Accepted Manuscript

Title: Preparation and characterization of low cost porous

ceramic membrane support from kaolin using phase
inversion/sintering technique for gas separation: Effect of
kaolin content and non-solvent coagulant bath

Author: Siti Khadijah Hubadillah Zawati Harun Mohd Hafiz

Dzarfan Othman A.F. Ismail Wan Norharyati Wan Salleh
Hatijah Basri Muhamad Zaini Yunos Paran Gani

PII: S0263-8762(16)30136-8
DOI: http://dx.doi.org/doi:10.1016/j.cherd.2016.06.007
Reference: CHERD 2304

To appear in:

Received date: 5-2-2016

Revised date: 27-5-2016
Accepted date: 6-6-2016

Please cite this article as: Hubadillah, S.K., Harun, Z., Othman, M.H.D., Ismail,
A.F., Salleh, W.N.W., Yunos, H.B., </sup>Muhamad Zaini, Gani, P.,Preparation and
characterization of low cost porous ceramic membrane support from kaolin using
phase inversion/sintering technique for gas separation: Effect of kaolin content and
non-solvent coagulant bath, Chemical Engineering Research and Design (2016),
http://dx.doi.org/10.1016/j.cherd.2016.06.007

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Highlights
 Ceramic membrane support from kaolin using phase inversion/sintering technique.
 Effect of kaolin content and non-solvent coagulant bath towards membrane support.
 High gas permeability and low rejection proved the suitability on gas separation.
 A low cost ceramic membrane support are obtained compare to previous work.

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Page 1 of 36
Preparation and characterization of low cost porous ceramic membrane support from

kaolin using phase inversion/sintering technique for gas separation: Effect of kaolin

content and non-solvent coagulant bath

Siti Khadijah Hubadillaha,b* , Zawati Harun,b,c, Mohd Hafiz Dzarfan Othmana, A.F. Ismaila,

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Wan Norharyati Wan Salleha, Hatijah Basrid, Muhamad Zaini Yunos b,c, Paran Ganie

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Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia,
81310 Skudai, Johor, Malaysia

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b
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.
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c
Department of Material and Design, Faculty of Mechanical and Manufacturing Engineering,
Universiti Tun Hussein Onn Malaysia, Parit Raja, Batu Pahat 86400, Johor, Malaysia
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d
Department of Technology and Heritage, Faculty of Science, Technology and Human
Development, Universiti Tun Hussein Onn Malaysia, 86400 Parit Raja, Batu Pahat, Johor Darul
Takzim, Malaysia.
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e
Department of Water and Environmental engineering, Faculty of Civil and Environmental
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Engineering, Universiti Tun Hussein Onn Malaysia, Parit Raja, Batu Pahat 86400, Johor,
Malaysia
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*Corresponding author at: Integrated Material Process, Advanced Materials and Manufacturing
Center, Universiti Tun Hussein Onn Malaysia, 86400 Parit Raja, Batu Pahat, Johor Darul
Takzim, Malaysia.Tel: +60 74537608; fax: +60 74536080

E-mail address: ctkhadeeja@gmail.com (S.K., Hubadillah)*

Page 2 of 36
Abstract

The aim of this study is to investigate the feasibility of using kaolin as a starting material in

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ceramic membrane support preparation using phase inversion/sintering technique at different

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kaolin content and non-solvent coagulant bath. The ceramic suspension was prepared by mixing

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the kaolin, polyethersulfone (PESf) as binder, N-Methyl-2-pyrrolidone (NMP) as solvent and

Arlacel as dispersant using a magnetic stirrer; drying and sintering process at temperature of

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1200ºC. By varying the kaolin contents, different morphologies of ceramic support were

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obtained due to the variations in viscosity of ceramic suspensions. Similarly, different non-

solvent coagulant bath was found to affect the membrane support structure through liquid-liquid
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demixing process and at the same time affected membrane support’s roughness, porosity, pore

size distribution and strength. All ceramic supports possessed high gas permeation with no
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separation capability, proven the suitability as ceramic membrane support. The cost for the

prepared ceramic membrane support in this work is as low as $5.97, prepared at 54.0 g kaolin
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content and immersed into distilled water.

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Keywords: Ceramic membrane support, Kaolin, Phase Inversion, Gas separation

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Page 3 of 36
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1. Introduction

The combination of excellent thermal and chemical stabilities has made ceramic membranes as

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an attractive alternative to polymeric membranes (Fung and Wang, 2014; Harun et al., 2014;

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Hubadillah et al., 2014; Kingsbury and Li, 2009; Othman et al., 2010; Paiman et al., 2015).

