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Journal of Membrane Science 307 (2008) 5361

Effect of carbon molecular sieve sizing with poly(vinyl pyrrolidone) K-15 on carbon molecular sievepolysulfone mixed matrix membrane
W.A.W. Razah, A.F. Ismail
Membrane Research Unit, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor, Malaysia Received 20 April 2007; received in revised form 29 August 2007; accepted 8 September 2007 Available online 14 September 2007

Abstract Mixed matrix membranes (MMMs) comprising polysulfone (PSF) Udel P-1700 and 30 wt% carbon molecular sieve (CMS) particles (<25 m) have been fabricated and characterized. CMS particles were treated in poly(vinyl pyrrolidone) kollidone 15 (PVP K-15) sizing bath solution (110 wt% in isopropanol) prior to embedment into the matrix solution to improve matrixsieve interfacial adhesion. This study investigated the effects of CMS sizing with PVP K-15 on the morphology and the gas separation performance of PSFCMS MMMs. The fabricated MMMs were characterized using TGA, DSC, FESEM, ATR-FTIR and single gas permeation test using high purity O2 and N2 . A dramatic improvement in CMSPSF adhesion was observed using FESEM micrographs upon incorporation of PVP K-15-sized CMS particles. ATR-FTIR results suggest the occurrence of intermolecular interaction between PVP K-15 sizing layer on the outer surface of CMS particles and PSF matrix. A substantial recovery of separation performance was achieved whereby the PSFPVP-sized CMS MMM exhibited 1.7 times higher O2 /N2 selectivity compared to that of unmodied MMM. 2007 Elsevier B.V. All rights reserved.
Keywords: Mixed matrix membrane; Gas separations; Carbon molecular sieve; Polysulfone membrane; Poly(vinyl pyrrolidone)

1. Introduction Mixed matrix material has been developed with the ultimate goal of encapsulating the molecular sieve entities within a high-performance continuous polymer matrix [15]. In gas separation technology, this hybrid material has stimulated a great research interest due to its potential to overcome unresolved limitations in conventional membrane materials. It is believed that this emerging approach is viable to synergistically combine the good features of both phases and overcome limitation in each medium. Porous nature of molecular sieve material provides the justication of high productivity and selectivity in mixed matrix membrane [4]. The polymer phase determines the minimum separation performance of the membrane and provides the desirable mechanical properties and economical processability of mixed matrix membrane.

Corresponding author. Tel.: +60 7 5535592; fax: +60 7 5581463. E-mail address: afauzi@utm.my (A.F. Ismail).

Currently, poor polymersieve adhesion becomes one of the critical issues in mixed matrix membrane development causing the realization of an ideal mixed matrix membrane becomes practically challenging [618]. Formation of sievein-a-cage morphology is the most common indication of poor polymersieve contact and MMMs with this morphology exhibit higher permeabilities and selectivities approaching those of the native polymer or even worse [618]. Since enhancement of selectivity by molecular sieves can only be achieved in the absence of these defects, concerted efforts have been directed to enhance the adhesion between these two phases [7]. Duval et al. [19] modied the zeolite surface with silane coupling agents to promote zeolitematrix adhesion. SEM micrograph revealed a good coupling between silane and zeolite but the selectivity was insignicantly affected. This is possibly due to inappropriate selection of silane agent that could effectively prevent the void formation or the silane agent itself may create additional non-selective and resistive layer in the interphase region [20]. Subsequent study by Yong et al. [21] showed that void-free zeoliteMatrimid MMMs were obtainable by employing a compatibilizer, 2,4,6-triaminopyrimidine (TAP). Despite

