Journal of Membrane Science 319 (2008) 306312

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Journal of Membrane Science

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Enhanced gas permeation performance of polyethersulfone mixed matrix hollow ber membranes using novel Dynasylan Ameo silane agent
A.F. Ismail a, , T.D. Kusworo a,b , A. Mustafa a
a Membrane Research Unit, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor Bahru, Malaysia b Department of Chemical Engineering, University of Diponegoro, Jl. Prof. Sudharto, Tembalang, Indonesia

a r t i c l e

i n f o

a b s t r a c t
This study is performed primarily to investigate the effect of chemical modication on zeolite surface towards gas separation performance of hollow bers mixed matrix membrane. In this study, polyethersulfone (PES)zeolite 4A mixed matrix hollow ber membrane for modied and unmodied zeolite was spun using dry/wet spinning technique. The modied zeolite 4A was prepared by treating the zeolite with Dynasylan Ameo (DA) silane agent to allow PES chains to be grafted on zeolite surface. The results from the Field Emission Scanning Electron Microscopy (FESEM), DSC and Fourier transform infrared spectroscopy (FTIR) analysis conrmed that chemical modication on zeolite surface had taken place. Sieve-in-a-cage morphology observed the poor adhesion between polymer and unmodied zeolite. FESEMs cross-section view indicated good compatibility between polymer and zeolite for PESmodied zeolite. The gas separation performance of the mixed matrix hollow ber membranes with modied zeolite were relatively higher compared to that of the hollow ber mixed matrix membranes with unmodied zeolite. PESmodied zeolite 20 wt% silane yielded signicant selectivity enhancement of 7.26 and 46.28 for O2 /N2 and CO2 /CH4 , respectively. 2008 Elsevier B.V. All rights reserved.

Article history: Received 24 September 2007 Received in revised form 13 February 2008 Accepted 29 March 2008 Available online 6 April 2008 Keywords: Gas separation membrane Mixed matrix membrane Amino silane Surface modication

1. Introduction Membrane processes have encompassed a wide range of application in gas separation where by gas separation via selective permeation through polymer membranes has become one of the fastest growing branches of the separation technology [1]. In particular, separation of CO2 /CH4 has received high attention due to the great signicance on industrial applications such as natural gas purication and CH4 recovery from landll gas. However, membrane separation needs to compete directly with traditional gas separation processes such as scrubbing, amine treatment and indirectly with the untreated use of the contaminated gas with low fuel value. Carbon dioxide needs to be removed from the natural gas before it can be distributed to consumer due to the presence of water, since CO2 can be very corrosive towards the gas pipe lines. Hence, separation of CO2 and CH4 is necessary in this process. In order to extend membrane application and compete successfully with the traditional CO2 /CH4 gas separation processes, great attention has been paid in fabricating high separation performance

Corresponding author. Tel.: +60 7 5535592; fax: +60 7 5581463. E-mail address: afauzi@utm.my (A.F. Ismail). 0376-7388/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2008.03.067

membrane. Modications on the physical and chemical structures of polymer lms have been carried out in order to achieve better separation characteristics. For the last two decades, the possibility of using synthetic membranes for industrial gas separations has attracted considerable interest since membrane separation technologies have the advantages of energy efciency, simplicity and low cost. However, for wider commercial utilization, there is still a need to develop membranes with higher permeate uxes and higher transport selectivities. Conductive polymers, due to their high gas transport selectivities, give rise to a new class of polymeric materials for membrane-based gas separation though poor mechanical properties obstruct the applications for this purpose. This problem leads to the exploration of a new idea of combining the conducting polymers with insulating polymers forming mixed matrix composite membranes. Mixed matrix composite membranes have received world-wide attention in the eld of material science in the last 2 decades [27]. As the consequence, it has been proposed as an alternative approach to obtain the high selectivity benets of molecular sieve materials (e.g., carbon molecular sieves (CMS), silica and zeolites) and to counter the costly processing of purely homogeneous molecular sieving membranes through incorporating these sieves