These advantages have resulted in ceramic membranes to show better durability under harsh
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condition such as gas separation application (Donelson et al., 2014; Isobe et al., 2007; Li and

Hwang, 1992). Consequently, porous ceramic membrane support has received intensive
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attentions because of their advantages being used in a broad range of applications (Bouzerara et

al., 2006; Isobe et al., 2013; Miao, 1999; Smart et al., 2013). Pore size distribution, total porosity
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ratio, surface quality and mechanical strength are among the major properties of the development
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of ceramic membrane support. The addition of top layer on the support which will be applied in

the subsequent preparation steps is of crucial importance to the integrity of ceramic membrane.
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Conventionally, most ceramic membrane support are usually made from expensive metal oxides

such as alumina, zirconia, titania or a combination of these oxides. However, significant efforts

have been made in recent years in membrane technology to develop new porous ceramic support

from kaolin (Bouzerara et al., 2006; Bouzerara et al., 2012; Emani et al., 2014; Sarbatly, 2011).

Kaolin is one of the most widely clay materials and has an important role in numerous industrial

Page 4 of 36
applications, such as provides low plasticity and high refractory properties (Bouzerara et al.,

2006); and preferred raw material for porous ceramics (Ganesh and Ferreira, 2009). It may

however be noted that most of the studies on kaolin were aimed at water and wastewater

application (Bouzerara et al., 2006; Sahnoun and Baklouti, 2013) and no attempt has been made

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for gas separation.

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Preparation of ceramic membrane using phase inversion technique is an emerging method for

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producing asymmetric ceramic membrane. In 2009, Li et al. had reported on the formation of

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macrostructures in a ceramic membrane from alumina using phase inversion technique is due to

the hydrodynamically unstable viscous fingering (Kingsbury and Li, 2009). Three years later,
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Wang and Lai extended this work by investigating the effect of different non-solvent coagulant

bath to distinguish characteristics according to the rules of the viscous fingering theory (Wang
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and Lai, 2012). In 2011, Sarbatly discovered that ceramic membrane from kaolin can be

successfully prepared by phase inversion technique (Sarbatly, 2011).

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Concerning to the costing problem in fabrication of porous ceramic membrane support towards
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gas separation application, therefore, this work aims to provide a thorough investigation on two

important fabrication parameters towards the quality of prepared porous ceramic membrane
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support from kaolin material. Firstly, this paper continues the effort of two works (Sarbatly,
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2011; Wang and Lai, 2012) to investigate the effect of non-solvent coagulant bath towards the

fabrication of low cost ceramic membrane support using phase inversion technique. The

composition for ceramic membrane support was adapted by work of Sarbatly (Sarbatly, 2011).

Secondly, this study was also examined the effect of non-solvent coagulant bath. In this regard, it

shall be noted that all supports will promote different morphologies according to previous

studies. In this study, ceramic membrane support’s characteristics which are surface roughness,

Page 5 of 36
pore size distribution, porosity and mechanical strength have been investigated. The gas

separation performance will also be investigated in term of gas permeation and selectivity.

2. Experimental

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2.1 Materials

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Kaolin powder with particle size ranging from 0.3 µm to 0.8 µm purchased from BG Oil Chem

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Sdn Bhd was used as the ceramic particles. Polyethersulfone (PESf) (UDEL) was used as the

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polymer binder, while N-methylpyrrolidone (NMP, QRëC™) was used as the solvent.

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2.2 Preparation of ceramic suspension
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The kaolin powder and PESf were dried in an oven overnight at 60ºC to remove all moisture.

Then, NMP and Arlacel was stirred at temperature of 60ºC prior to the addition of the kaolin
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powder. The suspension was then stirred for 48 h by using magnetic stirrer Yellow MAG HS 7

S2 (IKA) with a hot plate stirrer was set at 60ºC to ensure that the ceramic particles, solvent and
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additive were mixed well. The stirring was continued for another 48 h after the addition of PESf

to ensure that the polymer binder was fully dissolved. After that, the suspension was degassed
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with slow stirring at 80 rpm under vacuum at room temperature until no bubbles were observed.

Removing bubbles from the ceramic suspension was important to avoid defects, which usually

forming small holes on the precursors.

