Ceramics International 44 (2018) 4538–4560

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

Review article

Fabrications and applications of low cost ceramic membrane from kaolin: A T

comprehensive review
⁎
Siti Khadijah Hubadillaha, Mohd Hafiz Dzarfan Othmana, , Takeshi Matsuuraa,b, A.F. Ismaila,
Mukhlis A. Rahmana, Zawati Harunc, Juhana Jaafara, Mikihiro Nomurad
a
Advanced Membrane Technology Research Centre (AMTEC), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia
b
Department of Chemical and Biological Engineering, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5
c
Integrated Material and Process, Advanced Materials and Manufacturing Centre (AMMC), Faculty of Mechanical and Manufacturing Engineering, Universiti Tun Hussein
Onn Malaysia, 86400 Parit Raja, Batu Pahat, Johor Darul Takzim, Malaysia
d
Department of Applied Chemistry, Shibaura Institute of Technology, 3-7-5 Toyosu, Koto-ku, Tokyo 135-8548, Japan

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

Keywords: The application of low cost ceramic membrane from kaolin has attracted much interest due to its excellent
Ceramic membrane mechanical stability, chemical and thermal resistivity and most importantly, because it is cost effective, in some
Kaolin cases, compared to polymeric membranes. The advantage of kaolin based ceramic membrane is its thermal
Pressing properties that allow sintering at much lower temperature than alumina. Although many studies have been made
Extrusion
on the application of kaolin based ceramic membranes, detailed discussions were scarcely made and the in-
Phase inversion
formation on the fabrication of ceramic membrane from kaolin is very limited. This article is aimed to make a
comprehensive review on ceramic membrane from kaolin for its fabrication methods and applications. An at-
tempt is also made to show the future direction of the R and D on the kaolin based ceramic membrane.

1. Introduction
The world is poised at the brink of a severe environmental crisis
including pollution, global warming, waste disposal, overpopulation
and natural resource depletion. Environmental pollution due to rapid
industrialization is one of the most significant problems of the last
century. As the population increases and climate changes cause more
draughts, water scarcity is becoming more of an issue. Global warming
is also a big environmental concern, which is continuing to require
significant attention. Membrane technologies are known to be “world-
wide technology” due to its cost effectiveness, simple operation and
high energy efficiency [1]. Early investigation towards this technology
began from animals such as bladders of pigs, cattle or fish, and sausage
casings made of animal gut [2]. However, this investigation could not
be continued further due to non-reproducible product. In 1907, Bech-
hold introduced nitro cellulose membranes with graded pore size [3]
and the invention has been improved by others. Impressively, by the
early 1930s, microporous collodion membranes were ready and com-
mercially available in market. During the next 30 years, this early mi-
crofiltration membrane technology was expanded to other polymers,
notably cellulose acetate, from which membrane of asymmetric
structure was fabricated using phase inversion technique by Loeb and
Sourirajan [4]. Nowadays, membranes from various polymeric mate-
rials are widely commercialized around the world. It should be men-
tioned that it was reported that the demand of pure water flux has
driven the market for crossflow membrane equipment and membranes
worldwide from $ 6.8 billion in 2005 to $ 9 billion in 2008 [5].
However, due to the nature of polymeric membranes that are not able
to endure harsh conditions such as high temperature and severe che-
mical environment, much attention has been focused towards ceramic
membrane that has superior characteristics for long life-term.
In early 1960s, ceramic membrane has first been invented for the
filtration of beer and recovery of extract [6] and gas separation [7].
Both of these applications were achieved by using porous ceramic
membranes. In general, a ceramic membrane can be divided into two
types; (i) porous ceramic membrane and (ii) dense ceramic membrane.
Porous ceramic membrane received significant attention especially to-
wards water treatment and for being used as a support material.
Usually, ceramic membrane has a multilayer structure of one or more
different ceramic materials, called an asymmetric structure [8]. They
generally have a macroporous support that provides mechanical sup-
port, one or two mesoporous intermediate layers and a microporous

⁎
Corresponding author at: Advanced Membrane Technology Research Centre (AMTEC), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310 Skudai,
Johor, Malaysia.
E-mail addresses: dzarfan@utm.my, hafiz@petroleum.utm.my (M.H.D. Othman).

https://doi.org/10.1016/j.ceramint.2017.12.215
Received 13 September 2017; Received in revised form 20 December 2017; Accepted 28 December 2017
Available online 29 December 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
S.K. Hubadillah et al. Ceramics International 44 (2018) 4538–4560

Fig. 1. Schematic diagram of asymmetrically structured ceramic membrane [8].

(dense) structure, where actual separation takes place as shown in

Fig. 1. Accordingly, several steps are involved to fabricate this kind of Fig. 2. The number of publication on ceramic membrane from kaolin. The data is based
membrane structure, which will be discussed later more in detail. on the citation database Scopus in October 2016.
As ceramic membranes are receiving much more attention nowa-
days they are often compared to polymeric membranes. One of the
main advantages of ceramic membrane is having a capability to endure
extremely aggressive environments, such as highly acidic solution.
Table 1 depicts the advantages and disadvantages of the ceramic
membrane [9].
Ceramic membrane is made from metal oxide materials and most
commonly used ceramic materials are Al2O3, TiO2, ZrO2 etc. or the
combination of those [8]. Up to now, the commercialized ceramic
membranes are manufactured from alumina [10]. This is due to its
excellent structural, chemical and thermal stabilities. However, ceramic
membrane from alumina shows a drawback of high sintering tem-
perature (up to 1500 °C) because of which a compromise between
mechanical strength and porosity should be made when the membrane
is fabricated from micron-sized alumina powder [11]. At this high
sintering temperature, a large amount of heat is required in addition to
the alumina powder that itself is known to be a high cost material, thus
making the ceramic membrane extremely expensive. In addition, when
high sintering temperature is used, the fabrication process will be
prolonged. On the other hand, the use of the ceramic membrane in Fig. 3. Chemical structure of kaolin [28].
industrial application would be possible only when the membrane price
is in a range of 500$/m2 to 1000$/m2 [12]. that it shrinks excessively. Bentonite is a clay of volcanic origin with
Hence, there has been significant emphasis toward the preparation more colloidal matters and is always used to increase plasticity in
of low cost ceramic membranes, particularly using clay as the mem- ceramic bodies.
brane material. There are many different kinds of clays on the earth Among all types of clay, kaolin has received the most significant
such as kaolin, ball clay, fire clay, sagger clay and bentonite [13]. attention because of its unique physical properties, i.e. kaolin provides
Bauxite and diaspore are also categorized as different types of clay with low plasticity and high refractory properties to the membrane [14]. In
high-alumina contents. All of these clays have different compositions addition, kaolin exhibits hydrophilic behaviour [15], which is ex-
depending on the difference in geological conditions. Kaolin is a pri- tremely desired to prepare membranes for water filtration. Thus, low
mary clay that was formed by the weathering, coarse in particle size cost kaolin membrane offers a new insight into various separation/
and non-plastic compared to other clays. Ball clay is higher in iron purification applications such as oily wastewater treatment [16], sup-
content, more plastic and finer in particle size than kaolin. The dis- port for gas separation membrane [17,18] and catalytic substrates.
advantage of ball clay to be used in ceramic membrane fabrication is According to Hedfi et al. [19], kaolin is a preferred raw material for

Table 1
Advantages and disadvantages of ceramic membrane [9].

Advantages Disadvantages

Able to resist high temperatures up to 280 °C. A special development onto modules and system Brittle. Need a very careful handling.
could reach up to 700 °C.
Excellent corrosion resistance (towards organic solvents and a wide pH range). Most ceramic membranes are in disc or tubular shape; possess low surface
Suitable for cleaning and steam sterilisation area/volume ratio.
High mechanical strength.
Able to endure in harsh condition; e.g. high acid or alkaline solution. The investment cost of ceramic membrane is very high.
Possess long life time.
High membrane flux for porous membrane.

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2. Overview of Kaolin material