0376-7388/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2007.09.007

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achieving almost four times higher selectivity in CO2 /N2 and O2 /N2 compared to pure Matrimid, the O2 and CO2 permeability was decreased at least fortyfold. Mahajan et al., [7] on the other hand, proposed to maintain the polymer exibility during membrane formation by casting at temperature close to the Tg of the polymer matrix. Several workable MMMs using intermediate Tg polymers have been successfully fabricated using this approach [1113]. Conversely, this approach is not practical for high Tg polymers because it is very difcult to nd a non-volatile solvent with enough high boiling point to meet the required temperature during membrane formation [6]. The addition of plasticizer is also not practical because it could worsen the intrinsic gas separation performance of the polymer [1220]. Poly(vinyl pyrrolidone), PVP is a common chemical used as additive in casting solution for preparation of phase inversion PSF [2223]. It is known as an agent for suppressing macropore formation in phase inversion membranes. Otherwise, PVP is an established thermoplastic sizing in composite technology. The effectiveness of using PVP as a sizing agent to promote the adhesion between inorganic substrate with polymer matrix has been extensively reported in ber reinforced polymer matrix composites development [24,25]. The sizing technique, which is a surface coating approach deserves a noteworthy consideration and can be adapted in MMMs development. Sizing known as coating or nishes are widely used to protect ber surface from damage, improve the ber wetting by matrix and protect ber surface reactivity [26,27]. Sizing could increase the strength of the interphase by introducing more chemical reactive site and/or more surface area for adhesion [2831] involving neither complicated chemical reaction nor grafting process. The functional groups along sized bers can react and/or interact with the matrix, giving rise to strong interactions between the ber and the matrix [32,33]. Furthermore, the entanglement of polymer sizing and polymer matrix molecules via inter-diffusion mechanism strengthens the interphase adhesion [28]. Inspired by these successful ndings, the application of PVP can be potentially adapted for mixed matrix membrane development with the intention of improving the compatibility of the inorganic sieving material with the matrix polymer. In this study, the modication of CMS particles using sizing technique was explored. Physical deposition of PVP K-15, sizing agent onto the surface of CMS particles was employed
Table 1 Chemical structures and molecular weights of PSF and PVP Polymer Chemical structure

by treating the CMS particles in sizing bath solution containing 110 wt% PVP K-15 in isopropanol solution prior to embedment into the polymer matrix. In order to analyze the impacts of CMS sizing with PVP K-15 on the morphology and separation performance of membrane, MMM lms comprising 30 wt% of PVP K-15-sized CMS in polysulfone Udel P-1700 were fabricated and were characterized using TGA, DSC, FESEM and pure gas permeation test. 2. Experimental 2.1. Raw material A commercial Udel P-1700 polysulfone, purchased from Amoco Performance Inc., USA was chosen as the polymer matrix phase. It has an average molecular weight of 45,000. The solvent, n-methyl-2-pyrrolidone (NMP) supplied by Merck was used as received. The molecular sieve entities were carbon molecular sieve particles synthesized from polyacrilonitrile (PAN) precursor described elsewhere [34]. The pore sizes of which make them PAN-based CMS could range from 4 to 6 A, suitable for use as molecular sieve [35]. The CMS particle size was reduced to less than 25 m as veried by FESEM. Poly (vinylpyrrolidone) kollidone 15 or PVP K-15 with the average molecular weight of 10,000 was purchased from Merck, Germany. Reagent grade isopropanol (Merck, Germany) was used as the solvent to dissolved PVP K-15. Prior to any use, PSF and CMS particles were preconditioned in a vacuum oven at 100 and 250 C, respectively for 12 h to remove trapped moisture. Table 1 summarizes the chemical structures and molecular weights of PSF and PVP used in this study. 2.2. Preparation of PVP K-15-sized CMS The aky and white powder of PVP K-15 was dissolved in isopropanol to produce dilute solution with the concentration of 110 wt% PVP K-15. An intended amount of CMS particles was added to the PVP K-15 sizing bath solution and stirred at 30 rpm for 1 h. Then, the sized CMS were ltered from the excess solution using Whatman 40 lter paper. The sized CMS cake was rinsed with isopropanol to remove unadsorbed polymer before further drying in a vacuum oven at 50 C for 24 h. A similar range

Molecular weight

PSF (Udel, P-1700)

45,000

PVP K-15

10,000

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55

Fig. 1. Preparation of PSFPVP-sized CMS suspension.