Page 6 of 36
2.3 Fabrication of ceramic support from kaolin

Figure 1 and Table 1 show the preparation of flat-sheet ceramic precursor from kaolin by phase

inversion technique and its composition, respectively. Precursor is sample before sinter to obtain

final ceramic support. The prepared ceramic suspension was poured onto a clean and smooth

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glass plate of 15x15cm at room temperature using a casting knife. The thickness of the ceramic

support was controlled by using adhesive tape that sticked on the glass plate. The cast film was

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then immediately immersed into non-solvent coagulant bath. In this study, three different types

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of non-solvent coagulant bath were used which are distilled water, ethanol and mixture of 70%

NMP and 30% distilled water for 24 h to complete the phase inversion process. Next, solidified
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ceramic precursor was dried at room temperature for 24 h. Ceramic precursor was cut into the

desired shape prior to sintering process at a temperature of 1200ºC. The sintering process was
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run in two-step. The sintering temperature was increased from room temperature to 600ºC at a

rate of 2ºC/min to burn off the polymer completely leaving just ceramic particles. Then, the
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sintering temperature was further increased to 1200ºC at a rate of 5ºC/min. The temperature was
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then cooled down to room temperature at a rate of 5ºC/min.

2.4 Characterization methods

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2.4.1 Ceramic suspension measurement

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Viscosity of the suspension solution at different kaolin content was collected immediately prior

to the spinning process using Brookfield DV II + Pro Viscometer (model LVDV-II + P). The

suspension was prepared about 200 mL and spinned at 70 rpm using spindle no 2.

2.4.2 Morphological studies

Page 7 of 36
The overall cross section of the flat sheet ceramic support was examined using a JEOL JSM

7600F Field Emission Scanning Electron Microscopy (FESEM) at 50x and zoomed at 600x

magnification. These ceramic support samples were placed on a metal holder and sputter by gold

under vacuum for 3 mins. The same method was also used to snap the morphologies of ceramic

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support’s surface.

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2.4.3 Surface roughness

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The membrane support surface roughness was investigated by atomic force microscopy (AFM)

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(model: PARK XE-100, SCHAEFER Technologie GmbH). Surface roughness was obtained by

tip scanning. In this study scan size was 10 µm x 10 µm.

2.4.4 Porosity and pore size distribution

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The pore size distribution and porosity was measured using mercury porosimeter (Micromeritics,

Autopore IV, 9500) combined with Micrometrics software (version 1.09).

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2.4.5 Mechanical testing

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The mechanical strength of the samples were determined by three-point bending strength
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method. The three-point bending test was carried out with universal testing machine (AG-1

SHIMADZU). In this work, the bending strength (σb) of flat-sheet sample is calculated using the
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following equation (Hara et al., 2014):

where σb is bending strength, F is fracture force, L is membrane suppport span length, w is

membrane support width and t is membrane support thickness.

Page 8 of 36
2.5 Performance test of ceramic support from kaolin

In this work, single gas permeation measurement was conducted instead of mixed gas in order to

evaluate the gas permeation properties of the developed kaolin ceramic support and the

experimental set up as shown in Figure 2, which also provide the trends of the material. The gas

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permeation testing was carried out using pure CO2 (3.30Å), O2 (3.46Å) and N2 (3.64Å) as test

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gases at room temperature and pressure of 1 bar. Prior to the testing, the supports were exposed

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to a pure gas stream for approximately 10 min at a very low pressure in order to remove residual

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air and other gases before measuring gas permeation properties. The gas test was conducted for

each sample for three times to get the average value. From the gas permeation test, two
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membrane support performances were obtained: (1) gas permeation and (2) gas selectivity

(CO2/N2 and O2/N2), which were calculated based on equation (Chapman and The University of
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Texas at Arlington. Biomedical, 2007):
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where P is gas permeability (GPU), Q is flowrate (ml/s), L is membrane support thickness (cm),
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A is membrane support effective area (cm2) and Δp is pressure gradient (cm Hg). The selectivity

of gas was calculated as follows:

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where PA and PB are the gas permeation of pure gases of A and B, respectively.