Kaolin (Al2Si2O5(OH)4) can be simply defined as a type of clays

Fig. 4. FESEM image of kaolin [17].
porous ceramic membranes due to its crystal order, chemical compo-
sition and mineralogical properties. These excellent properties of kaolin
have promoted the research to develop low cost ceramic membranes
from kaolin. Fig. 2 shows the results of ‘Scopus’ search, which reveals
that the number of articles published over the last decade (2006–2016)
for ceramic kaolin membrane increased significantly.
The use of kaolin for the fabrication of ceramic membrane was first
reported in 1999 by Huang and co-workers [20] for nitrogen separa-
tion. The ceramic membrane was in disc configuration fabricated by
mixing sodium carboxymethylcellulose (CMC), water, kaolin and alu-
mina, followed by the processes of drying, milling, sieving, pressing at
400 pounds, thereby sintering at 1400 °C. In their work, many steps
were involved to produce a disc-shaped membrane, and pressing and
sintering are highly energy consuming, making the production very
expensive. A year later, Liu and Chou [21]produced disc-like kaolin by
extrusion method. Furthermore, slip casting and tape casting methods
were also adopted to make disc-like ceramic membrane from kaolin.
The extrusion process has also been applied to produce tubular ceramic
membrane from kaolin. Phase inversion technique, popular in the
fabrication of polymeric membrane, was also adopted, showing that it
is an excellent approach towards production of low cost ceramic
membrane with an asymmetric structure. The hollow fibre configura-
tion having a large surface area/volume ratio could also been produced
by combining the phase inversion technique with the sintering process.
Although there are many fabrication methods applied for the produc-
tion of low cost ceramic membrane from kaolin,only limited reports are
available on the fabrication details.
This article is a comprehensive review of kaolin as a ceramic ma-
terial, fabrication of ceramic membrane from kaolin and applications of
kaolin membranes. At the end of this review, we critically assess the
potential venues of future research aimed at the low cost production of
ceramic membranes from kaolin.
formed naturally in the earth. It is labelled as a soft clay, white in color,
earthy and formed by the silicate mineral decomposition by chemical
weathering, like feldspar [22]. The historical name of kaolin is derived
from the Chinese term ‘kauling’, named after a hill near the Jauchau Fu,
China. The term kaolin is first used in 1867 by Johnson and Blake [23].
In 1921, kaolin was first used in research to study its heating and
cooling behaviour [24]. In this study, kaolin was heated for 4 h in an
electric furnace at temperature ranging from 110 to 1400 °C. It was
found that the structure of kaolin was changed due to the heat applied,
i.e. kaolin changed to an isotropic structure at temperature above
900 °C and became granular and more refractive at temperature of
1200 and 1300 °C. Nowadays, a large amount of information on
thermal transformation of kaolin is available. An extensive review on
phase transformation of kaolinite clay was written by Chakraborty
[25]. These studies are very important because they provide informa-
tion on the structural change during the sintering process.
Fig. 3 shows the chemical structure of crystal kaolin in which 1:1
type of non-swelling dioctahedral form is shown. Gruner [26] is the first
person who reported that kaolin has alternating octahedral alumina and
tetrahedral silica sheets, the alumina sheet sitting on top of the silica
sheet. The apical oxygen atoms from the silica are shared with the
aluminium atoms of the upper layer [27]. Based on this structure, it is
called non-swelling dioctahedral form because the bonding between
two layers are by van der waals forces and strong hydrogen bonds.
Therefore, no interlayer swelling can be observed. As a result, a platy
structure of kaolin can be observed under scanning electron microscopy
(SEM) as shown in Fig. 4.
There are several methods to study the structure of kaolin, as
summarized below.
1) X-ray Fluorescence (XRF)
The first kaolin found in the world has the main constituents of
46.54% SiO2, 39.5% Al2O3 and 13.96% H2O [23]. Furthermore, it is
recommended that the total of Fe2O3 and TiO2 is below 0.90% [29], as
they are responsible for the dark color of final products after firing or
sintering. Table 2 lists the consolidated information of kaolin compo-
sitions obtained by various researchers by XRF analysis. Based on the
table, the compositions of clays are not the same. This is because the
properties of kaolin are different depending on the origin and source of
the kaolin collected. Kaolin is abundantly available in many countries
of different weather and temperature. The United States has a promi-
nent position in the world kaolin production with estimated 5.7 million
metric tons of kaolin. (Fig. 5).
2) X-ray Diffraction (XRD)
XRD is a well-known analysis for studying the crystal structure and
phase transformation of kaolin into metakaolin, spinel and mullite. The
identification of crystalline phase was made by comparing the peaks

Table 2
XRF analysis of kaolin powder.

No Chemical compositions (wt%) Refs.

SiO2 Al2O3 Fe2O3 TiO2 MgO CaO Na2O K2O LOI

1 48.40 37.00 0.25 0.002 0.05 0.31 0.13 0.46 13.4 (Sainz et al., 2000)
2 54.5 29.4 1.4 2.8 0.2 0.2 0.2 0.2 11 (Xu and Van Deventer, 2002)
3 51.52 36.9 0.96 – 0.08 0.58 – – 13 (Hubadillah et al. [31])
4 60.28 30.38 0.70 0.25 0.17 0.22 0.11 6.02 – (Ghouil et al., 2015a)

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S.K. Hubadillah et al.
Fig. 5. Kaolin producing countries.
(Source: USGS, Mineral Commodity Summary 2011).
Fig. 6. XRD analysis for kaolin [30].
Fig. 7. XRD analysis of kaolin transformation into metakaolin [31].
generated by the diffraction patterns with charts using JCPDF software
registered in the ICDD (International Centre for Diffraction Data). Fig. 6
shows the XRD pattern of kaolin powder as received [30]. This crystal
structure is transformed into amorphous metakaolin when heated at the
range of 500–925 °C as shown in Fig. 7. The amorphous structure will
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Ceramics International 44 (2018) 4538–4560
turn back into the crystal structure when the sintering temperature
more than 925 °C.
3) Thermogravimetry and differential thermal analysis (TG and DTA)
The most valuable property of kaolin, making a name in the ceramic
industry, is that it can be molded into any desired shape and then by
heating the water may be driven away and it can turn into durable
product. From the TG thermal curve (solid black line in Fig. 8) loss of
water occurs in two regions. The first desorption of water is in the range
from ambient to 110 °C. This region is necessary to avoid formation of
cracks during sintering process, i.e. clay membrane should be dried at
room temperature or at around 100 °C before the temperature is further
increased in the sintering process [32,33]. Then the sharp weight loss
occurs in a range 400–600 °C. This is due to the loss of water and de-
hydroxylation of the silicate lattice in kaolin [34]. For DTA (Fig. 8 solid
red line), two peaks are observed corresponding to endothermic and
exothermic. At 540 °C an endothermic peak appears corresponding to
the dehydroxylation, turning crystal kaolin into amorphous metakaolin
while the exothermic peak at 995 °C represents spinel crystallization.
The formation of mullite occurs at temperatures up to 1200 °C.
In 1959, Brindley and Nakahira [36] gave a well-integrated picture
of the sequence of events from the initial layer structure of kaolinite,
through a residual layer structures in metakaolin, followed by a cubic
spinel type phase and finally chain type structure in mullite as follows:
Al2 Si2 O5 (OH )4 450 °C 2 (Al2 O3 0. 2SiO2 ) + 2H2 O
Kaolin ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Metakaolin
2Al2 O3 0. 2SiO2 925 °C 2Al2 O3. SiO2 + SiO2
Metakaolin ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Spinel
2Al2 O3 0. 3SiO2 1100 °C 2 (Al2 O3 0. 3SiO2 + SiO2 );
Spinel ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Pseudomullite
2 (Al2 O3. SiO2 ) 1400 °C 3Al2 O3 0. 2SiO2 + SiO2
Pseudomullite ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Mullite + Cristobalite
The transformation from kaolinite to spinel and/or mullite also is
used to fabricate the ceramic membrane. In particular, mullite is one of
the most important candidate materials for porous ceramic membranes
due to its excellent high temperature stability, mechanical properties,
low creep rate, low thermal expansion coefficient and low thermal
conductivity [37]. Therefore, the next section will address the fabri-
cation technique in which the above phase transformation occurs.
3. Fabrication of ceramic membrane from kaolin
3.1. Slip casting
Slip casting is useful for making a complex shape that is non-con-
centric and irregular such as pottery (Fig. 9). The solution or the mix-
ture used in slip casting is often called slip or slurry. Algerian and
French call it barbotine [38]. Usually, it is a mixture of kaolin and
water. Before slip casting was introduced, traditional methods such as
throwing, jiggering, jollying and pressing were mainly used by the
ceramics manufacturer. In 1790, slip casting was first used in France by
Monsieur Tendelle in conjunction with the porcelain manufacturing. By
1814, the slip casting was introduced to Sèvres [39].
Mohammadi and Pak [41] was the first to report the fabrication of
ceramic membrane from kaolin using slip casting combined with elec-
trophoretic method. They focused on preparing a kaolin support for
zeolite NaA membranes with better consistency. The kaolin used in the
study was obtained from the Zenooz mine in Marand, Iran, with
58.62 wt% SiO2and 28.8 wt% Al2O3 after wash. The slurry was pre-
pared by adding 400 g of kaolin and 400 cm3 distilled water. In order to
reduce the viscosity, they added 1.3 g of commercial tripolyphosphate
and obtained a desired slurry density of 1.5 g/cm3, which was crucial to
prevent the slurry from being stuck to the mould. Then, the slurry was
poured into the space between anode and cathode shown in Fig. 10.
Since kaolin is charged negatively it moves toward anode and deposits
S.K. Hubadillah et al.
on it. Voltage and current used in electrophoresis was 10 V and 0.25 A,
respectively. Lastly, the tubular ceramic membrane was sintered at 800,
900, 1050 and 1200 °C for 3 h. As shown in Fig. 11, membrane porosity
increased with an increase in sintering temperature, resulting in turn
increased flux. However, the separation factor for this membrane is low
due to the large pore size, thus it is recommended for the membrane
support.
In 2007, Zyryanov and Karakchiev [43] initiated the advanced ap-
plication of low cost ceramic membrane from kaolin towards catalytic
membrane reactors (CMRs) and solid oxide fuel cells (SOFCs). In their
study, the membranes were characterized in terms of shrinkage, XRD
analysis and porosity. Kaolin used in this study was obtained from
various locations in Ukraine and Russia. The slip casting method was
used to fabricate thin-walled tubes with a closed-end with addition of
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Ceramics International 44 (2018) 4538–4560
Fig. 8. TG and DTA analysis of kaolin [35].
Fig. 9. The principle of slip casting [40].
Fig. 10. Electrophoretic deposition (EPD) setup [42].
sodium carbonate and liquid glass (electrolyte additions) in the slurry
which was cast into gypsum molds. The slurry was also sonicated at
44 kHz using a UZDN ultrasonic processor and aged at temperatures
ranging from 30 to 40 °C for 1–4 weeks, followed by degassing in va-
cuum to improve the viscosity of the slurry and enhance the strength of
green bodies. They have found that the optimum sintering temperature
was 1380 °C to obtain porosities more than 34%. Shrinkage mismatch
between the supports and ceramics were reduced to an acceptable level.
They also concluded that slip casting method was an attractive casting
process for producing porous ceramic supports of complicated shape for
CMRs and SOFCs.
Later, Zyryanov [44] extended the previous study to develop mul-
tilayer mixed conducting oxide membranes. The same kaolin material
and slip casting method were used with some modification; i.e. The
S.K. Hubadillah et al. Ceramics International 44 (2018) 4538–4560