of PVP bath solution has been studied to size carbon and glass ber in Refs. [30,36]. This working range was chosen because of several considerations. First, conformation of the bound polymer chains on solid surface may vary with increasing polymer solution concentration [36]. A dilute PVP solution is needed to wet the particle surface and provide easy access to the polymer chains to conform. However, a very dilute solution reduces the possibility of chain attachment. As a result, some part of the CMS surface will be left unoccupied. The possibility of chain attachment is likely to increase by increasing the concentration of PVP in bath solution. Therefore, a suitable concentration of PVP bath solution that can easily wet the particle surface and provided sufcient chain attachment at the same time was selected within this bath concentration range. In addition, damping effect of PVP on carbon surface was encountered when PVP K-15 bath concentration used exceeding 10 wt%. A thick layer of PVP formed on the CMS surface and prolonged drying duration was required. This problem was also reported in Refs. [30,36]. 2.3. Fabrication of membrane There are several approaches to prepare polymersieve suspension. For this study, 25 wt% PSF in NMP solution was rst prepared by dissolving pre-dried PSF pellets in NMP and stirred for 12 h at temperatures of 6070 C. In separate ask, the intended amount of PVP-sized CMS was wet with small amount of NMP. Then, the PSF dope solution was gradually added into the ask containing wet CMS and stirred at 30 rpm. PSF dope solution addition and stirring process were repeated until a homogenous suspension solution was obtained. The sequence for preparation of PSFPVP-sized CMS suspension is summarized in Fig. 1. The following casting process was performed using the protocol outlined in Fig. 2. Forming a ne nonsupported mixed matrix membrane lm is a very challenging task because the membrane lm becomes more opaque, brittle and easy to break during testing upon inclusion of CMS particles. This phenomenon has been discussed in Refs. [4,17,21]. In this study, it was found that the thickness of workable membrane lms could range from 60 to 70 m and were kept in vacuum oven at 60 C prior to characterization to avoid contamination by moisture or impurities. 2.4. Polymer and membrane characterization Thermogravimetry analysis (TGA) using Mettler Toledo thermogravimetry analyzer (TGA TSO800GC1) was performed

Fig. 2. Casting procedure of mixed matrix membrane at elevated temperature.

in order to determine the weight of sizing (Wsizing ) on the surface of the CMS particles. One gram of sized CMS was heated in N2 atmosphere from 30 to 800 C with the heating rate of 10 C min1 and the weight of sizing and estimated sizing thickness was calculated using the following expressions: Wsizing = Wi Wf 100 Wf Wi W f PVP 1000ACMS (1) (2)

estimated sizing thickness on CMS =

where Wi represents the initial weight of the sized CMS (g), Wf is denoted for the nal weight of CMS sample after heating (g), PVP is the density of PVP (1.1 kg m3 ) and ACMS is the surface area of CMS (151.53 m2 g1 ). Considering that the strength of interfacial adhesion is also inuenced by the compatibility of sizing polymer with polymer matrix, it is vital to verify the miscibility of these two polymers during fabrication [37]. In order to determine the miscibility of PSF/PVP blend, the glass transition temperature (Tg ) of the polymers was analyzed with differential scanning calorimetry (Mettler Toledo DSC 822e). Sample was cut into small pieces, weighed and placed into pre-weighed aluminum crucible. Then, the sample was heated from 30 to 300 C with a heating rate of 10 C min1 in the rst cycle to remove the thermal history. The sample was cooled from 250 to 30 C at the rate of 10 C min1 . The same heating procedure was repeated in the second heating cycle. Tg of the sample was determined as the midpoint temperature of the transition region in the second heating cycle. Attenuated total reection fourier transformed infrared (ATR-FTIR) was used to correlate the changes in chemical environment on the CMS surface before and after sizing process. The pre-dried sample of either unsized CMS or sized CMS was pressed against a 45 incidence germanium element. The IR-spectra were recorded on Thermo Nicolet 5700 ATR-FTIR spectroscopy, which is supplied by Thermo Nicolet Corporation and Spectra Tech, USA. Based on the IR-spectra, a qualitative difference in the distribution of functional groups on the surface of sized CMS and unsized CMS could be made. In addition, the miscibility of PVP K-15 in PSF matrix was conrmed by ana-