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into a process able polymeric matrix. This heterogeneous or hybrid membrane concept combines the advantages of each medium: high separation capabilities of the molecular sieves, the desirable mechanical properties and economical processing capabilities of the polymers. Although the interphases on zeolite (inorganic composites) occupy an extremely small volume fraction (i.e., less than 10%), it appears to have a signicant effect on the separation performance of mixed matrix membranes [4]. The origins of the imperfect interphases are complicated. Poor compatibility between molecular sieve and polymer matrix where by the tendency to develop voids between polymer and zeolite phases are very high, uneven shrinkages and stresses of these two components during the mem et al. [4] brane formation may be some of the possible causes. Suer also stated in their previous studies that, polymer chain rigidication and partial pore blockage of zeolites have been hypothesized and partially conrmed to form the lower gas permeation data of mixed matrix membranes. Tantekin-Ersolmaz et al. [5] reported that mixed matrix membranes developed from glassy polymers and zeolites showed enhanced separation behaviour. However, attempt in fabricating mixed matrix membranes using glassy polymers and zeolites has resulted in the presence of voids at the polymerzeolite interface, thus reducing the separation performance of the composite membrane relative to the pure polymer [6]. As the applications for polymer-based organicinorganic composites membranes expand, new challenges arise. One of these challenges is to synthesize both higher performance membranes that are more durable. Therefore, it is important to overcome these challenges that prevents successful introduction of inorganic molecular sieve materials into an organic polymer matrix. Many studies have been attempted to improve the interaction between the polymer and molecular sieve in order to enhance the separation performance [7]. The chemical modication on the surface of molecular sieve is one of methods to improve the interaction of polymer and molecular sieve. Generally, chemical modication is used silane coupling agents, such as (3-aminopropyl)-triethoxy silane, N--(aminoethyl)-aminopropyltrimethoxy silane, (-glycidyloxypropyl)-trimethoxy silane and (3-aminopropyl)-dimethylethoxy silane [811]. In addition to overcome the existence defects, several different silane coupling agents were successfully employed to improve adhesion between the polymer and zeolite. However, the resulting permeabilities were slightly lower, and ideal selectivities were largely unchanged when compared to the pure polymer. Therefore, the present work proposes an alternative preparation of mixed matrix hollow ber membranes for O2 /N2 and CO2 /CH4 separation by introducing a novel Dynasylan Ameo (DA) silane coupling agent on zeolite surface and then investigating its effects on the separation performance of mixed matrix hollow ber membranes. To our knowledge, there is no documentation on the use of DA silane agent to modify zeolite surface for PES zeolite mixed matrix hollow ber membrane.

Table 1 Spinning condition and process parameter No. 1 2 3 4 5 6 7 8 9 10 11 12 13 Spinning conditions Spinning solution Binary mixture Zeolite concentration Amino silane concentration Polymer concentration (by weight) Spinneret temperature ( C) Spinneret o.d./i.d. Bore uid ow rate (ml/min) Dope pressure (bar) Range of air gap distance (cm) Coagulant Coagulant temperature ( C) Drying procedure Value PES, zeolite, aminosilane/NMP 25/75 20 wt% 10, 15 and 20 wt% 25% 25 0.6 mm/0.3 mm 0.83 1 10 H2 O 25 2 days in water at room temperature 4 h in methanol at room temperature 2 days air dry at room temperature

ticle size was 2 m. In order to remove the adsorbed water vapor or other organic vapors, all zeolite particles were dehydrated at 300 C for 3 h before use. 2.2. Fabrication of asymmetric mixed matrix hollow ber membrane The polymer solution was consisted of 25 wt% PES, 75% NMP and 20 wt% of zeolite in total solid. The homogeneous polyethersulfone were prepared according to the following procedure; while stirring the inorganic molecular sieve particles were dispersed into the solvent, followed by the addition of a desired amount of polyethersulfone. Then, the solution was stirred for another 24 h at higher speed. Before spinning, the prepared homogeneous solution was degassed under vacuums for 3 h. Asymmetric mixed matrix hollow ber membranes were prepared using a dry-jet wet spinning process. The spinneret has an o.d. and i.d. of 0.6 and 0.3 mm, respectively. The extrusion rate of the spinning dope was controlled either by nitrogen pressure or pump ow rate using an adjusting valve. The internal coagulant was controlled by a syringe pump. The external coagulant bath was lled with tap water at room temperature. The nascent ber appeared at the end of the centrally located needle of the spinneret and passed through an air gap before entering the coagulant bath. After coagulation, the hollow ber was guided through the roller and then coiled into the storing tank. The hollow bers were kept in the storing tank for 24 h to remove NMP and then transferred to a second tank containing fresh methanol for 1 h to remove residual NMP completely. The bers were dried at room temperature for 3 days. The detailed spinning conditions for the treated and untreated membranes are shown in Table 1. 2.3. Chemical modication method of zeolite surface Dynasylan Ameo silane coupling agents are silicon-based chemicals that contain two types of reactivity inorganic and organic in the same molecule. A typical general structure is shown as below (RO)3 SiCH2 CH2 CH2 X where RO is a hydrolyzable group, ethoxy and X is an organofunctional group of amino. The silane coupling agent will act as an interface between an inorganic substrate, zeolite 4A and an organic material, polyethersulfone to bond, or couple, these two dissimilar materials. Chemical modication on zeolite 4A surface consists of three steps. Firstly, the mixture of ethanol (EtOH) solution (EtOH 95%, H2 O 5%) plus DA silane plus zeolite 4A were stirred in a vessel