Fig. 11. SEM images of (1) cross section and (2) surface morphologies of ceramic membrane prepared from kaolin using electropholetic method at different sintering temperature; (A)
900 °C, (B) 1050 °C, and (C) 1200 °C.

to compare slip casting and pressing method. Kaolin used in the study
Table 3 was taken from Balikesir-Sindirgi region and it was alunitic type, con-
Sample coded [46].
taining SO3 content of 4–13.5%. This kaolin has never been used in the
Obtained from Coded as
ceramic industry due to the disadvantage of producing membranes with
very high porosity and fragileness by sintering process. Therefore, they
Supports comminuted by a ball mill investigated three different types of slurries; (1) having highest alunite
and formed through slip casting content, (2) having lower alunite content compared to slurry (1), and
K1 kaolin SB1
K2 kaolin SB2
(3) with no alunite. They also classified the membranes according to the
K3 kaolin SB3 membrane fabrication method as shown in Table 3. As a result, ceramic
Supports comminuted by a jet mill membranes with the highest alunite content had the highest porosity.
and formed through slip casting Membrane PBIK-1000 and SB1-1100 which sintered at 1000 °C and
K1 kaolin SJ1
1100 °C had the porosity of 45.67% and 49.75%, respectively (Fig. 12).
K2 kaolin SJ2
K3 kaolin SJ3 Besides it was also revealed that pressing method was easier to handle
Supports comminuted by a ball mill the shrinkage problem than slip casting. As well, pressing method could
and formed through dry pressing produce membranes of higher mechanical strength.
K1 kaolin PB1K
K2 kaolin PB2K
K3 kaolin PB3K 3.2. Tape casting
Supports comminuted by a ball mill
and formed through dry pressing Tape casting is a fabrication technique to produce thin ceramic
K1 kaolin PJ1K
sheets from ceramic slurry that casted in a thin layer onto a flat surface,
K2 kaolin PJ2K
K3 kaolin PJ3K and then dried and sintered. This technique is a well-known technique
for ceramic membrane production. Tape casting was introduced by
Glen N. Howatt in the mid-1940s during the Second World War for
slurry was prepared by adding sodium electrolytes, 20–50% of micro- production of thin piezoelectric materials [47]. In 1947, Howatt [48]
crystal cellulose (MCC) and 1–10% Al(OH)3 powder to increase the published his first paper on fabrication of thin ceramic sheets for ca-
porosity and enhance the thermal stability. The membrane was used for pacitors. The slurry was prepared by mixture of staybelite, albalyn,
partial oxidation of methane (POM) application. However, the pre- ethocel type 50, toluol, V-495 resin, diethyl oxalate and TiO2. The
liminary results were not satisfactory since partial oxidation reaction slurry was tape cast through a 325-mesh screen as shown in Fig. 13. In
did not take place satisfactorily. This might be due to the difficulty in 1952, this method was patented in US for producing high-dielectric
controlling the membrane thickness by the slip casting method [8]. high-insulation ceramic plates [49]. Consequently, the invention of
Seven years after Zyryanov’ work, the slip casting method was re- Howatt has been further developed, which made an impact on the
explored. In 2014, Alfiyan and Susanto [45] used slip casting method to ceramic industry.
fabricate ceramic support with excellent mechanical strength. In their In 1961, a modern tape casting was introduced based on Park's
work membranes were fabricated by changing the fly ash content while patent [50] and it has been used up until now. The tape casting was
kaolin concentration was maintained at 30 wt%. They could produce a modified and combined with the doctor blade as shown in Fig. 14. This
dense ceramic membrane by this way. tape casting method was also called as green tape casting. It is a thermal
Most recently, a study was conducted by Ediz and co-workers [46] forming process well suited for fabrication of mesoscale devices. The

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Fig. 12. SEM images of the membrane with highest porosity; (A) SB1-1100 and (B) PB1K-1100, at different magnification; (1) 150× and (2) 5000× [46].

following steps are involved: (1) preparation of ceramic slurry with

A) appropriate viscosity, (2) tape casting and (3) sintering. A ceramic
slurry in aqueous or solvent-base was continuously dispensed onto a
moving substrate from a hopper or other suitable plumbing. It was
critical to make sure that the viscosity of the slurry was in the range of
100–130 Poise (10−1 Ns/m2). The slurry was moved under the doctor
blade that could be adjusted into desired thickness as shown in Fig. 15.
Then, the cast film was dried in an oven. The advantage of tape casting
is that the ceramic sheet can be cut into a desired shape, whether it is in
circular, square or rectangular.
In 2008, Nandi and co-workers [53] published a work on tape
B) casting. In their work, the slurry composition was 40 wt% kaolin,15 wt
A. Belt % quartz, 25 wt% calcium carbonate, 10 wt% sodium carbonate, and
B. Gear and belt drive 5 wt% boric acid and sodium metasilicate. Each component had its own
C. Extruding hopper function. Kaolin provides low plasticity and high refractory to the
D. Adjustable supports membrane, quartz contributes to mechanical and thermal stability,
E. Springs calcium carbonate acts as forming agent while sodium carbonate and
F. Drying oven boric acid act as colloidal agents to improve homogeneity of the slurry.
G. Staonary bar The usefulness of these properties have been mentioned in many lit-
H. Rolls eratures [14,19]. To fabricate the low cost ceramic membrane from
kaolin using tape casting, they used gypsum in the shape of a circular
compact disc with 55 mm diameter and 5 mm thickness or rectangular
shape with desired shape. For the case of circular shape, a SS316 ring
was used to control the shape and thickness of the membrane's pre-
cursor. Here, SS316 ring is a 3 by 10 mm round ring that made by
stainless steel. The slurry was tape casted using a casting knife on the
ring. After that, they carefully removed the ring and consequently ap-
Fig. 13. Howatt's first tape casting system. plied a pressure of 2 kg at 24 h. Lastly, the precursor was subjected to
two different heating sequence as follows:

i) Dried at room temperature for 24 h → Dried at 100 °C in hot air oven

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S.K. Hubadillah et al.
Fig. 14. Schematic diagram of tape casting process using a doctor blade [51].
Fig. 15. Schematic diagram for precision tape casting doctor blade [52].
Fig. 16. SEM image of composite membrane before coating [55].
(low heating rate), followed by heating at 250 °C.
ii) Sintering at 850 °C, 900 °C, 950 °C and 1000 °C with heating rate of
2 °C/min and holding time of 5 h.
Nandi et al. dip-coated their low cost ceramic membrane (ca130$/
m2) with a thin layer of cellulose acetate. Figs. 16 and 17 present SEM
images of top surface membrane before and after coating, respectively.
Interestingly, results of the membrane filtration showed that the com-
posite membranes could be used for microfiltration or ultrafiltration
depending on their pore sizes. Fouling of the cellulose acetate/ceramic
composite membrane was also studied for treatment of oily-wastewater
[54] and it was concluded that the flux decline of the membrane was
caused by cake formation.
Jana et al. fabricated ceramic membranes of different pore sizes
from kaolin by changing the amount of kaolin in the slurry and
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Ceramics International 44 (2018) 4538–4560
sintering at different temperatures (850 °C, 900 °C, 950 °C and 1000 °C)
[56]. The tape casting method was the same as that reported by Naidi
et al. but this time a dice made of perspex sheet was used instead of
SS316 ring. Perspex is a solid transparent plastic made of polymethyl
methacrylate. Through this, the thickness of ceramic membrane can be
controlled easily due to is transparent properties. It was found that the
pore size as well as permeability and flexural strength increased while
the porosity decreased with increasing sintering temperature. Most
importantly, the membrane made from the slurry with 18 wt% kaolin
showed the highest mechanical strength. The higher the kaolin content
the better was the membrane due to kaolin's low plasticity. Fig. 18
shows the SEM image of ceramic membrane as the effect of sintering
temperature. A careful observation revealed that the porous structure of
ceramic membrane is highly dependent on sintering temperature.
Mittal et al. also fabricated low cost hydrophilic ceramic-polymeric
composite membranes for treatment of oily wastewater [14]. The
support ceramic membrane was made by tape casting using a slurry
containing 23.08 wt% of kaolin. They found that the membrane was
low cost, hydrophilic and effective for oily-wastewater treatment. Jana
et al. also reported the use of the ceramic membrane support for re-
moval of mercury and arsenic [57].
The main drawback of tape casting is however imprecision in shape
that is caused by corrosion of the plaster mould. Moreover, tape casting
takes a very long time when a slurry with fine powders is cast. An at-
tempt was made to overcome the problem by pressing, but, this also
increases the processing cost. Another attempt was to use two types of
carbonate (calcium and sodium) in different amounts for pore forming
agents. Kaur et al. found that the optimum calcium carbonate and so-
dium carbonate concentration were not more than 20 wt% and not
more than 10 wt%, respectively [58]. Another attempt was to mix ac-
tivated carbon in a slurry containing kaolin, quartz, feldspar, boric acid,
sodium metasilicate, titanium dioxide and water. Activated carbon was
used to enhance porosity during the sintering process [59].
3.3. Pressing method
Pressing method is a well-known forming method used in ceramic
industry. In addition, it is known to be the simplest fabrication process
for ceramic-based product as no slurry preparation is needed. Selected
powders with calculated weight will be discharged into the non-flexible
steel or tungsten carbide, thus, pressed with desired pressure. In 1930s,
Westman made three publications on the pressing method [60–62]. In
1971 Hirata and Higashiyama prepared ceramic membranes with a
diameter of 15 mm and a thickness of 2–3 mm, by mixing desired
amounts of lead, silver and copper (I) sulphide with kaolin and pressing
at pressure of 0.1 MPa [63]. They have also used cadmium, silver and
copper (I) sulphides [64] as the additives and pressing was conducted at
lower pressure than before. In addition, hot pressing method at tem-
perature of 200–500 °C was also used. All membranes were used as ion
selective membranes.
In 1999, an article published by a group of researchers from
National Tsing-Hua University, Taiwan have introduced pressing
method towards ceramic membrane fabrication from kaolin [20].
Huang et al. fabricated kaolin membrane by pressing the slurry of
kaolin, CMC (binder), water and alumina at 4000 pounds for 2 min,
followed by sintering at 1400 °C. The ceramic membrane's outer dia-
meter and thickness were 38 mm and 1.6 mm, respectively. Antsiferoz
and Gilev prepared membranes using sialon, which was synthesized
from silica and alumina obtained from kaolin [65]. The membrane was
pressed using a steel mould at pressures from 25 to 200 MPa. A highly
porous ceramic membrane with an average porosity of ~60% was
successfully prepared.
Comparing to slip and tape casting, pressing method received
more attention for the fabrication of ceramic membrane from
S.K. Hubadillah et al. Ceramics International 44 (2018) 4538–4560