3. Results and Discussions

3.1 Ceramic membrane support morphology

Page 9 of 36
The kaolin ceramic membrane supports were prepared with ceramic dope suspensions consisting

of 54.0 g, 67.5 g, 81.0 g and 94.5 g kaolin contents, and immersed into three different types on

non-solvent coagulant bath (distilled water, ethanol, and mixture of 70% NMP and 30% distilled

water). The cross-section images of the prepared ceramic supports at different kaolin contents

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and immersed into distilled water as coagulant bath are shown in Figure 3. As can be seen,

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ceramic support prepared at 54.0 g kaolin content comprised of asymmetric structure with finger-

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like structures originating from top of support surface with the length of about 20% of support

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thickness. The remaining region occupied by sponge-like voids. Longer finger-like structures

was formed when kaolin content reached at 67.5 g and forming pear-shape structure. A similar
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structure was reported by Lee et al (Lee et al., 2015) who used alumina in their work. M3

resulting from 81.0 g kaolin content has same asymmetric structure with M2, but the length of
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finger-like structures was reduced and and the cross-section was occupied mostly by sponge-like

pores. Conversely, M4 shows asymmetric structure without finger-like structures which was
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replaced by dense layer with thickness at about 40-50µm, measured from FESEM images.
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As reported by Kingsbury (Kingsbury and Li, 2009), asymmetric structure consisting finger-like

and sponge-like voids can be obtained by ceramic membrane from phase inversion technique.
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The work also revealed that a structure without finger-like voids can also be obtained due to the

effect of ceramic suspension viscosity. The same situation also described by Othman et al.
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(Othman et al., 2010). Therefore, to investigate the effect of viscosity on ceramic support

morphology, four different kaolin contents ranging from 54.0 to 94.5 g were used to vary the

suspension viscosity as shown in Figure 4. Paiman et al. (Paiman et al., 2015) also used the same

method to study the effect of ceramic contents towards the viscosity of ceramic suspension

which in their case, yttria-stabilized zirconia (YSZ) was used. From the data in Figure 4, it is

Page 10 of 36
clear that the suspension viscosity value of 11,000 cP at 54.0 g kaolin content slightly increased

to approximately 15,000 cP when 67.5 g kaolin content was used and this value further increased

to 26,000 cP at 81.0 g kaolin content. The further addition of kaolin content resulted a

dramatically viscosity increases to 47,000 cP at 94.5 g kaolin content. This result is in line with

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the expectation, because an increase in ceramic powder contents reduced the amount of NMP,

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which in this study the composition of PESf was fixed. Consistent with finding by Othman et al.

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(Othman et al., 2010), for M4, no observable finger-like structure due to high viscosity of the

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suspension which above its threshold.

Figure 5-E1(i) to E4(i) show the overall kaolin ceramic membrane support morphology from
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immersion into ethanol as non-solvent coagulant bath at different kaolin contents at

magnification of 50x and Figure 3-E1(ii) to E4(ii) show the FESEM images when zoomed at
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600x magnification at top of support cross section. As can be seen, there was no observable

finger-like structure in support cross section at magnification of 50x. Furthermore, Figure 3-E1
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(i) to E3 (i) shows an increase in dense layer from 11.3 to 331.5 µm on top of the support with
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the increased of kaolin contents from 54.0 g to 67.5. For support E1 and E2, sponge-like voids

were formed under the thin dense layer and occupying about 90% of support thickness while for
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support E3, were reduced to 70%. However, surprisingly, when E1 (i) and E2 (i) were zoomed at

high magnification, as shown in Figure 3-E1 (ii) and E2 (ii), a small finger-like structures can be
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observed under dense layer of support. Further increased in kaolin content at 81.0 g resulting the

elimination of these finger-like structure, which in this work thick dense layer of 331.5 µm was

obtained, as shown in Figure 5-E3 (i). This finding is believed resulting from the condition of

solvent/non-solvent exchange that leads to a change of polymer solution from

thermodynamically stable to an unstable state (Hilal et al., 2015). Under this condition, the small

Page 11 of 36
finger-like structures were predicted to be formed on top of the support due to slow precipitation.

The dense layer obtained might be resulted from the effect of sintering process which showing

the densification of very small finger-like structures, thus causing a decrease in porosity (Othman

et al., 2010). More information on effect of sintering would help us to establish a greater degree

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of accuracy on this matter. Therefore, a further study investigating the effect of sintering on this

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type of membrane support would be very interesting. The most significant findings to emerge

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from this study is that the absence of finger-like structure and formation of dense top layer,