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lyzing the spectra shifts or the intensity changes of characteristic groups of PSF and PVP K-15 in PSF/PVP blend. Gas permeation properties for mixed matrix membranes were determined using variable-volume constant-pressure method with a permeation cell described elsewhere [38]. Each pure gas (99.97% purity) was tested in the sequence of N2 and O2 and measured three times for each membrane. The measurement was performed at 30 C at 1.5 bar. The pure gas permeability was determined using the following expression: Pi = Vi l At p (3)

where i represents the gas penetrant i, Vi is the volume of gas permeated through the membrane (cm3 , STP), l the membrane thickness (cm), A the effective membrane area (cm2 ), t the permeation time (s) and p is the transmembrane pressure drop (cmHg). The selectivity was obtained using Eq. (4): i/j = Pi Pj (4)

where i/j is the selectivity of gas penetrant i to gas penetrant j, Pi and Pj are the permeability of gas penetrant i and j, respectively. Field emission scanning electron microscope (FESEM) was used to qualitatively analyze the morphology of the fabricated membrane lms and observed the compatibility between the sieves and the polymer matrix. Prior to testing, the lm samples were fractured in liquid nitrogen in order to achieve a clean break. The samples were then mounted on a stainless steel stand with carbon tape and coated with 15 nm of gold using a sputter coater. 3. Results 3.1. Effects of carbon molecular sieve sizing with poly(vinyl pyrrolidone) K-15 on polysulfonecarbon molecular sieve interphase From the thermal gravimetry analysis, the estimated sizing level on the CMS particles after sizing in 10 wt% PVP K-15 in isopropanol solution bath was about 10.2 wt% and the siz ATR-FTIR analysis was ing thickness was approximately 7 A. also performed in order to correlate the changes in the chemical environment on the CMS surface before and after the sizing process. This technique, which probes approximately the rst 2 m of the sample surface was used to verify the deposition of PVP K-15 on the CMS surface. The analytical evaluations of the ATR-FTIR spectra of the unsized CMS and PVP-sized CMS are presented in Fig. 3. They are consistent with the earlier reports [36,39,40]. A qualitative difference in the distribution of functional group on the sized CMS and the unsized CMS can be noted. Based on the FTIR analysis presented in Fig. 3, the highlighted regions represent the presence of two important characteristic bands for PVP K-15. The infrared absorption at 1654 and 1289 cm1 , respectively corresponds to the amide I carbonyl (-C O) band and amide III (CN stretching) band of PVP [41,42]. The surface of unsized CMS on the other hand is

Fig. 3. Infrared spectra for PVP K-15, unsized CMS and PVP K-15-sized CMS.

almost inert with no apparent appearance of characteristic peak. However, the presence of characteristic peaks of PVP could be observed in the sized CMS spectra. The emergence of these peaks becomes more prominent in the spectrum of CMS surface, which was sized in 10 wt% PVP K-15 bath solution. This nding supports that PVP was successfully deposited on the carbon surface. The most sufcient and stable sizing level was achieved by sizing the CMS particles in 10 wt% PVP K-15 bath solution compared to sizing using 1 and 5 wt% PVP K-15 bath concentration. This is because as the concentration of PVP in bath solution increases, the possibility of PVP chains to successfully adsorb and conform onto the CMS surface was also increased. Adsorption of PVP chains per area of CMS increased, thus forming a stronger adherence to the surface [43]. The peak at 2360 cm1 in FTIR spectra presented in Fig. 3 could be attributed to CO2 peak. CO2 peaks are common in IR spectra (2349 cm1 ) because of presence in air. There is a possibility that the background correction run was not often enough to compensate for environmental conditions and can be easily detected within such a low absorbance range (<0.02). The compatibility or the miscibility of PVP K-15 in the PSF matrix was further proven by measuring the glass transition temperature, Tg of the polymer blend using DSC. Composition of PSF/PVP measured for DSC is 32:1. Analysis using DSC has been widely used in previous researches to study the miscibility of polymer blend. Sionkowska [42], Kapantaidakis et al. [44], Zeng et al. [45] and Walsh and Roston [46] have performed DSC