Fig. 17. SEM images of composite membrane after coating under different conditions [55].

kaolin. Most recently, Nomura et al. made a number of publications
on the adsorption membrane prepared by the pressing method [66].
Table 4 summarizes kaolin membranes fabricated by the pressing
method.
3.4. Extrusion
Extrusion is another well-known fabrication method for ceramic
membrane, basically for tubular configuration. Instead of injection
mould, extrusion is performed by the die at its exhaust. Extrusion was
first invented in 1619 by John Etherington for brick production. The

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S.K. Hubadillah et al. Ceramics International 44 (2018) 4538–4560

Fig. 18. SEM images of membrane morphology at different composition and sintering temperature [56].

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 Table 4
Ceramic Membrane from kaolin prepared by pressing method.

No Year Material (powder) Information on slurry preparation with kaolin material Pressing Pressure Sintering Highest porosity Highest mechanical Ref.
(MPa) temperature (°C) (%) strength (MPa)
S.K. Hubadillah et al.

1 1999 Kaolin, CMC, alumina The slurry containing kaolin, CMC, alumina and water was 400 pounds 1400 – – (Huang et al. [20])
mixed, dried, milled, sieved and pressed.
2 2006 Kaolin (domestic), dolomite The slurry was prepared by mixing kaolin and 15 wt.5 75 1000–1300 41.94 (1000 °C) 15 (1200 and (Bouzerara et al., 2006)
dolomite powders and wet milling. Before pressed, the slurry 1250 °C)
was dried.
3 2008 Kaolin, Al(OH)3 The powders were milled together and AlF3 was mixed 8 1300–1550 55 (72.5 wt% Al2O3 65 (60 wt%, 1550 °C) (Chen et al., 2008)
together as additive. In this study, the Al2O3 was varied from 1300 °C)
50 to 72.5 wt%, derived from industrial Al(OH)3.
4 2009 Kaolin, magnesium carbinate The powders were milled with ethanol as a liquid medium, 200 1300–1600 36 (5/100, 1400 °C) 25.84 (10/100, (Dong et al., 2009)
referred to as KM. 20 wt% from this KM solution was mixed 1600°C)
with the coarse mullite-corundum powder (M). There are
five different slurries at different ratio KM/M: 0/100, 5/100,
10/100, 15/100 and 20/100. The pressing method used in
this study was cold pressing.
5 2011 Kaolin, quartz, calcium carbonate, The composition for slurry preparation is 40 wt% kaolin, 50 900–1000 40 (900 °C) 32 (1000 °C) (Vasanth et al., 2011b)
sodium carbonate, boric acid, sodium 15 wt% quartz, 25 wt% calcium carbonate, 10 wt% sodium
metasilicate carbonate, 5 wt% boric acid and 5 wt% sodium metasilicate.
All these powders were ball milled at 40 rpm prior to
fabrication process via pressing method.
6 2011 Kaolin Kaolin used in this study was collected in India. The slurry 50 850–1000 46 (900 °C) 30 (1000 °C) (Monash and
was prepared dry and subjected directly to pressing method Pugazhenthi, 2011a)
after ball milling with PVA at 40 rpm.
7 2011 Kaolin, ball clay, feldspar, pyrophyllite, All the powders were mixed with 4 ml of 2 wt% PVA solution 50 950 45 (I) 28 (I) (Monash and
quartz in a ball mill to produce circular disk shaped membrane. The 38 (3 G) 31 (3 G) Pugazhenthi, 2011b)

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slurries prepared were divided into three and labelled as 37 (6 G) 33 (6 G)
membrane I, 3 G and 6 G. The difference was the content of
calcium carbonate and titanium dioxide in the slurries.
8 2011 Kaolin, quartz, calcium carbonate 50 g of kaolin, 25 g of quartz and 25 g of calcium carbonate 50 900–1000 30 (900 °C) 46 (1000 °C) (Vasanth et al., 2011a)
were ball milled at 40 rpm for 20 min. Prior to the pressing
method, the mixture was sieved using 30 mesh standard
screen.
9 2012 Kaolin, quartz, calcium carbonate Prior to the pressing method, all of the powders were ball 50 900 °C 30% 34 (Vasanth et al., 2012)
milled at 40 rpm for 20 min and sieved. No water or binder
was used.
10 2013 Kaolin The slurry was prepared by mixing kaolin as main 71 1100 °C 37.88% (1100 °C) 15 (Sahnoun and Baklouti
component, orthophosphoric acid as binder and corn starch [84])
as porosity agent. After that, the slurry was matured for 48 h,
dried at 150 °C, ground and sieved. Then, the powder was
pressed.
11 2013 Kaolin, diatomite The main component in this study is diatomite. Effect of 18.7 900–1200 – 60 (15 wt% kaolin, (Ha et al., 2013)
kaolin content was studied by changing the content from 0 to 1200 °C)
100 wt% on the mechanical strength of diatomite
membrane. The slurry preparation took place by adding
diatomite, kaolin and distilled water in the ball mill. PEG
was used as binder.
12 2013 Kaolin, quartz, calcium carbonate, The slurry preparation and fabrication method were adapted 50 900–1000 38 (1000 °C, 17.25 (1000 °C, (Emani et al., 2013)
sodium carbonate, boric acid, sodium from previous work by Vasanth et al. (Vasanth et al., 2011b). Membrane A) Membrane C)
metasilicate 4 mL of 2 wt% PVA was added into the slurry and sieved
prior to fabrication method.
13 2013 Kaolin, talc, alumina W40 All powders were mixed directly in dry slurry and milled for Not report 1460 and 1510 33 (1460 °C, 20 wt% 153.6 (1510 °C, 8 wt (Chang et al., 2013)
2 h. Then, the powders were mixed with PVA solution and kaolin) % kaolin)
dried in oven at 50 °C.
(continued on next page)
Ceramics International 44 (2018) 4538–4560
 Table 4 (continued)

No Year Material (powder) Information on slurry preparation with kaolin material Pressing Pressure Sintering Highest porosity Highest mechanical Ref.
(MPa) temperature (°C) (%) strength (MPa)

14 2013 Kaolin, sawdust, feldspar The compositions were selected on try and error and 9.81 550, 700, 850 14–34 2 (850 °C) (Bose and Das, 2013)
S.K. Hubadillah et al.

reported in the manuscript. All powders were ball milled

prior to pressingusing a press50 mm outer diameter and
height.
15 2013 Kaolin, alumina, starch The powders were mixed with appropriate composition to 39.2 1400 – – (Martí-Calatayud et al.,
produce appropriate slurry for pressing. Different starch 2013)
contents were added into slurry for studying the effect of
pore agent.
16 2014 Kaolin, quartz, calcium carbonate, 40 wt% kaolin, 15 wt% quartz, 25 wt% calcium carbonate, 25 (PM1), 39 (PM2), 900 37 (PM1) – (Emani et al., 2014b)
sodium carbonate, boric acid, sodium 10 wt% sodium carbonate, 5 wt% boric acid and 5 wt% 73 (PM3)
metasilicate sodium metasilicate were used for slurry preparation.
17 2014 Kaolin, quartz, calcium carbonate, 40 wt% kaolin, 15 wt% quartz, 25 wt% calcium carbonate, 25 (M1), 39 (M2), 73 900 37.4 (M3) – (Emani et al., 2014a)
sodium carbonate, boric acid, sodium 10 wt% sodium carbonate, 5 wt% boric acid and 5 wt% (M3)
metasilicate sodium metasilicate were used for slurry preparation.
18 2014 Kaolin, α-Al2O3 The slurry was prepared by mixing α-Al2O3 with different 70 1450–1525 20 (4.2 wt% kaolin, 180 (8.4 wt% kaolin, (Donelson et al., 2014)
kaolin contents (4.2, 8.4, and 12.6 wt%), deionized water, 1450 °C) 1525 °C)
pre-dissolved binder mixture, PVA and PEG 300. All the
materials were ball milled and partially dried at 40 °C. Prior
to pressing process, the slurry was re-dried overnight at
40 °C.
19 2014 Kaolin (Algerian halloysite, DD3), Kaolin used in this study was halloysite type, having hallow 75 1100–1250 45.6 (1100 °C) 67 (1100 °C) (Harabi et al., [85])
calcium carbonate nano-rodes shape. In the work, two methods have been used
for comparison; pressing and extrusion method. For pressing,
the slurry was prepared by wet milling the kaolin with 15 wt
% calcium carbonate, drying and pressing.