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which was contradicted from support that immersed into distilled water (Figure 3). This is

because, ethanol is less strong non-solvent coagulant bath compared to distilled water. As
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mentioned by Mulder (Mulder, 1996), ethanol promoting slow demixing process as it not good

coagulant as water, thus increases the rate of low precipitation and inhibited finger-like structure.
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Figure 6-N1(i) to N4(i) and 4-N1(ii) to N4(ii) illustrate the morphologies of ceramic support

from kaolin that used the mixture of 70% NMP and 30% water as the coagulant bath at
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magnification 50x and 600x, respectively. NMP was added into water coagulant bath to delay the
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liquid-liquid demixing during support fabrication process. This unique technique has been

applied to PVDF membrane in which possessed higher carbon dioxide flux (Rafiq et al., 2011).
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Figure 6-N1 (i) and (ii) show ceramic supports prepared from 54.0 g kaolin content and

immersed into mixture of 70% NMP and 30% distilled water. As observed, large macrovoids
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were formed in the membrane support cross section for about 50% of support thickness which

might be disturbed membrane support mechanical strength (Figure 11), that will be discussed

later. As reported by some researchers (Hilal et al., 2015; Young and Chen, 1995), immersing

casting solution into weak coagulant bath was delayed demixing process in which resulting the

formation of sponge-like structure with the absence of dense skin layer. In this work, the mixture

Page 12 of 36
of 70% NMP and 30% distilled water is the weakest coagulant compare to distilled water and

ethanol (Wang and Lai, 2012). It is believed that the large macrovoids were formed due to lowest

viscosity (11,117 cP), promoted unstable condition when phase inversion took place. However,

these macrovoids were eliminated when kaolin contents increased from 54.0 g to 81.0 g as

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shown in Figure 6-N2 (i) to N4 (i), forming sponge-like voids. Sponge-like voids with graded

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pores size distribution can be observed for N2 and N3 and uniform pores size for N4, as can be

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seen clearly in Figure 4-N2(ii) to N4(ii). It is suggested that kaolin content up to 67.5 g promotes

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an optimum viscosity value of ceramic suspension to be immersed in the weakest non-solvent

coagulant bath (mixture of 70% NMP and 30% distilled water).

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As mentioned in the literature, membrane surface plays important role in formation of

subsequent step separation layer, in which the same for the membrane support. Therefore, further
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discussion on the effect of different types non-solvent coagulant bath towards membrane support

surface are shown in Figure 7-M1 to M4, E1 to E4 and N1 to N4 for immersion into distilled
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water, ethanol and mixture of 70% NMP and 30% distilled water, respectively. Based on the
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result, the surface of kaolin ceramic support immersed into distilled water was denser compared

to that of immersed into ethanol and mixture of 70% NMP and 30% distilled water. In order to
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support the FESEM images, the surface roughness value was obtained using atomic force

microscopy (AFM). From the AFM, the 3D images and membrane support average roughness
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(Ra) are obtained and shown in Figure 8. From Figure 7, it is observed that the pore size is

reduced with increased kaolin content but no significance change when different non-solvent

coagulant bath was used. However, average roughness (Ra) value from Figure 8 provides a

significant value. The smoothest and roughest support was obtained by immersing into distilled

water and mixture of 70% NMP and water, respectively. What is interesting in this data is that

Page 13 of 36
the support without dense layer produced the smoothest membrane support. The result is in

agreement with previous work (Sukitpaneenit and Chung, 2009) that found faster precipitation

induced smoothest support surface, which was found in this work. Detailed explanation on such

mechanism can be found elsewhere (Hilal et al., 2015).

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3.2 Pore size distribution

Figure 9 shows the pore size distribution of the prepared membrane support that immersed into

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different types of non-solvent coagulant bath at different kaolin contents using mercury intrusion

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measurements. According to the obtained data, all ceramic supports show different pore size

distribution. Two significant pore sizes have been recognized for support immersed into distilled
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water, three pores for ethanol and single pores for support immersed into mixture of 70% NMP

and 30% distilled water. For support immersed into distilled water, a peak at 0.93 µm is believed
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representing the finger-like pores on top of the membrane support cross section M1. As the

ceramic suspension was increased from 54.0 g to 67.5 g, the peak of finger-like pores at 0.93 µm
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shifted to 1.1 µm, indicating the finger-like voids increase for M2. This peak was observed to be
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remained for M3 with reduced intensity, indicated that the pore size of M2 and M3 are almost

the same. For instance, this peak remained for M4 and this was contradicted to the FESEM
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image shown in Figure 3 (M4) that showed no observable finger-like structure. It is suggested

that this peak represents sponge-like voids in which the size are relatively large. Accordingly, the
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value of finger-like void was shifted from 1.1 µm to 0.27 µm, resulting the formation of dense

layer on top of the support prepared at 94.5 g kaolin content (M4).