2. Experimental 2.1. Material selection Polyethersulfone by Solvay Advanced Material (USA). The polymers were dried in a vacuum oven at 120 C overnight before dope preparation; N-methyl-pyrrolidinone (NMP) from Merck was used as the solvent due to its low toxicity. The inorganic ller molecular sieve involved was zeolite 4A purchased from Aldrich and the par-

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by a motor driven stirrer under room temperature for 4 h. Ethanol was chosen in this study due to its strong interaction with water and its relatively benign nature. Secondly, the mixture was then ltered through a lter paper and the residue was washed thoroughly with ethanol to remove the unreacted silane. Finally, the modied zeolite was dehydrated at 110 C for 2 h in a vacuum oven to remove the adsorbed water vapor or other organic vapors before it was ready to be used in preparation of dope solution. 2.4. Post-treatment procedure In order to seal the membrane defects, an assembled hollow ber (PESzeolite 20 wt% silane) was immersed in a coating solution containing 3 wt% polydimethylsiloxane in n-hexane for 24 h. This duration of time was needed to cure the silicon rubber coating in drying oven at 60 C. Afterwards, the performance of the prepared membrane was measured using pure oxygen, nitrogen, methane and carbon dioxide gases permeation tests. 2.5. Characterization of asymmetric mixed matrix hollow ber membrane A Supra 35 VP Field Emission Scanning Electron Microscopy (FESEM) was used to investigate the asymmetric structure and to determine the dimension of the bers. Membrane samples were fractured in liquid nitrogen. The membranes were mounted on an aluminium disk with a double surface tape and then the sample holder was placed and evacuated in a sputter-coater with gold. The changes in the chemical structure caused by modication using silane treatment were identied using Fourier transform infrared spectroscopy (FTIR). The IR absorption spectra were obtained at room temperature in a range from 4000 to 500 cm1 with a spectral resolution of 8 cm1 and averaged over 16 scans. The glass transition temperature of each hollow ber membranes was determined using differential scanning calorimetry (Mettler Toledo DSC 822e). A small piece of hollow ber membrane sample was rst stored under vacuum at 100 C for 24 h to remove adsorbed water; then weighed and placed into aluminium DSC pans. The scanning range was 50320 C with scanning rate of 10 C min1 in the rst DSC cycle to remove thermal history and then cooled from 320 to 25 C at the rate of 10 C min1 ; nally the second cycle was carried out using the same procedure. 2.6. Module fabrication and gas permeation experiment The hollow ber membranes were tested in a pure gas system using a variable using variable-volume constant-pressure method the upstream pressure was maintained at up to 10 bar and the downstream pressure was effectively atmospheric. Permeation experiments were carried out at room temperature. The permeance was measured after the steady state was reached, which took about 10 min. Five bers with a length of 15 cm were assembled into a bundle. One end of the bundle was sealed with epoxy resin while the shell side of the other end was glued onto an aluminium holder using hysol epoxy adhesive. The prepared bundle was tted into a stainless steel tube, the i.d. of which was 2.2 cm, respectively. The permeance or pressure-normalized ux, (P/L), is calculated by: P L = Qi ( p)(n Dl) (1)

(cm). Permeances are expressed in gas permeation units, GPU (1 GPU = 1 106 cm3 (STP) cm2 s1 cm Hg1 ). The ideal separation factor (gas A over gas B) of the hollow ber membrane was determined by = (P/L)A (P/L)B (2)