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20 2014 Kaolin The powder was pressed without any addition of water and Randomly 950 30.4 57 (Hedfi et al. [19])
additives. (best pressure was
reported at 19 and
26 MPa)
21 2014 Kaolin, α-Al2O3, titanium dioxide, The main component in this work was α-Al2O3. Kaolin was 80 1200–1300 °C 50 (1300 °C) 20 (1300 °C) (Liao et al., 2014)
carbon powder used as sintering aid together with titanium dioxide. Porosity
agent was carbon powder, and PVA as adhesive. The slurry
was prepared by mixing all the ingredients with appropriate
amounts of water in agate mortar, ball milling, drying and
sieving.
22 2014 Kaolin, bentonite, talc, sodium borate All powders were pressed without any addition of additives. 1000 °C 34% 28 (Lee et al., 2014)
23 2015 Kaolin, bentonite, talc, sodium borate, In the work, the main components were kaolin, bentonite, 50 1000 °C 34.4% 53 (Lee et al., 2015)
magnesium carbonate, calcium and talc. Sodium borate, magnesium carbonate, calcium
carbonate, strontium carbonate carbonate and strontium carbonate were used to increase the
mechanical strength of membrane. PEG was also added as
binder. The slurry was prepared by mixing all the powders
with distilled water and milling in polypropylene jar for
24 h. The slurry was dried at 100 °C for 24 h before being
pressed.
24 2015 Kaolin, talc, α-Al2O3, silica, For slurry preparation, 55 wt% of kaolin and 45 wt% of 70 1400 40 – (Krivoshapkina et al.,
microcrystalline cellulose microcrystalline cellulose were milled. PVA was added and 2015)
acted as binder.
25 2015 Kaolin, lignite The membrane prepared was pressured at different 23 950 46 57 (Hedfi et al., 2015)
compositions of kaolin and lignite.
(continued on next page)
Ceramics International 44 (2018) 4538–4560
 Table 4 (continued)

No Year Material (powder) Information on slurry preparation with kaolin material Pressing Pressure Sintering Highest porosity Highest mechanical Ref.
(MPa) temperature (°C) (%) strength (MPa)

26 2015 Kaolin, quartz, calcium carbonate, In this study, there are three slurries prepared and labelled as 49 900 40 (CM1) – (Kaniganti et al., 2015)
S.K. Hubadillah et al.

sodium carbonate, boric acid, sodium CM1, CM2 and CM3. For CM1 and CM2, all powders were
metasilicate, PVA dry sieved with 425 µm and 212 µm prior to pressing. For
CM3, sieving step was not performed. All the slurries were
ball milled. The pressing was performed using a hydraulic
press.
27 2015 Kaolin, α-Al2O3, industrial Al(OH)3, AlF3 All the materials were ball milled. There are two types of 8 1300–1550 36 (Kaolin) – (Chen et al., 2015)
slurries; kaolin only and mixture of kaolin, α-Al2O3, 50 (Kaolin, α-Al2O3,
industrial Al(OH)3. AlF3 was used as additive. The powder industrial Al(OH)3)
were ball milled for 12 h. Binders and lubricant were added
prior to the pressing process.
28 2015 Kaolin (alunitic type) The ceramic membrane preparation was compared within 8.83 900–1300 45.67 (ball milled, 38.89 (jet milled, (Ediz et al., [46])
two different fabrication methods; slip casting and dry 1000 °C, K1 kaolin) 1200 °C, K1 kaolin)
pressing. For pressing method, the slurry was prepared by
ball milling and sieving. There are three types of kaolin
labelled as K1, K2 and K3. Instead of different types of
fabrication method, different type of mills were used (ball
mill and jet mill). Water and PVA were also mixed into the
slurry. Prior to the pressing process, the slurry was dried.
29 2015 Kaolin, commercial diatomite, bentonite, The slurry was prepared using 48.6 wt% diatomite, 18.8 wt 50 1000–1100 34.1 (1100 °C) 32.2 (1000 °C) (Eom et al., 2015)
talc, sodium borate, barium carbonate % kaolin, 14.8 wt% bentonite, 14.8 wt% talc, 2 wt% sodium
borate, 1 wt% barium carbonate and distilled water. The
slurry was milled and PEG was used as binder.
30 2015 Kaolin, alumina There are seven slurries prepared with different starch 39.2 1100 and 1400 70 (1100 °C) – (Lorente-Ayza et al.,
contents (0–30 wt%). Starch was used as porosity agent. The 2015)

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ratio of alumina and kaolin was 50:50. The slurry was
prepared by milling all powders with acetone in ball mill.
31 2015 Kaolin, activated carbon, calcium In this study, there are several steps. First is the preparation 6.89 1400 26.3 (5 wt% – (Khumbudda et al.,
carbonate of cristobalite from rice husk. Second is the preparation of activated carbon) 2015)
ceramic membrane support from kaolin. The support was
prepared using pressing method. For slurry preparation,
85–87.5 wt% kaolin, 10 wt% cristobalite, 2.5 wt% activated
carbon and 5 wt% calcium carbonate was mixed with
deionized water, heated, stirred and evaporated. Then, the
slurry was pressed into disc shape. Lastly, the ceramic disc
was transformed into ANA zeolite by synthesizing process in
autoclave aging.
32 2015 Kaolin, limestone, potassic feldspar, Three slurries were prepared with different compositions and 25 1100 (F1) – 6.8 (F1) (Simão et al., 2015)
albite, quartz, white clay labelled as F1, F2 and F3. Fi consists of 25 wt% kaolin while 1180 (F2, F3) 18.2 (F2)
F2 and F3 consist of 50 wt% kaolin. Powders were milled 29.5 (F3)
with water for 5 h, sieved, dried and disaggregated.
33 2015 Kaolin, alumina, starch 40 wt% kaolin, 40 wt% alumina and 20 wt% starch were 39.2 1400 – – (Marti-Calatayud et al.,
milled with distilled water for slurry preparation. Then, the 2015)
slurry was dried under IR lamps, moisturized with PVA
solution as binder.
34 2016 Kaolin, commercial bauxite Transformation of mullite from kaolin and bauxite based on 200 1300–1600°C (2 h) 32% (1500 °C) 125 (1600°C) (Zhu et al., 2016)
the chemical composition of mullite (3Al2O3.2SiO2). The
powder was ball milled with alcohol using zirconia ball. The
ratio is 1:3:2 = powder: zirconia ball: alcohol. After that, the
slurry was dried at 100 °C for 3 h. The slurry was mixed with
PVA to avoid cracking during pressing process.
35 2016 Kaolin, alumina Kaolin was mixed with alumina at different ratios in a range 66 1250 °C 28% (1250 °C) 14 MPa (Issaoui et al., 2016)
of 4 to 16 wt%. The mixture was mixed without any addition
of water.
(continued on next page)
Ceramics International 44 (2018) 4538–4560
S.K. Hubadillah et al. Ceramics International 44 (2018) 4538–4560

Ref. first extrusion machine was a hand-operated piston extruder as illu-

strated in Fig. 19. In 1807, the invention was further used by Hosten-
(Hedfi et al., 2016)
berg of Petersburg as a fabrication tool for drainage pipes production
known as drainpipe extruder [67]. Nowadays, extrusion machine is
designed to be automatic, combined the mixing and extrusion process
known as “pugmill mixer”. Fig. 20 shows an example of pugmill mixer
(Brand: NVS-07; Shimpo, USA). This pugmill mixer is equipped with a
variety of die shapes that are compatible to the machine to enable to
Highest mechanical

form desired ceramic membrane module. Moreover, the machine comes

together with clay cutter and roller shelf. The access for cleaning and
strength (MPa)

38 (1200 °C)

maintenance is very satisfying.