For kaolin ceramic support immersed into ethanol, the pore size distribution indicates different

pore size obtained. For supports E1 and E2, three types of pores have been recognized, which are

the dense layer, small finger-like voids and sponge-like structure. For support E1, the data shows

Page 14 of 36
a pore size distribution consisting of a peak at approximately 1.2, 1.5 and 5.1 µm, which are

believed representing the pores of dense layer, sponge-like and small finger-like structure. For

E2, the peak of 5.1 µm was absent due to the finger-like structure was eliminated at high

suspension viscosity. In addition, the peak at 0.55 µm and 0.75 µm, representing pores of dense

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layer and sponge-like structure. These peaks were remained for E3 with intensity reduced just a

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little. Finally, the peaks were totally eliminated and a peak at approximately 0.17 µm was

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appeared, representing symmetric structure of the support prepared at 94.5 g kaolin content.

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N1 to N4 represent the support immersed into the mixture of 70% NMP and 30% distilled water.

For support N1, the data show a pore size distribution and it was different with supports N2 to
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N4. A significant peak was observed at 25.1 µm, indicating large macrovoids as present in

FESEM image (Figure 4-N1(i)). However, this peak has been eliminated when kaolin content
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increased up to 67.5 g, replacing a peak at 0.87 µm that represented sponge-like pores. This peak

decreased in size from 0.87 µm to 0.75 µm when 81.0 g kaolin content was used. Further
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addition of kaolin content at 94.5 g resulting a pore size value of 0.75 µm. Overall, the pore size
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distribution revealed the order of PSDmixture70%NMP+30% water > PSDethanol > PSDwater in which PSD

represents pore size distribution. Therefore, this concluded that strong non-solvent coagulant
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produced smaller pore size with asymmetric structure while vice versa for weakest non-solvent

coagulant bath.
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3.3 Porosity

The effect of non-solvent coagulant bath and kaolin content are further studied by measuring the

porosity using mercury intrusion analysis, as shown in Figure 10. The purpose in measuring the

porosity is to identify the average value of pore size contributed in the support. As expected, the

porosity decreases with increasing kaolin content, for example for support immersed into

Page 15 of 36
distilled water, the porosity decreases from 23.2% to 18.1% with increasing kaolin content from

54.0 g to 94.5 g, respectively. For the effect of non-solvent coagulant bath, the trend was similar

to the pore size distribution result (Figure 9), in which mixture 70% NMP and 30% distilled

water > ethanol > distilled water. It was found that the porosity for all supports are in the range

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of 15% to 30% which obeyed the limitation (Othman et al., 2010) except for support that

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prepared at 54.0 g kaolin content and immersed into mixture of NMP and distilled water. The

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porosity of the support that prepared at 54.0 g kaolin content is 93.4 %. However, this result is

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expected because the FESEM images showing large macrovoids (Figure 6-N1 (1)) and pore size

distribution data showing a peak at 25.1 µm (Figure 9 (A)).

3.4 Membrane support mechanical strength

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It is interesting to observe the change in the mechanical strength of ceramic membrane support

from kaolin prepared by phase inversion technique at different kaolin content and non-solvent
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coagulant bath. Figure 11 shows the mechanical strength of ceramic membrane support that

measured using three point bending test. As shown, the mechanical strength increases with
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increasing kaolin content for all cases. For example, the mechanical strength increased

significantly from 10.3 MPa to 30.3 MPa when the kaolin content increased from 54.0 to 94.5 g
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that immersed into distilled water. Among all ceramic membrane supports, the highest
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mechanical strength were exhibited by the supports that was immersed into strong coagulant, i.e.

distilled water. A middle value was obtained by supports immersed into ethanol and show

decreasing trend similar to distilled water. Another similar trend can also be observed to supports

immersed into mixture of 70% NMP and 30% distilled water. As expected, the mechanical

strength for membrane support prepared at kaolin content of 54.0 g and immersed into the

mixture of 70% of NMP and 30% of distilled water shows the lowest value of 1.1 MPa.

Page 16 of 36
However, this value increases from 27.2 MPa to 28.2 MPa when kaolin content increased from

67.5 to 94.5 g, respectively. The lowest value in the mechanical strength was most likely due to

the existence of large macrovoids (Figure 6-N1(i)) while the increment was due to increase in the

mass of ceramic particle contributes to the mechanical strength for almost all ceramic supports

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whether by effect of kaolin content or non-solvent coagulant bath or both of them. Thus, this

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work suggested that large macrovoids sacrificed the mechanical strength.