3. Results and discussion 3.1. Characterization of polyethersulfone mixed matrix hollow ber membrane for unmodied and modied zeolites The interface between a polymer matrix and inorganic ller plays an important role in the performance of mixed matrix membranes. A silane coupling agent generally can enhance the adhesion between polymer matrix and inorganic ller [12]. Therefore, in this study, the effects of chemical modication on zeolite surface with 3-aminopropyltriethoxysilane (Dynasylan Ameo) for fabricated PESzeolite mixed matrix hollow ber membrane were examined. Hence, the characterization and comparison of polyethersulfone for unmodied and modied zeolite would be further discussed. FESEM characterization was carried out on the fabricated membrane in order to determine the qualitative analysis of hollow ber mixed matrix membrane. The FESEM micrographs of the polyethersulfonezeolite mixed matrix hollow ber membrane are shown in Figs. 1 and 2. Fig. 2 illustrates the partial cross-sectional area of representative spun hollow ber mixed matrix membrane, PESmodied zeolite; the gure clearly reveals the presence of some macrovoids under the skin layer. While, as shown in Fig. 2, the thickness of active skin layer was observed to be approximately around 279.1 nm. Foremost, by referring to Figs. 1 and 2, the differences in adhesion between PES with modied zeolite and PES with unmodied zeolite can be successfully distinguished. The addition of silane in mixed matrix hollow ber membrane caused the polymer coating on the zeolite particles to be apparent while without silane clean zeolite particles can be seen in the polymer matrix in other words it showing sieve-in-a-cage morphology in mixed matrix hollow ber. The revealing of submicron gaps around the sieves may be formed due to poor adhesion between the polymer and zeolite particle. Therefore, based on Figs. 1 and 2, it can be concluded that the DA silane coupling agent has improved the zeolitepolymer adhesion. The unselective voids were primarily due to poor adhesion between the ller and the polymer, creating channels between the interphases or cages surrounding the ller. These channels introduced a less resistant path for the gas to bypass the ller particles, cancelling the intended role of the llers. Moreover, the poor adhesion of polymer and zeolite was likely to cause surface ruptures in some areas of the active layer. These could be seen in Fig. 1(b) at 5000 magnication. This result is in agreement with the previous study by Mahajan and Koros [6] which suggested that these defects were formed as a result of polymer and sieve surface incompatibility. When PES is reinforced with zeolite 4A, the unselective voids region between polymer and zeolite are involved in a complex interplay of physical and chemical factors. These factors are related to adhesion, physical strength and expansion coefcient of the membrane fabricated. A very destructive force affecting adhesion is the migration of water to the hydrophilic surface of the inorganic reinforcement. Water attacks the interface, destroying the bond between the polymer and reinforcement, but fundamentally amino silane will create a water-resistant bond at the interface between the zeolite 4A and PES. These unique chemical and physical properties of amino silane will enhance the bond strength, thus it provides a stable bond between two.

where Qi is the volumetric ow rate of gas i at standard temperature and pressure, p is the trans-membrane pressure drop (cmHg), n is the number of tested bers; D is the outer diameter of the bers (cm); l is the effective length of the bers

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Fig. 2. SEM picture of asymmetric polyethersulfone mixed matrix hollow ber with treated zeolite 4A using 20% silane concentration at the: (a) cross-section and (b) outer surface image layer.

Fig. 1. SEM picture of asymmetric polyethersulfoneuntreated zeolite 4A mixed matrix hollow ber membrane at the: (a) cross-section and (b) outer surface image layer.

The molecular formula for Dynasylan Ameo is H2 N(CH2 )3 Si(OC2 H5 )3 . The silicon at the centre is connected to two different functional groups; the organophilic amino group (NH2 ) and the ethoxy group (C2 H5 O). Surface treatment of zeolites with DA silane coupling agent was carried out to produce silanol groups through hydrolysis reaction [13]. Silanol groups, a product of a hydrolysis reaction, react with hydroxyl groups found on zeolite surfaces to form siloxane bonds (SiOzeolite) through a condensation reaction. The DA silane agent consists of three ethoxy groups that are three reactive centres which can be used for the formation siloxane bonds with the zeolite channel. These SiOzeolite bonds formed a stable structure on the surface of zeolite. Upon the hydrolysis, ethanol was released. On the other hand, the organophilic amino group reacted with the polymer chain. Fig. 3(a) and (b) shows the chemical structure of DA and chemical modication on zeolite surface, respectively. The hydrolysis reaction and condensation reaction are shown in Fig. 4. Due to the stable structure of SiOzeolite bonds on the surface of zeolite, the presence of voids surrounded on zeolite surface was nally reduced as shown in Fig. 2. Hence, this good compatibility between polymer matrix and zeolite would nally diminish gas penetrants via unselective voids of zeolite and simultaneously high gas separation performance of membrane is able to be achieved.