Two types of extruders known as screw and plunger are schemati-
cally shown in Fig. 21. Plunger extruder offers the advantage of a
smaller chance of contamination due to wear [68]. However, a sig-
nificant pressure loss can occur in the cylinder, thus, affecting the
Highest porosity

nozzle pressure. For screw extruder, the ram pressure and nozzle
pressure are about the same. Slurry preparation for the extrusion pro-
41 (1100 °C)

cess is completely different from the pressing process. In extrusion, the

moisture content of the slurry is higher than 15% anddepending on the
(%)

material, it can reach as high as 20–22%. There are five steps involved
in ceramic extrusion process as shown below [69]:
temperature (°C)

Blending → Pugging → Extrusion → Cutting and Drying → Sintering

1100, 1150 and

During blending, the moisture content of the slurry is controlled by

Sintering

1200 °C

mixing the powders with suitable binder, surfactant, deflocculant,

coagulant, lubricant, plasticizer and preservatives. For lubricants, there
are many common lubricants used like stearates, silicones, petroleum
oil, and colloidal talc.
Pressing Pressure

The first demonstration of the extrusion method used for ceramic

membrane from kaolin was reported in 2005 [70]. This study was fo-
cused on the preparation of mullite ceramic membrane with high
(MPa)

strength and porosity from kaolin by sintering process. Kaolin used in

23

this study was obtained from WBB cooperation with average particle
size of ~40 µm. The main components of the kaolin were silica and
The powder was pressed without any addition of water and
Information on slurry preparation with kaolin material

alumina with percentage of 51.9% and 34.1%, respectively. Prior to the

slurry preparation, the powder mixture consisting of alumina, sodium
carbonate and kaolin was crashed in dry stage, followed by four times
sieving by 60 mesh for homogenization. Then, the slurry was prepared
in the blending step by combining the homogenized powder with
25–35% of distilled water. In comparison to the slurry in pressing
method, the distilled water content used for extrusion was high so that
the moisture could be controlled at an average of 20% as required to
prevent the slurry from sticking to die, disturbing the shape of extruded
slurry.
Asghari continued the investigations [71] using two different grades
of kaolin to produce tubular ceramic membranes, which were further
used as a support for thin-layer mordenite zeolite. In their study, the
additives
Kaolin, lignite, alumina
Material (powder)
Table 4 (continued)

2016
Year
No

36

Fig. 19. First extrusion machine [67].

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S.K. Hubadillah et al. Ceramics International 44 (2018) 4538–4560

Fig. 20. Pugmill mixer with various types of die.

(Source: shimpoceramics.com).

Fig. 21. Diagram for extruder type, (a) screw (extruder) and (b) plunger (piston).

Fig. 22. SEM images of surface morphology ceramic membrane (A) before and (B) after layering with mordenite zeolite [71].

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S.K. Hubadillah et al. Ceramics International 44 (2018) 4538–4560

Fig. 23. SEM images of (a) Taxenna kaolin halloysite and (b) Tamazert kaolin type.

slurry was prepared by combining kaolin powders with 16.8% of
deionized water. The slurry was then extruded through die in dimen-
sion of 11 mm inner diameter and 15 mm outer diameter, dried and
sintered at 1250 °C for 2.5 h, by which kaolin was transformed to
mullite. The tubular membrane was further processed by coating thin
mordenite zeolite layer through hydrothermal process. The membrane
was further treated by strong alkaline solution to remove free silica.
Fig. 22 shows the SEM surface images before and after layering with
mordenite zeolite.
The extrusion method seems to be favoured for ceramic membrane
production from kaolin in tubular configuration which has higher area
per volume ratio compared to flat, planar and disc configured mem-
branes. For this reason, more than 20 publications have been made
after the first invention in 2005. Table 5 summarizes the publications
on ceramic membrane fabrication from kaolin via the extrusion
method, depicted from ‘Scopus’ search in October 2016. From the table,
simple mixing of kaolin and distilled water has been widely employed
for slurry preparation, while methocel and amijel were sometimes
mixed into the slurry as dispersant to improve the rheological proper-
ties. It is interesting to mention that the sintering temperature is in the
range of 800–1250 °C except for the case when alumina is added in the
slurry, for which sintering temperature as high as 1600 °C is required. It
is therefore clearly proved that kaolin is not only cheap in terms of
material, but may also reduce the cost of fabrication step using extru-
sion technique. However, this technique can be employed to produce
ceramic membrane of a symmetric shape. As well, an additional layer
needs to be deposited on the surface of this tubular membrane to make
it useful for the separation purposes. This method is therefore very time
consuming.
coagulation bath. As a result, an excellent osmotic membrane was
fabricated with flux of 5–11 gallons of 0.05% NaCl water per sq. foot
per day from a saline brine containing 5.25% NaCl, under operating
pressure of 1500–2000 psig, through a small desalination cell as shown
in Fig. 25. Nowadays, phase inversion is a well-known fabrication
technique for producing high flux membranes.
The early development of phase inversion-ceramic membrane was
reported by Luyten and co-workers [74] for the preparation of LaSr-
CoFeO3−x membranes to produce cost-effective oxygen. The ceramic
membrane was prepared in hollow fibre configuration to develop
membranes modules with a higher surface/volume ratio. The phase
inversion technique for polymeric membrane was modified by pre-
paring a mixture of appropriate ceramic powders as major component
while reducing the polymer content. Polymer acted as binder in the
mixture and is burned off during sintering process. The mixture is often
called dope suspension, ceramic suspension or powder suspension. As a
typical suspension preparation method, ceramic powders with solvent
are milled for 1 day (usually ball mill is used), followed by further
mixing for more than 1 day after addition of polymer. Then, the sus-
pension is extruded through a double cylinder nozzle that is placed
close to the non-solvent bath. Nowadays, spinneret with double [75]
and triple orifice [32] are designed for single and double layer ceramic
hollow fibre membrane, respectively. Recently, quadruple orifice was

3.5. Phase inversion/sintering technique

Phase inversion can be defined as transformation of polymer solu-

tion from liquid to solid state, induced by various methods, whether by
wet and/or dry process [73]. Wet process involves the immersion
technique of the polymer solution into non-solvent coagulant bath
while dry process is performed by exposing it to a non-solvent atmo-
sphere. This method was first invented for polymeric membrane in
early sixties by Loeb and Sourirajan [4] via wet phase inversion process.
In their work, the casting dope was prepared by mixing cellulose
acetate, acetone and aqueous magnesium perchlorate. The cast flat film
of the polymer solution was directly immersed into ice-cold water as a Fig. 24. Photographic image of double screw extruder [72].

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 S.K. Hubadillah et al.

Table 5
Ceramic membrane from kaolin prepared by extrusion method.

No Year Information on slurry preparation and extrusion method Sintering temperature (°C) Ref

1 2006 To prepare the tubular ceramic membrane, 81.7 wt% kaolin, 10 wt% Amidon, 4 wt% Methocel, 4 wt% Amijel and 0.3 wt% PEG 1500 were mixed first. Then, 37.2 wt 1250 (Saffaj et al., 2006)
% of water and 0.24 wt% of Zusoplast were added and let to blend for 30 min. Prior to the extrusion process, the slurry was aged for 2 days.
2 2010 Industrial kaolin was used with dolomite in different contents in a range from 10 wt% to 30 wt%. The powders were ball milled with water and aged before extrusion 1100–1300 (Zhou et al., 2008)
process.
3 2010 Kaolin was mixed with water and tubular membrane was formed through extrusion process. The size of tubular membrane was 9 mm inner diameter, 14 mm outer 1250 (Abbasi et al., 2010b)
diameter and 30 cm length.
4 2010 Mullite-alumina membrane was synthesized from kaolin and α-alumina powder. The slurry preparation was done by mixing powders and water. Then, the slurry was 1250 (Abbasi et al., 2010a)
extruded to tubular form with ceramic's green bodies at length of 30 cm.
5 2011 Kaolin and α-alumina was used to synthesize mullite which was the main objective of this work. Analysis of kaolin showed that kaolin contains kaolinite (SiO2 and 1250 (Shokrkar et al., 2011)
TiO2), illite, quartz and feldspar. The slurry was prepared by blending the mixture of kaolin and water.
6 2011 In this work, the slurry was prepared by mixing kaolin with 28–31% of distilled water. Green bodies with 10 mm of inner diameter, 14 mm of outer diameter and 1250 (Abbasi et al., 2011)
length of 30 cm were extruded from the slurry.
7 2012 In this work, three fabrication steps were applied. A comparison study was made by fabricating ceramic membranes from kaolin using extrusion and roll pressing to 1050 (Bouzerara et al., 2012)
produce tubular and disc shape membrane, respectively. Slip casting was applied for forming a microfiltration layer on the membrane.
8 2012 Prior to the slurry preparation, kaolin DD2 type was crushed and calcined at 540 °C for 1 h and sieved. For slurry preparation, kaolin was mixed with 28 wt% of 1150 (Boudaira et al., 2012)
calcium carbonate, 3 wt% of methocel, 3 wt% of amijel and appropriate amount of water.
9 2012 The aim of this work was to prepared mullite microfiltration ceramic membrane that was synthesized from kaolin. The slurry composition was in a range of 62–69 wt 1250 (Abbasi et al., 2012)
% kaolin and 31–38 wt% distilled water. After kaolin and water was blended to form a slurry, the slurry was extruded through cylindrical die.
10 2013 In the work, industrial grade α-alumina was the main component while kaolin acted as plasticizer together with talc. A green bodies in tubular configuration were 1450 (Liu et al., 2013)