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3.4 Gas permeation and selectivity

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Figure 12 portrays the carbon dioxide (CO2), oxygen (O2) and nitrogen (N2) permeability as a

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function of support that prepared at different kaolin content in which is immersed into different

types of non-solvent coagulant bath (distilled water, ethanol and mixture of 70% NMP and 30%
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of distilled water). No trend can be observed due to the large pore of ceramic membrane support.

However, all samples show high flux for CO2, O2 and N2, in which proved the feasibility of
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porous ceramic membrane support as a medium for gas separation application.

Further investigation on the effect of non-solvent coagulant bath was discussed in term of gas
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selectivity as shown in figure 13 to confirm that supports require additional separative layer in
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order to be served as a good membrane. As expected, the result shows poor gas selectivity with

values not more than 1. According to Isobe et al., gas permeability coefficient of a porous body
Ac

is known to increase markedly by Knudsen diffusion where its pore size is larger to mean free

path of gas (Isobe et al., 2013). Besides, pore sizes for the obtained support in this work are

found to be significant larger according to the porosity, pore size distribution, and morphology

measurement. As a result, high gas flux is obtained and gas selectivity ended up as around 1,

with no separation capability. Thus, it is concluded that the prepared ceramic membrane

Page 17 of 36
supported in this work is promising medium for used in future by adding separation layer on top

of the ceramic membrane support.

3.5 Cost analysis

t
The corresponding variation of ceramic membrane support produced for 15 x 15 cm and 46 mm

ip
circular-disk-shaped from one suspension. This analysis obtained as the detailed membrane

cr
produced as the membrane casted in the square shape at first, then formed towards 46 mm

us
diameter circular-disk-shaped. The cost analysis for each membranes shown in Table 5. Based

on the raw materials used for preparing ceramic membrane in this work, the manufacturing cost
an
of ceramic membrane is evaluated to be MYR 23.93/m2 ($5.97), MYR 24.81/m2 ($6.19), MYR

25.69/m2 ($6.41) and MYR 26.56/m2 ($6.63) for support prepared at kaolin content of 54.0 g,
M
67.5 g, 81.0 g and 94.5 g, respectively. In comparison, the ceramic membrane made with α-

alumina, nickel (II) oxide and zinc oxide cost around $500/m2, $310/m2 and $270/m2,
ed

respectively (Vasanth et al., 2011). In addition, refer to previous studies polymeric membranes

cost around $50-200/m2 whereas inorganic membranes (metal, carbon and ceramic membrane)
pt

are claimed to be more expensive such as $500-1000/m2 (Mittal et al., 2011).

ce

4. Conclusion

Symmetric and asymmetric kaolin ceramic supports prepared from phase inversion technique
Ac

were obtained by varying two parameters which are kaolin content and non-solvent coagulant

bath. In this study, not all ceramic supports consist common structures obtained by phase

inversion technique (finger-like structure and sponge-like voids). Finger-like structure obtained

when immersed into distilled water, dense layer on top of the support can be obtained by

immersion into ethanol while mixture of NMP and water as coagulant produced symmetric

Page 18 of 36
ceramic support. Dense and smooth surface structure can be obtained by immersion into distilled

water due to fast precipitation rate. The viscosity of ceramic suspension can be enhanced by

increasing the kaolin content in which played important role in ceramic support for structure

formation. Two types of pore size was obtained from support immersed in distilled water,

t
meanwhile three when immersed into ethanol and then one after immersed into mixture of NMP

ip
and water. Nevertheless, gas rejection show very low value, but the permeability analysis shows

cr
an excellent values. In addition, the cost to produce the ceramic membrane supports in this work

us
are very cheap compare to previous work.

Acknowledgements an
The financial support from the Ministry of Higer Education with Research Grants Scheme vot
M
A022 is acknowledged with gratitude. The authors would like to thank Mr Fazlannuddin Hanur

bin Harith, for support with gas performance testing.

ed

References
pt

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ce

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t
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ip
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cr
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mechanical properties of porous alumina ceramics with unidirectionally aligned pores. Journal of
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Ac

Page 21 of 36
TABLES

Table 1: Composition of the ceramic dope suspension for ceramic membrane support

Membranes Composition (g) Non-solvent

Kaolin NMP PESf Arlacel Coagulant Bath
M1 54.0 150.75 27 1 Distilled water
M2 67.5 150.75 27 1

t
81.0 150.75 27 1

ip
M3
M4 94.5 150.75 27 1
E1 54.0 150.75 27 1 Ethanol

cr
E2 67.5 150.75 27 1
E3 81.0 150.75 27 1
E4 94.5 150.75 27 1

us
N1 54.0 150.75 27 1 70% NMP + 30%
N2 67.5 150.75 27 1 water
N3 81.0 150.75 27 1
N4 94.5 150.75 27 an 1