Fourier transform infrared spectroscopy analyses were carried out on each of mixed matrix membrane fabricated. Through this analysis, infrared spectrum measurement based on the absorption band changes of functional groups in fabricated hollow ber mixed matrix membrane was used to determine if there was a presence of chemical bonding. Therefore, this analysis was primarily used to identify whether the chemical modication on zeolite surface had taken place. The reactions as described in Figs. 3 and 4 can be proven through these differential spectra. Therefore, the change of vibration band position of PESunmodied zeolite (0 wt% silane), pure liquid silane, (3-aminopropyl)-triethoxy methyl silane as well as PESmodied zeolite has been examined throughout FTIR analysis. Fig. 5 presents the FTIR spectroscopy of PES mixed matrix membrane with untreated zeolite 4A and modied surface of zeolite with different concentration of silane agent in the region of the 4000400 cm1 , respectively. The adsorption peak at 1700 and 1580 cm1 appearing in the spectrum of PESzeolite represent the stretching vibration of C O and bending vibration of NH. The adsorption peaks at 2913 cm1 was related to aliphatic CH (CH3 and CH2 ). The increasing of silane concentration in the treatment of zeolite caused a signicant increase in the relative intensity of this peak. These indicated that the silane coupling agent is adhered to the surface of zeolite. The results showed that the OH groups of zeolite surface reacts with silanol group of Dynasylan Ameo generated by hydrolysis to form modied zeolite surface with organic compound on the surface. Moreover, from Fig. 5 the small

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Fig. 3. (a) Chemical structure of (3-aminopropyl)-triethoxy methyl silane; (b) chemical modication on zeolite surface.

Fig. 4. Hydrolysis and condensation reaction of silane coupling agent.

intensication and broadness of the band at 3400 cm1 was also observed with the increasing of silane concentration. The absorption at 3400 cm1 was associated to vibration of hydrogen bonding (NH). The increasing of NH band showed that there is a considerable amount of PES chains adhered on zeolite surface. In other words the chemical modication on zeolite surface had successfully taken place. The free silanol groups on the zeolite surface are the most reactive groups and may provide the side for the physical and chemical adsorption of the silane coupling agent. Therefore, the FTIR spectra in the region of 2000600 cm1 are analyzed in Fig. 6 to study the change of bands with different silane concentration. From Fig. 6, the weak absorption peak near 920 cm1 is the overlapping bond of the asymmetric stretching of SiOSi with SiOC stretching vibration and they are originated from the bond between the OH bonded to the Si atom on the zeolite surface and the OH bonded to the Si

Fig. 5. FTIR spectra recorded in the region of 4000400 cm1 for (a) pure liquid silane, (b) PESzeolite 0 wt% silane, (c) PESzeolite 10 wt% silane, (d) PESzeolite 15 wt% silane, and (e) PESzeolite 20 wt% silane.

Fig. 6. FTIR spectra recorded for PESmodied zeolite in the region of 2000400 cm1 : (a) 0 wt% silane, (b) 10 wt% silane, (c) 15 wt% silane and (d) 20 wt% silane.

A.F. Ismail et al. / Journal of Membrane Science 319 (2008) 306312 Table 2 The effect of silane concentration on the glass transition temperature of polyethersulfonezeolite mixed matrix hollow ber membranes Membrane Untreated zeolite 10 wt% DA silane 15 wt% DA silane 20 wt% DA silane Tg ( C) 219.05 222.12 222.47 224.51