4554
formed by extrusion.
11 2014 The kaolin used in this work was obtained from Zenooz mine in Marand, Iran. Blending process took place by mixting kaolin and distilled water. 1250 (Abbasi and Mowla [37])
12 2015 In this work, waste kaolin from kaolin processing factory (CAULISA industry S/A) was blended with bentonite, water and diesel oil. After that, the slurry was 850–1000 (Chaves et al., 2015)
homogenized and extruded through extruder (vacuum extruder, Verdés model 051) using a die (VC 131 steel) to form tubular ceramic bodies. Two drying stages
were applied, (i) normal drying at room temperature and (ii) drying in oven.
13 2015 The slurry was prepared by blending 75 wt% Taxenna kaolin halloysite and Tamazert kaolin type (Fig. 23), 19 wt% calcium carbonate, 3 wt% Amijel and 3 wt% 1100–1250 (Ghouil et al., 2015a)
methocel. After all materials were blended the slurry was aged with addition of water to improve rheological properties.
14 2015 This work was aimed to prepare anorthite ceramic membrane support. Firstly, kaolin DD3 type was crushed and calcined at 520 °C, and sieved at 200 µm. Then, the 800–1100 (Guechi et al., 2015)
crushed kaolin was blended with calcium oxide, amijel, methocel and water.
15 2015 15 wt% of kaolin, 18 wt% of ball clay, 6 wt% of feldspar, 15 wt% pyrophyllite, 28 wt% quartz and 18 wt% calcium carbonate was used for slurry preparation. 950 (Vinoth Kumar et al., [83])
Appropriate amount of Millipore water was added. The slurry was extruded through piston force at velocity of 0.007 m/s.
16 2015 Kaolin and ball clay were sieved and blended in pugmill manufactured by METVISA company. Then, water and diesel oil as lubricant were added for completing 900–1100 (Silva et al., 2015)
preparation of slurry. The slurry was then extruded by extruder (Verdés, model 051).
17 2015 79 wt% of kaolin DD3, 15 wt% calcium carbonate and 3 wt% of amijel were mixed with some amount of water to have a moisture controlled slurry. A highest 1150–1300 (Harabi et al., 2015)
mechanical strength of 75 MPa was obtained at sintering temperature of 1200 °C.
18 2015 Kaolin was obtained from Sukabumi Mineral Mine, Indonesia with 66.56 wt% of silica content. Kaolin was used for about 56.08–59.25 wt% with 37.25 wt% of ball 1050 (Fatimah et al., 2015)
clay, and 2.5 wt% of sawdust. After blending with 1 l of water, the well-prepared slurry was extruded using a Brent hand extruder.
19 2015 Kaolin and diatomite were mixed using ball mill with distilled water. 15 wt% of methyl cellulose was used as binder and the slurry was aged for 2 days at room 900–1200 (Ha et al., 2015)
temperature. The slurry was extruded by a double screw extruder (KTE−50S, Kosentech, Korea). Fig. 24 shows the photographs of the double screw extruder. The
final green bodies were in the form of flat tube-type dimensions.
20 2016 In the study, three ceramic membrane supports were prepared; (i) alumina, (ii) diatomite-kaolin and (iii) pyrophyllite-diatomite. For diatomite-kaolin, the slurry was 1200–1600 (Ha et al., 2016)
prepared by mixing kaolin, methyl cellulose and distilled water. The extrusion process took place by using a double screw extruder (KTE−50S, Kosentech, Korea).
21 2016 The tubular ceramic membrane's green bodies in this work were prepared by extrusion method of a blended mixture containing clay (Kaolinite, quartz and 1150–1250 (Ghouil et al., 2015b)
muscovite), calcium carbonate, amijel and methocel.
Ceramics International 44 (2018) 4538–4560
S.K. Hubadillah et al.
Fig. 25. Small desalination cell used by Loeb and Sourirajan [4].
designed and used by Li's research group at Imperial College London
[76]. Fig. 26 shows the pictures of the spinnerets of various designs.
After spinning, the ceramic hollow fibre precursor was cut into a de-
sired length and dried at room temperature. Finally, sintering process at
temperature of 600 °C took place to burn off the polymer, and further
sintering at higher temperature (1225 °C) allowed the growth between
ceramic particles.
Finger-like and sponge-like voids are the two types of pores that are
commonly observed in cross-sectional image of ceramic membranes
prepared by the phase inversion technique. The finger-like structure is
considered as a defect formed by the agglomeration of ceramic particles
and lack of de-airing, which lowers the mechanical strength [74]. Ac-
cording to Luyten formation of the finger-like structure should be
avoided. On the other hand, the finger-like structure may be desirable
since there is less resistance for the fluid flow through the finger-like
structure than the sponge-like structure. No definite conclusions have
been achieved so far on the desirability of the finger-like structure.
Kingsbury and Li examined various parameters that affect the forma-
tion of finger-like structure in ceramic membrane [75]. The parameters
were solvent composition consisting 1-methyl-2 pyrrolidone (NMP) and
water, bore fluid flow rate, extrusion pressure, air gap and ceramic
suspension viscosity. Each parameter was found to affect the formation
of either finger-like or sponge-like structure. Among others, the increase
of the suspension viscosity reduced the finger-like structure. Hence,
they defined the threshold viscosity as the viscosity where the finger-
like turns into sponge–like structure. They have also introduced a
concept of ‘viscous fingering’ based on the well-known fluid mechanism
that occurs at the interface between fluids of different viscosities. The
phenomenon was further studied by Wang and Lai [78] by investigating
the effect of non-solvent type in the coagulant bath on the formation of
finger-like structure Distilled water, ethanol and a mixture of 1-methyl-
2 pyrrolidone (NMP) and distilled water were used as nonsolvents in
the coagulation bath.
Fig. 26. Pictures of (A) tube in-orifice [77], (B) triple-orifice [76], and (C) quadruple-orifice [76].
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Ceramics International 44 (2018) 4538–4560
The first ceramic membrane was prepared from kaolin by the phase
inversion technique by Sarbatly et al. [79]. The ceramic membranes
were prepared in flat sheet configuration for different kaolin/PESf ra-
tios in the slurry and sintering temperatures. Fig. 27 shows the cross-
sectional SEM images of the ceramic membranes for different kaolin/
PESF ratios, whereas Fig. 28 shows the cross-sectional images for dif-
ferent sintering temperatures. The pore size of the membrane was found
to decrease from 11 to 8 µm when the kaolin content in the slurry was
increased from 27.0 to 94.5 g when sintering temperature was fixed to
1400 °C. As for the effect of sintering temperature, the same trend was
observed in which the pore size of membrane decreased from 16 to
9 µm with increasing sintering temperature from 1100 to 1500 °C. This
observation was ascribed to the grain growth on the membrane surface
during sintering process.
Hubadillah et al. further studied the effect of non-solvent coagulant
bath [17] and the effect of kaolin particle size [18]. The kaolin content
used was 54.0 g kaolin which was adapted based on Sarbatly's work
[79]. Hubadillah et al. found that the viscosity of ceramic suspension
increased as the powder size decreased. According to their work, the
sponge-like structure was improved by having homogeneity when the
ceramic membrane was prepared using smaller particle size at 54.0 g
kaolin content and sintering temperature of 1200 °C, both of which are
much less than Sarbatly's work. The effect of non-solvent coagulant
bath was further studied by using distilled water, ethanol and, a mix-
ture of 1-methyl-2 pyrrolidone (NMP) and distilled water as the coa-
gulants. It was found that distilled water resulted in the best ceramic
membrane morphology, having a dense and smooth surface and a cross-
section with finger-like structure. It may be because distilled water is
the strongest non-solvent coagulant as Wang et al. pointed out [78].
However, ceramic membrane made from kaolin was not strong enough
particularly in flat sheet configuration due to its highly porous nature
and difficult to handle during operation.
Table 6 lists advantages and disadvantages of all the fabrication
methods so far discussed. Based on this comparison, it can be concluded
that the phase inversion technique is the most appealing due to its
ability to produce ceramic membranes in asymmetric structure with
unique finger-like and sponge-like structure. Moreover, the pore
structures can be controlled by adjusting the fabrication parameters
such as ceramic content, types of coagulation bath and sintering tem-
perature. This means that desired membrane structure can be obtained
easily for some certain applications. Most importantly, this technique
can be applied to produce ceramic membranes in hollow fibre config-
uration with high surface/volume ratio and with improved perfor-
mance when assembled into a membrane module.
4. Application of ceramic membranes made from kaolin
Kaolin is a low cost ceramic material that has superior character-
istics while ceramic membrane in general is workable in severe con-
ditions, such as high temperatures and harsh chemical environments.
Kaolin shares all those advantageous features of the ceramic membrane.
In 1999, Huang and co-workers [20] were the first who developed
S.K. Hubadillah et al.
Fig. 27. Cross-sectional SEM images of ceramic membrane from kaolin at different kaolin/PESF ratio [79].
ceramic membrane from kaolin for gas separation. However, the
ceramic membrane had low separation capacity due to its large pore
size. Thus, they coated polyaniline layer and successfully produced a
composite membrane for nitrogen separation. The substrate ceramic
membrane from kaolin with pore size of 1 µm was as cheap as $ 0.35
per piece while the price of commercial disks was about $7.00 per piece
at that time. The experimental setup for the nitrogen separation is
shown in Fig. 29. In our recent work [18], a low cost ceramic mem-
brane has been successfully developed with high gas fluxes (CO2, O2
and N2) of more than 300 GPU. The membrane can be used as a sub-
strate for the composite gas separation membrane.
Water pollution, especially oily wastewater is currently considered
as one of the major threats to aquatic environment [80]. Also, the
maximum allowable discharge limit is 20 mg/L oil concentration. The
membrane separation seems one of the best methods to solve this
problem [81]. Nandi et al. [82] used the low cost ceramic membranes
made from kaolin with an estimated cost of 220$/m2 in disc config-
uration for the treatment of oily wastewaters with two different oil
concentrations of 125 and 250 mg/L. An allowable oil concentration
was achieved in the permeate (< 10 mg/L) with a rejection of 98.8%
and a flux of 5.36 × 10−6 m3/m2 s. Emani et al. [16], on the other
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Ceramics International 44 (2018) 4538–4560
hand, obtained a rejection of 98.52% with a flux of 22.14 × 10−6 m3/
m2 s by using a disc configured membrane prepared by pressing
method. A very high rejection of 99.98% with flux of 3.16 × 10−5 m/s
was obtained by Kumar et al. [83] by using tubular ceramic membrane
made from kaolin.
Due to many advantages offered by the ceramic membrane from
kaolin, much attention has been paid not only to oily wastewater se-
paration, but also as a substrate for catalyst immobilization, for the
preparation of composite membranes for gas separation as well as for
water treatment. Table 7 summarises some applications of ceramic
membrane made from kaolin based on fabrication method, configura-
tion and structure.
The use of cost effective ceramic membranes from kaolin is still
relatively new and despite the improvement made, there still are some
challenges to be overcome. As discussed in Section 3.5, there are ad-
vantages in employing the phase inversion/sintering technique to de-
velop excellent low cost ceramic membrane in terms of structure and
properties. To the best of our knowledge, no investigations have been
conducted on spinning hollow fibres based on kaolin material.
S.K. Hubadillah et al.
Fig. 28. Effect of sintering temperature on ceramic membrane made from kaolin [79].
5. Future direction and challenges
In a relatively short space of time since 1999, when the first ceramic
membrane from kaolin in disc shape was reported to lower the cost
while improving membrane properties in terms of configuration,
structure and hence performance, many successful applications have
been reported. Moreover, all available fabrications methods for ceramic
membrane have been compared. As a result, an enormous potential of
the phase inversion/sintering technique was identified. However, some
challenges and questions still exist in this method to be addressed by
further investigations.
One of the problems accompanying the use of ceramic membrane
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Ceramics International 44 (2018) 4538–4560
from kaolin, prepared in flat sheet configuration is the difficulties to
handle the membrane when they are in operation. Based on our pre-
vious work [17,18], the final product is very porous as the intrinsic
nature of the phase inversion technique to produce asymmetric struc-
ture in the membrane. The problem can potentially be solved by de-
veloping ceramic membrane in hollow fibre configuration whose me-
chanical strength can be enhanced due to the change in pressure
distribution in the membrane. As well, hollow fibres offer the ad-
vantage of large surface to volume ratio.
Most of the works on the preparation of ceramic hollow fibre
membranes by phase inversion/sintering technique were focusing on
the fabrication parameters such as bore fluid flow rate, extrusion rate
S.K. Hubadillah et al. Ceramics International 44 (2018) 4538–4560

