water and used as freezing medium to fabri-
cate porous ceramics with lamellar pore channels and spherical pores in
ceramic walls by stepwise freeze casting. Lamellar pore sizes decrease,
but the porosity does not evidently change after adding DPM to the
slurries. When the DPM content is 10%, the dispersed DPM droplets are
solidified at 10 °C and subsequently pushed into the ceramic walls when
the ice crystal is directed to grow to form spherical pores. The com-
pressive strength does not decrease (24.75 MPa). When the DPM con-
tent increases to 25%, some DPM droplets coalesce and form large
droplets. Finally, large pores were formed on the pore walls, and the
specific surface area is 0.566 m2/g; the calculated interception rate for
titan yellow was 44.16%. The porous ceramic with double-pore struc-
ture shows high specific surface area. In addition, the adsorption rate
and filtration efficiency can be improved effectively when applied in
Fig. 8. Specific surface area of porous alumina with different DPM contents in the the fields of filtration and adsorption. The properties of porous ceramics
emulsion. must be further improved, and experiments on adsorption and filtration
are currently in progress.
spherical pores is large under loading. The compression of the cavity
fluid can enhance the rigidity of porous ceramics due to the large in-
Acknowledgement
ternal surface area of spherical pores [32]. Therefore, the average value
of compressive strength is slightly improved at 24.75 MPa. Compared
The authors would like to acknowledge the support from the
with other shapes, spherical pores enhanced the strength of the porous
National Natural Science Foundation of China (No. 51572217), the
ceramic. The increase in the DPM content led to an excessive number of
National Natural Science Foundation of Shaanxi Province (No.
spherical pores, thereby reducing the stability of lamellar pore walls.
2016JQ5058) and China Postdoctoral Science Special Foundation
The spherical pore sizes of porous ceramic are large, and the part is
(2016T90937).

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