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Table 3 Effect of silane concentration on the gas separation performance of polyethersulfonezeolite mixed matrix hollow ber membranes at room temperature and 10 bar Membrane Single gas permeance (GPU) CO2 Untreated 10 wt% DA silane 15 wt% DA silane 20 wt% DA silane 33.77 20.25 10.17 6.67 CH4 11.81 1.32 0.451 0.232 O2 8.94 3.47 3.03 2.71 N2 4.19 1.27 0.987 0.567 Selectivity CO2 /CH4 2.86 15.43 22.57 28.75 O2 /N2 2.13 2.74 3.07 4.78

atom of the silane molecule (OHOH interaction). Through the samples, the band detected at 1002 cm1 is attributed to nonbridging OH stretching vibration representing the H-bonding that occurred between the H atom of OH group bonded to the Si atom of (3aminopropyl)-triethoxy methyl silane and oxygen atoms bonded to Si atoms on the zeolite surface (OOH interaction). With increasing silane concentration a small intensication of absorption was detected at 1408 cm1 which indicates a strong bend of CH2 stretching. The peak located near 11201050 cm1 indicating the presence of NH bond exists in PESmodied zeolite 15 wt% silane and PESmodied zeolite 20 wt% while the peak around 1654 cm1 represents the CN stretching vibration. The inuence of silane modication on the glass transition temperature of PESzeolite mixed matrix hollow ber membranes are tabulated in Table 2. The Tg of the mixed matrix hollow ber membranes increased about 14 C with the increasing of DA silane concentration on the surface treatment of the zeolite particles as depicted in Table 2. This phenomenon indicates that the surface modication of zeolite using DA silane coupling agent affects the mechanical properties of continuous phase as suggested in the previous study [3]. The increase of Tg might be due to the zeolite restricts the movement of the polymer chains by the formation of hydrogen bonding between the zeolite particles and polymer. However, Li et al. [14] observed that the main factors caused the increase of Tg with an increase of zeolite loading is due to a fair interfacial interaction between polymer and zeolite. Based on Table 2 it can be concluded that the zeolite surface modication using DA silane coupling agent could induced the adherence between polymer matrix and zeolite particles. 3.2. Effect of chemical modication of zeolite surface on gas separation performance Although the improvement on adhesion between zeolite and polymer surface was clearly observed by FESEM, the great signicant criteria required by a good membrane was the ability to show high gas separation performance. Thus, in this study the effect of chemical modication on zeolite surface towards gas separation performance was carried out to identify the membrane effectiveness. The gas permeation properties of every hollow ber mixed matrix membrane were measured using a variable-pressure constant-volume method. The permeability of each gas through each cast of membrane was measured at least for 3 runs. The permeabilities for pure gases O2 , N2 , CO2 , and CH4 and the calculated ideal separation factor for O2 /N2 , CO2 /CH4 gas pairs for different polymer concentration of PI/PESzeolite mixed matrix membranes are tabulated in Table 3. Generally, the three main pathways of gas transport through the mixed matrix membranes are through dense layer of PES matrix, highly selective zeolite sieve and non-selective gaps or voids between the matrix and sieve particles. As presented in Table 3, the trend of permeability of PES mixed matrix hollow ber membrane as a function of silane concentration and untreated zeolite were similar for all gases studied indicated that similar

permeation mechanism for all of the membranes. Based on data presented in Table 3, the O2 /N2 and CO2 /CH4 selectivity values for untreated zeolite were very low. These might indicate the Knudsen diffusion behaviour in the membrane due to the presence of severe voids between zeolite particles and agglomeration as shown in Fig. 1. Table 3 also shows that the permeability of all gases decreased with increasing silane concentration in PES modied zeolite while selectivity of these tested gases increase with the increasing amino silane concentration. The increase in selectivity may be due to the formation of better contact as well as good adhesion between polymer and zeolite phases. The leakage through the unselective voids was reduced after modication as observed from FESEM micrographs. Silane as adhesion promoters had reduced the micro voids around zeolite surface hence resulting in an increase of selectivity of tested gases O2 /N2 and CO2 /CH4 . Tsukruk and Bliznyuk [15] suggested that the presence of (3-aminopropyl)-triethoxy methyl silane with chain length of on the top of zeolite surface for modi(59) 1010 m (59 A) ed zeolite had successfully reduced the direct partial blockage of zeolite induced by polymer chain and nally increased the gas permeability of hollow ber mixed matrix membranes. Moreover, the thin (3-aminopropyl)-triethoxy methyl silane layer on zeolite surface had not only reduced the pore blockage of zeolite, but also diminished the transport of gas penetrants via the unselective voids due to better adhesion between (3-aminopropyl)-triethoxy methyl silane and the polymer matrix (PES) and the existence of various functional groups in this space (i.e., CH2 and CH3 ). Therefore, the originally high selectivity nature of zeolite remains almost intact and the resultant mixed matrix membranes have a higher permeability as well as high in selectivity as reported by Li et al. [14]. As can be seen in Table 3, the silane treated zeolite lled hollow ber mixed matrix membrane improved the O2 /N2 and CO2 /CH4 selectivities. However, the improved selectivities were still lower compared to neat PES hollow ber membrane. The results indicated that the silane treatment induced to enhance the adherence but this improvement did not completely reduce the interface void between polymer and zeolite particles. 3.3. Effect of silicone coating and thermal curing on gas separation performances As discussed in Section 3.2, the unselective voids were not completely eliminated in the PESzeolite modied. Therefore, the inuence of silicone rubber coating and thermal curing on the gas transport and gas separation properties of fabricated hollow ber mixed matrix membrane polyethersulfonemodied zeolite (20 wt% silane) was studied. Gas separation performance of coated membrane bers was also inuenced by thermal curing time. In this study the coated membrane bers was dried in a vacuum oven at temperature 60 C for 2 days. These fabricated membranes were selected due to their better separation properties compared to other silane concentration. Gas separation performance of this fabricated membrane was improved