Table 6
Advantages and disadvantages of ceramic membranes from kaolin fabricated by different methods.

Ceramic membrane from Advantages Disadvantages

kaolin's fabrication method

Slip Casting ➢ Cheap ➢ Difficult to control the wall thickness

➢ Simple technique ➢ The slurry is hard to prepare, exact ratio of powder and water is
➢ Able to produce membrane in any shape, based on the mould required
Tape Casting ➢ Cheap ➢ Only flat sheet membrane can be obtained, usually disc shape
➢ Easy fabrication process
➢ Can combine with phase inversion technique to produce flat
sheet membrane
➢ Ease in controlling the membrane's thickness using doctor blade
Pressing Method ➢ Produce high strength membrane ➢ Expensive
➢ Uniform structure can be made ➢ Only flat disc can be obtained
➢ Only symmetric structure is produced, usually needs additional step
for separation layer
Extrusion ➢ Produce ceramic membrane in tubular configuration ➢ Limited complexity of parts
➢ High production volume ➢ Only symmetric structure produced
➢ Cheap ➢ Repetitive sintering steps that make the fabrication time consuming
➢ Only water and powders are used, environmental friendly and costly
method
Phase Inversion/Sintering ➢ Simple ➢ The organic solvent in suspension such as NMP will be potentially
Technique ➢ Cheap released in the environment, implicating bad environmental
➢ Can be produced in both flat/disc or hollow fibre configuration effects
➢ Produce asymmetric structure with finger-like and sponge-like
voids that enhance the flux and separation capability in single
step
➢ Very high surface/volume ratio
➢ High mechanical strength
➢ High production volumes
➢ Desired structure can be obtained by varying some parameters
(kaolin contents, suspension viscosity, bore fluid flow rate, etc.)

would be very beneficial since it can provide a support for the devel-
opment of composite membranes with high fluxes. Particularly, ceramic
hollow fibre membranes with an asymmetric structure and a high sur-
face to volume ratio would be able to compete economically with
polymeric membranes in some applications.

6. Concluding remarks

Fig. 29. A schematic diagram of setup for nitrogen (N2) separation using first ceramic
membrane from kaolin [20].
and ceramic/polymer ratio. However, there may be some other para-
meters that are crucial for the spinning of ceramic hollow fibres; the
addition of pore forming agents seems one of such parameters. As al-
ready mentioned, there is a threshold viscosity of the suspension above
which undesirable sponge-like structure is formed [75]., Although re-
ducing the viscosity below the threshold value leads to favourable
finger-like structure, the ceramic membrane so produced is low in
mechanical strength due to the lack of grain growth between the kaolin
particles. This problem can potentially be solved by the addition of pore
forming agents. Pore forming agents such as starch [84]and calcium
carbonate (CaCO3) [85]have proven to improve the morphological
structural of ceramic membrane prepared by the pressing method. It
would be interesting to test if the pore forming agents improve the
ceramic membrane prepared by phase inversion/sintering technique.
Besides the above mentioned pore forming agents, polyvinyl pyr-
rolidone (PVP) and polyethylene glycol (PEG) are the most commonly
used in polymeric membrane to increase the length of finger-like voids
[86–89]. The success in fabrication of low cost ceramic membrane from
kaolin with many finger-like voids and sufficient mechanical strength
Kaolin is one of the most used low cost ceramic material in pro-
duction of low cost ceramic membrane. Kaolin based ceramic mem-
brane has received much attention in many applications as filters as
well as supports and substrates of composite membranes. Among the
five fabrication methods, slip casting, tape casting, pressing method,
extrusion and phase inversion, pressing method and extrusion have
been used in most of investigations until now. However, both of them
can produce only symmetric membrane structure. Besides, the mem-
branes made by the pressing method are very expensive.Combined
technique of phase inversion and sintering has drawn much attention
recently since it allows the fabrication of ceramic membranes with an
asymmetric structure having unique finger-like voids. Nevertheless,
phase inversion/sintering technique has so far been limited to flat sheet
configuration with poor mechanical strength. Hence, fabrication of
ceramic hollow fibre membranes from kaolin is suggested to enhance
the mechanical strength and the surface/volume ratio, simultaneously,
which may potentially lead to the fabrication of a high performance and
economically feasible ceramic membranes for some applications.
Acknowledgement
The authors gratefully acknowledge the financial support from the
Ministry of Education Malaysia under the Higher Institution Centre of
Excellence Scheme (Project Number: R.J090301.7846.4J192),
Universiti Teknologi Malaysia under the Research University Grant Tier
1 (Project number: Q.J130000.2546.12H25), Nippon Sheet Glass
Foundation for Materials Science and Engineering under Overseas
Research Grant Scheme (Project number: R.J130000.7346.4B218) and

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Table 7
Low cost ceramic membrane from kaolin used for different applications.

No. Year Fabrication method for ceramic Membrane Membrane Application Ref
membrane from kaolin configuration structure

1 2003 Slip casting Tubular Symmetric Support for zeolite membranes (Mohammadi and Pak
[41])
2 2007 Tape casting Flat disc shape Symmetric Microfiltration (liquid and gas permeation) (Nandi et al. [53])
3 2007 Slip casting Gypsum form (not state) Symmetric Catalytic membrane reactor (Zyryanov et al. [43])
4 2011 Tape casting Flat disc shape Symmetric Oil-water separation (Mittal et al. [14])
5 2011 Tape casting Flat disc shape Symmetric Support for crosslinked chitosan on top for (Jana et al. [57])
mercury and arsenic removal
6 2011 Phase inversion Flat sheet Asymmetric Water filtration (Sarbatly [79])
7 2012 Pressing method Flat disc shape Symmetric Microfiltration of chromium (VI) (Vasanth et al., 2012)
8 2012 Extrusion Tubular Symmetric Oily wastewater treatment (Abbasi et al., 2012)
9 2015 Pressing method Flat disc shape Symmetric Carbon monoxide oxidation (Krivoshapkina et al.,
2015)
10 2015 Pressing method Flat disc shape Symmetric Oily wastewater treatment (Eom et al., 2015)
11 2015 Extrusion Tubular Symmetric Water filtration (Fatimah et al., 2015)
12 2015 Extrusion Flat sheet Symmetric Oily wastewater treatment (Shokrkar et al., 2011)
13 2016 Phase inversion Flat sheet Asymmetric Support for gas separation (Hubadillah et al., 2016a)
14 2016 Phase inversion Flat sheet Asymmetric Support for gas separation (Hubadillah et al., 2016b)
15 2016 Pressing method Flat disc shape Symmetric As porous ceramic support for liquid dye (Issaoui et al., 2016)
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