W.A.W. Razah, A.F. Ismail / Journal of Membrane Science 307 (2008) 5361 Table 2 Glass transition temperature of PSF, PVP and PSF/PVP blend Polymer PSF PVP PSF/PVP Composition 1 1 32:1 Tg ( C) 183.01 188.04 183.93 Table 3 Peak assignments of polysulfone Wavenumber (cm1 ) 1585 1504, 1488 1323, 1294 1241,1014 1151 Probable assignment

57

Benzene ring stretch Aromatic carbon groups (skeletal vibration) Sulfonate groups vibration Antisymmetric COC stretch RSO2 R

analysis to study the miscibility of their polymer blend. Tg of pure PSF, pure PVP and PSF/PVP blend are presented in Table 2. DSC curves for these polymers are also depicted in Fig. 4. The DSC scan for PSF/PVP blend exhibited a single Tg located at 183.93 C, which is consistent with the miscibility character of PSF/PVP K-15 mixture. As suggested by Walsh and Roston [46], the Tg of a miscible blend can be predicted using simple

series, parallel and logarithms models. Series model : Parallel model : x1 x2 1 = + Tgb T g1 T g2 Tgb = x1 Tg1 + x2 Tg2 ln Tgb = x1 ln Tg1 + x2 ln Tg2 (5) (6) (7)

Logarithms model :

where x1 and x2 is the composition of polymer 1 and polymer 2, respectively, Tgb the glass transition temperature of polymer blend, Tg1 the glass transition temperature for polymer 1 and Tg2 is the glass transition temperature for polymer 2. The Tg of PSF/PVP blend obtained from DSC results is in a good agreement with predicted value proposed by these three models. This nding further conrmed the miscibility of PVP in PSF. In order to further understand the nature of the PSF/PVP K15 mixture at molecular level, the blend was studied by means of ATR-FTIR spectroscopy. Although ATR-FTIR probes approximately the rst 2 m of the sample surface, in this study it was assumed that the resultant spectrum could represent the whole part of the blend lm. Studies of molecular interaction in polymer blending system using FTIR has been performed and discussed in Refs. [4245]. The spectra of immiscible polymers are basically the sum of the spectra components in pure polymers. In contrast, any specic interactions occurring between the characteristic groups of pure polymers in miscible blend were indicated by frequency shifts or absorption intensity changes [4245]. FTIR spectra for pure PSF, PVP K-15 and PSF/PVP K-15 blend are presented in Fig. 5 for comparison. The probable peak assignment for pure PSF and PVP K-15 are summarized in Tables 3 and 4, respectively. These results are consistent with [38,4245]. Comparison of PSF/PVP K-15 blend spectrum with the spectra of PSF and PVP K-15 reveals the occurrence of interactions between the characteristic groups of PSF and PVP K-15 in the miscible blend. These interactions are indicated by frequency shifts involving several characteristic groups and absorption intensity changes. The strongest shift which is about 24 cm1 has been detected for amide carTable 4 Peak assignments of poly(vinyl pyrrolidone) Wavenumber (cm1 ) 1654 1493/1461/1423/1374 1289 1071 Fig. 4. DSC curves of (a) pure PSF, (b) pure PVP and (c) PSF/PVP blend. Probable assignment Amide C O and CN stretch vibration CH deformation of cyclic CH2 groups Amide III band (CN stretch) CO