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Table 4 Effect of silicone rubber coating on gas permeation properties of polyethersulfonemodied zeolite (20 wt% silane) mixed matrix hollow ber membrane at room temperature and 10 bar Membrane Single gas permeance (GPU) CO2 Uncoated PESsilane Coated PESsilane Coated neat PES 6.67 1.62 4.73 CH4 0.232 0.035 0.163 O2 2.71 0.574 1.05 N2 0.567 0.079 0.207 Selectivity CO2 /CH4 28.75 46.28 29.02 O2 /N2 4.78 7.26 5.07

As proven by the results obtained from FESEM and FTIR analysis, Dynasylan Ameo silane was successfully used to improve the adhesion between the polymer and zeolite surface. Consequently, this modication yielded good compatibility between PESzeolite 4A which in turns enhanced the gas separation performance of hollow ber mixed matrix membranes. The gas separation performance of hollow ber mixed matrix membrane PESzeolite 4A was enhanced through coating using silicone rubber solution. This silicon rubber coating was able to seal the defect of the outermost skin of membrane ber. Acknowledgements We gratefully acknowledge nancial support from the Ministry of Science, Technology and Innovation (MOSTI). The authors also would like to thank Ms. Osy for helping in gas permeation testing. References
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and comparison between coated and uncoated membrane was made. Table 4 shows the comparison of permeability and selectivity for tested gases between coated, uncoated PESmodied zeolite (20 wt% silane) and coated neat PES hollow ber membrane. From the tabulated data obtained, it can be observed that the PESmodied zeolite hollow bers membrane coated with silicon rubber yield low permeability and high selectivity in the separation of O2 /N2 and CO2 /CH4 compared to the uncoated PESmodied zeolite and neat PES bers. As shown in Table 4 the highest membrane selectivity yielded from the hollow ber mixed matrix PESmodied zeolite (20 wt% silane) coated membrane was 7.26 and 46.28 for O2 /N2 and CO2 /CH4 , respectively. This is probably due to the defects of the outermost skin bers that sealed by the silicone coating. The surface structure of the membrane was improved by reducing the defects on the ber surface, hence resulting in high selectivity and low permeability. From the highest selectivity yield of 7.28 for O2 /N2 and 46.28 for CO2 /CH4 , it can be concluded that this silicone rubber coating can successfully suppress gas transport of Knudsen diffusion mechanism. Hence, the gas transport mechanism that dominated this coated bers are a combination of molecular sieving and solution diffusion. This phenomenon indicated that the voids generated by the unfavourable interaction between polymer and zeolite phases can be eliminated by combination of silane surface treatment and silicon coating. 4. Conclusions Polyethersulfone mixed matrix hollow ber membranes were successfully tailored in this study by incorporating polyethersulfonemodied and unmodied zeolite 4A. The effects of chemical modication on zeolite surface were investigated. In order to improve the fabricated polyethersulfonemodied zeolite membrane, the effects of silicone rubber coating and thermal curing on the fabricated modied ber were also studied. The corresponding conclusions were drawn from the test results obtained are: Hollow ber mixed matrix membrane was successfully fabricated and analyzed in terms of separation properties and FESEM analysis as well as FTIR analysis to examine the morphology or structure of fabricated hollow ber mixed matrix membrane.