Table 2: Cost analysis of the prepared membranes from the unit cost of raw material
M
Raw materiala Unit price Amount of raw material used Cost of one suspension
(kg/MYR) for preparation of each (MYR)
membrane (kg)
ed

M1 M2 M3 M4 M1 M2 M3 M4
E1 E2 E3 E4 E1 E2 E3 E4
N1 N2 N3 N4 N1 N2 N3 N4
pt

(x10-3) (x10-3)

Kaolin 65 3.51 4.39 5.27 6.14

ce

54.0 67.5 81.0 94.5

(Al2Si2O5(OH)4)

Polyethersulfon 170 4.59 4.59 4.59 4.59 4.59 4.59 4.59 4.59
Ac

e (PES)

N-methyl-2- 105 15.83 15.83 15.83 15.83 15.83 15.83 15.83 15.83
pyrrolidone
(NMP)

Total cost/ ceramic dope suspension 23.93 24.81 25.69 26.56

a
Supplied by BGOIL CHEM SDN BHD, Malaysia

Page 22 of 36
 t
ip
cr
FIGURES

us
an
M
d
te
c ep
Ac

Figure 1 Flat-sheet ceramic precursor from kaolin prepared via phase inversion technique (before sinter)

Page 23 of 36
 t
ip
cr
us
an
M
d
te
c ep
Ac

Figure 2 Gas permeation testing setup

Page 24 of 36
 M1 M2

t
ip
cr
50 µm 50 µm

us
M3 M4

an
M

50 µm 50 µm
ed

Figure 3: FESEM images of the cross section prepared at different kaolin contents and immersed
pt

into distilled water

ce
Ac

26

Page 25 of 36
 t
ip
cr
us
an
M
Figure 4: Viscosity of ceramic suspension at different kaolin content
ed
pt
ce
Ac

27

Page 26 of 36
 t
ip
cr
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an
M
ed
pt
ce
Ac

Figure 5: FESEM images of the (i) overall cross section (ii) zoomed at 600x magnification
prepared at different kaolin content and immersed into ethanol

28

Page 27 of 36
 t
ip
cr
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an
M
ed
pt
ce
Ac

Figure 6: FESEM images of the (i) overall cross section (ii) zoomed at 600x magnification
prepared at different kaolin content and immersed into mixture of 70% NMP and 30% distilled
water

29

Page 28 of 36
 t
ip
cr
us
an
M
ed
pt
ce
Ac

Figure 7: FESEM images of membrane surface prepared at different kaolin content and
immersed into different coagulant

30

Page 29 of 36
 t
ip
cr
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an
M
ed
pt

Figure 8: Membrane surface roughness on the effect of different types of non-solvent coagulant
bath
ce
Ac

31

Page 30 of 36
 t
ip
cr
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an
M

Figure 9: Pore size distribution for membrane fabricated at different kaolin content and
ed

immersed into different non-solvent coagulant bath; (A) 54.0 g; (B) 67.5 g; (C) 81.0g; (D) 94.5 g
pt
ce
Ac

32

Page 31 of 36
 t
ip
cr
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an
M
Figure 10: Porosity of the kaolin ceramic membrane as a function effect of non-solvent coagulant
ed

bath
pt
ce
Ac

33

Page 32 of 36
Figure 11: Bending strength for membrane fabricated at different non-solvent coagulant bath and
kaolin content

t
ip
cr
us
an
M
ed
pt
ce
Ac

34

Page 33 of 36
Figure 12: Effect of different types of non-solvent coagulant bath of ceramic membrane prepared
at different kaolin content and immersed into different non-solvent coagulant bath towards gas
permeation

t
ip
Cont. Figure 12.

cr
us
an
M
ed
pt
ce
Ac

35

Page 34 of 36
 t
ip
cr
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an
M
ed
pt
ce
Ac

Figure 13: Effect of different types of non-solvent coagulant bath of ceramic membrane prepared
at different kaolin content and immersed into different non-solvent coagulant bath towards gas
selectivity

36

Page 35 of 36
Graphical Abstract (for review)

t
ip
cr
Graphical Abstract

us
Distilled water

an
M
Phase inversion technique
d
Ethanol

te
94.5 g kaolin
150. 75 g NMP
ep
27 g PESf
1 g Arlacel
c
Ac

Mixture of NMP +
water

Page 36 of 36