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bonyl group (C O) (16541679 cm1 ), the secondary shift which is about 12 cm1 can be observed for sulfonate groups (13231322 cm1 and 12941293 cm1 ) and COC stretching mode (12411240 cm1 ). Obvious changes in absorption intensity are detected for sulfonate group (stretching vibration at 1150 cm1 ) and aromatic carbon group (skeletal vibration assigned at 1322 and 1293 cm1 ). In addition, a peak located at 1289 cm1 which assigned for amide III band (CN stretching mode) is no longer observable in the PSF/PVP K-15 blend spectrum. Probably the frequency of this peak has shifted or its absorption intensity has been reduced and overlapped with the sulfonate group vibration of PSF at 1294 cm1 . As a result a single peak at 1293 cm1 appears in PSF/PVP K-15 blend spectrum. Kapantaidakis et al. [44] reported that a similar trend of the absorption intensity changes were also observed for sulfonate groups and aromatic carbon groups in their PI/PSF blend polymer. This analysis suggests the occurrence of interactions and mixing of PSF and PVP K-15 at the molecular level. The spectra shifts and intensity changes of characteristic groups of PSF and PVP K-15 could be attributed to the inter-molecular interaction within PSF/PVP K-15 blend. In agreement with Sionkowska [42] and Zeng et al. [45], the spectra shift of bands such as the signicant shifting of amide carbonyl group band in PVP and the sulfonate group band in PSF suggests the interactions between PSF and PVP have occurred. The good compatibility between these two polymers can be rationalized by interaction mainly contributed by C O group in PVP chain and sulfonate group in PSF chain. This result was supported by Kapantaidakis et al. [44] who studied the miscibility between PI/PSF blend. The occurrence of interaction at molecular level due to C O group in PI and sulfonate group in PSF has been observed.

3.2. Effects of carbon molecular sieve sizing with poly(vinyl pyrrolidone) K-15 on polysulfonecarbon molecular sieve mixed matrix membrane morphology A qualitative assessment was conducted by using FESEM images in order to compare the morphology of the fabricated MMM containing PVP-sized CMS and MMM containing untreated CMS. Fig. 6 reveals the comparison of the crosssectional images of the unmodied MMM and MMM containing PVP-sized CMS. Both of these membranes were loaded with 30 wt% of CMS. In all FESEM images, CMS particles (<25 m) were randomly distributed and were securely entrapped within 6070 m thick PSF layer. Based on this observation, PVP K-15 sizing has a dramatic inuence on the morphology of PSFCMS MMM. The existence of sub-micron scaled voids could be easily distinguished in the cross-sectional images of unmodied MMM (Fig. 6(a) and (b)). The shaded arrows pointing at the interphase region highlight the occurrence of void surrounding the CMS particle in MMM containing unsized CMS. However, the introduction of PVP-sized CMS into PSF matrix resulted in an almost void-free morphology (Fig. 6(c) and (d)). The PSF matrix adhered intimately on the carbon surface suggesting that the compatibility of the PVP-sized CMS with the matrix was considerably improved. The images revealed in the FESEM micrographs are supported by the ndings from the ATR-FTIR spectra analysis. In unmodied MMM, voids or gaps formation was probably caused by weak interaction between PSF matrix and the inert CMS surface. The stress generation during membrane vitrication process could easily detach the weakly bound polymer chains from the CMS surface. In contrast, PVP K-15 sizing layer which conformed on the outer surface of the CMS promoted the

Fig. 5. Infrared spectra for pure PSF, PVP K-15 and PSF/PVP K-15 blend.

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59

Fig. 6. Comparison of FESEM micrographs for the cross-section of PSFCMS mixed matrix membrane with 30 wt% CMS loading: (a) containing unmodied CMS under 1000 magnication, the white bar indicates 10 m; (b) containing unmodied CMS under 2500 magnication, the white bar indicates 1 m; (c) containing PVP-sized CMS under 1000 magnication, the white bar indicates 10 m; (d) containing PVP-sized CMS under 2500 magnication, the white bar indicates 1 m.

interaction with the surrounded PSF matrix by introducing more reactive side groups such asC O that can form specic interaction with sulfonate group of PSF. The interaction between PVP K-15 and PSF matrix has been conrmed via ATR-FTIR results. This nding indicates the occurrence of intimate mixing at molecular level between the PVP K-15 sizing layer and PSF matrix. In addition, it is envisioned that as PSFPVP interphases are in contact, some of the PVP chains possibly migrate into the PSF region via inter-diffusion mechanism. The inter-diffusion mechanism between polymer interphases was also discussed by Sperling [43] and Laot [37]. These chains nally entangled within the PSF network and strengthen the interphase region. 3.3. Effects of carbon molecular sieve sizing on gas permeation of mixed matrix membranes The gas permeation results for unmodied MMMs and MMMs containing PVP-sized CMS are listed in Table 5. The O2 and N2 permeability for PSFPVP-sized CMS MMMs were higher than those of pure PSF membranes and lower than those of the unmodied PSF-CMS30 MMMs. These MMMs exhibited the highest O2 /N2 selectivity, which was almost 1.7 times of the selectivity in unmodied MMMs.

The gas transport through mixed matrix membrane can occur through three main pathways, which are through dense PSF matrix, highly selective CMS and/or through non-selective gaps or voids between the matrix wall and sieve particles. Dense PSF matrix provides a very selective but highly resistive pathway to the gas ow. Gas transport through CMS particles is less resistive than that of dense PSF matrix and offers the most selective pathway because CMS is capable of discriminating between size and shape differences of the gas penetrants. The gaps or voids conversely allow the bypassing of gas through its unselective and non-resistive pathways. The gas transport through the gaps
Table 5 Comparison of gas permeation between PSFCMS30 and PSFPVP K-15-sized CMS mixed matrix membranes for O2 and N2 Membrane PSF PSF-CMS30 PSFPVP-sized CMS
a

CMS (wt%) 0 30 30

PO2 (barrers) 1.58 (0.28)a 6.77 (0.01) 6.52 (0.23)

PN2 (barrers) 0.29 (0.04) 1.82 (0.06) 1.08 (0.04)

O2 /N2 5.50 3.69 6.05

Values in parenthesis is standard deviation; 1 barrer = 1 1010 (cm3 STP cm (cm2 s cmHg)).

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is assumed to be the Knudsen diffusion. As supported by the FESEM images in Fig. 6(a) and (b), a gross bypassing of gas could occur through the submicron gaps between the polymer matrix wall and the CMS particles in PSF-CMS30. Since the gas transport through those unselective gaps has been assumed to be the Knudsen diffusion, the degree of increment in N2 permeability became larger and exceeded the degree of increment of O2 permeability due to gas ow through CMS pathway. As a result, these membranes exhibited higher O2 and N2 permeability with poor selectivity compared to pure PSF membrane. On the other hand, the FESEM images in Fig. 6(c) and (d) reveal that the interfacial gaps were almost invisible in PSFPVP-sized CMS MMMs structure indicating that the gap size between the polymer matrix wall and CMS particles has been extensively reduced. The transport resistance of this pathway increased and suppressed the permeation of gas via Knudsen diffusion mechanism. More penetrant gases were directed to ow through CMS pathway. This was supported by a substantial reduction in N2 permeability for PSFPVP-sized CMS MMMs, which was about 41% from the N2 permeability in PSF-CMS30. A considerable improvement in O2 /N2 selectivity was also achieved by using PSFPVP-sized CMS whereby the selectivity was enhanced from 3.69 to 6.05. The ndings of this study prove that the PVP K-15 sizing layer not only capable of inducing the interfacial adhesion of PSF matrix and CMS particles but also allowing the gas transport through these two phases to proceed without creating additional non-selective and resistive layer in the interphase region. 4. Conclusions In this study, MMMs were successfully fabricated by combining polysulfone, Udel P-1700 and PVP K-15-sized CMS. CMS sizing with PVP K-15 has brought a dramatic impact on the adhesion of the CMS and PSF matrix. ATR-FTIR analysis demonstrated that the sizing agent (PVP K-15) has been successfully deposited onto the external surface of CMS and intimate interactions at molecular level between miscible blend of PSF matrix and PVP K-15 sizing polymer has also been established. The FESEM images revealed a considerable improvement in the interfacial adhesion between PSF matrix and CMS particles was achieved in PSFPVP K-15-sized CMS MMMs compared to that of unmodied PSFCMS MMMs. The voids or gaps surrounding the CMS was reduced to a great extend suggesting that the PVP K-15 sizing layer has successfully bridged the matrix and sieve phases by physically inducing the molecular interactions with both PSF matrix and CMS particles. With the absence of interfacial voids, a substantial recovery of separation performance can be achieved without adversely worsen the gas permeability or sacricing selectivity. Acknowledgements The author would like to express sincere gratitude to National Science Fellowship (NSF) from Ministry of Science, Technology and Innovation Malaysia (MOSTI) for the nancial support.

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