Journal of Membrane Science 267 (2005) 7889

The effects of 1,3-cyclohexanebis(methylamine) modication on gas transport and plasticization resistance of polyimide membranes
Lu Shao a,b,c , Tai-Shung Chung a, , S.H. Goh b , K.P. Pramoda c
b

Department of Chemical & Biomolecular Engineering, National University of Singapore, 10 Kent Ridge Crescent, Singapore 119260, Singapore Department of Chemistry, National University of Singapore, 10 Kent Ridge Crescent, Singapore 119260, Singapore c Institute of Materials Research and Engineering, 3 Research Link, Singapore 117602, Singapore Received 11 January 2005; received in revised form 10 May 2005; accepted 1 June 2005 Available online 18 July 2005

Abstract We have identied that 1,3-cyclohexanebis(methylamine) (CHBA) can be effectively used as a new cross-linking agent for the chemical modication of polyimide membranes. We have also observed that the combined effects of diamino cross-linking and thermal annealing would signicantly change the chemical compositions, micro-structure, gas sorption, gas transport properties and plasticization resistance of polyimide membranes. The membranes physicochemical changes after diamino cross-linking and thermal annealing were characterized by FTIR-ATR, XPS, gel content, UV, SEM-EDX and TGA and the possible reaction mechanisms during chemical modication and annealing have been proposed. Interestingly, it is found that the chemical reactions between diamino and polyimides are reversible during thermal annealing and the membrane micro-structures are modied and charge transfer complexes (CTCs) are formed during the post-treatments. The gas sorption and gas transport properties of membranes before and after modications are reported and discussed. The gas sorption concentration continuously decreases with an increase in the degree of cross-linking and the subsequent thermal annealing. Experimental results illustrate that thermal annealing not only improves CO2 /CH4 selectivity of the cross-linked membranes but also greatly enhances the plasticization resistance by the formation of CTCs. The critical plasticization pressure is signicantly improved from about 300 psia of the original samples to more than 720 psia of the cross-linked and 200 C thermal treated samples. Based on the experimental results, a novel approach to enhance plasticization resistance of polyimide membranes by means of diamino cross-linking and followed by thermal annealing is elucidated. 2005 Elsevier B.V. All rights reserved.
Keywords: Diamino cross-linking; Thermal annealing; Polyimides; Gas transport; Plasticization resistance

1. Introduction Synthetic polymeric membranes used as functional materials for gas separation are promising because the membrane separation systems have many advantages compared with the traditional separation methods [15]. Materials for gas separation must have characteristics of both high permeability and selectivity. The former increases productivity while the latter raises products purity. Both are essential to lower the capital and operation costs for membrane systems [6]. In

Corresponding author. Tel.: +65 874 6645; fax: +65 779 1936. E-mail address: chencts@nus.edu.sg (T.-S. Chung).

addition, materials with improved anti-plasticization properties are desirable and essential for uses in harsh environments [7]. Among many polymeric materials, polyimides have been widely studied for gas separation [5,810]. A variety of new polyimides has been synthesized with diverse dianhydrides or diamines to achieve high gas separation performance during the last two decades [2,4,5,6,1116]. However, the synthesis of new polyimides may not be economically practical for large-scale applications. Therefore, many researchers focused their studies on chemical and physical modications of commercially available or existing home-made polyimides in order to improve their gas separation performance [1732]. Among

0376-7388/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2005.06.004

L. Shao et al. / Journal of Membrane Science 267 (2005) 7889

79

different modication methods, the cross-linking method seems to be the most promising approach. The effects of UV photo cross-linking on the gas transport performance were investigated by Kita et al. [19] and Liu et al. [20]. Thermally induced cross-linking reactions of Matrimid were carried out on dense membranes and hollow bers separately by Bos et al. [21] and Krol et al. [22], and their effects on the suppression of plasticization had been studied. It was concluded that the formation of charge transfer complexes (CTCs) at elevated temperatures may enhance the plasticization resistance. Wind et al. [2325] cross-linked copolyimides containing free carboxylic acid with diol crosslinking agents at elevated temperatures and suggested covalent cross-linking were more promising to improve the gas separation properties and plasticization resistance. Most recently, several diamino cross-linking agents of polyimides, such as para- and meta-xylenediamine [2629], PAMAM (polyamidoamine) dendrimer [30,31] and diaminobutane (DAB)-dendrimers [32] have been discovered in our group. Some of them show effectiveness to modify polyimide membranes at room temperature. These approaches seem to be promising because not only they enhance gas separation performance but also have the advantages such as the simplicity of treatment and the availability to all kinds of aromatic polyimides. However, according to Wind et al. [2325], thermal treatment has great inuence on gas separation properties for the diol-induced cross-linked polyimide membranes because it may sway the reaction balance and change the degree of cross-linking. Besides, the chemical reaction between diamino and polyimides is reversibly driven by the thermal treatment as pointed out by Yun et al. [33]. Therefore, it is anticipated that thermal annealing should affect the gas separation performance of the diamino cross-linked polyimide membranes. To our best knowledge, up to date, there is no report on this subject for gas separation using 1,3-cyclohexanebis(methylamine) (CHBA) as the modication agent.

This study has two objectives. We would like to investigate if 1,3-cyclohexanebis(methylamine) (CHBA) can be effectively used as a brand new cross-linking agent for the chemical modication of polyimide membranes, and to dene the effects of thermal annealing on the separation performance of CHBA cross-linked polyimides. The coupling effects of cross-linking and thermal annealing on the chemical compositions, micro-structures, gas sorption and gas transport properties of 6FDA-durene membranes are investigated and characterized by FTIR-ATR, XPS, gel content, UV, SEMEDX, TGA, gas sorption and transport tests. Specially, their combined effects on the plasticization resistance are studied. The possible mechanisms during cross-linking and thermal annealing are proposed.

2. Experimental 2.1. Materials and dense membrane preparation The chemical structure of 6FDA-durene is shown in Fig. 1. It was synthesized in our lab and the details of synthesis have been described elsewhere [26]. The dense membrane preparation follows the same procedure described in [26]. After controlled evaporation, the nascent lms were dried in vacuum at 250 C for 24 h to remove the residual solvent. Membranes with thickness in the range of 50 5 m were chosen for testing and characterization. 2.2. Membrane chemical modication and thermal annealing The cross-linking reagent, 1,3-cyclohexanebis(methylamine) (CHBA), was purchased from Aldrich and used as received. The structure is also illustrated in Fig. 1. Ten percent (w/v) of CHBA solutions in methanol were prepared. The chemical modication was performed by immersing

Fig. 1. Chemical structures of 6FDA-durene and cross-link agent (CHBA).

80

L. Shao et al. / Journal of Membrane Science 267 (2005) 7889

the membrane lms in the solution for a stipulated period of time. The lms were then washed with fresh methanol immediately after removal from the reagent solution in order to wash away residual CHBA solution, followed by drying naturally at room temperature for about 1 day to ensure the complete removal of methanol solvent. The thermal annealing was performed by a CenturionTM Neytech Qex vacuum furnace. The cross-linked membranes were annealed under vacuum (about 20 mmHg) for 24 h at elevated temperatures (in the range of 100250 C), and then naturally cooled down. 2.3. Characterization The FTIR-ATR measurements were performed using a Perkin Elmer FT-IR Spectrometer Spectrum 2000 to characterize the chemical reaction. X-ray photoelectron spectroscopy (XPS) was utilized to determine the surface chemical compositions of the samples. The XPS measurements were carried out by an AXIS HSi spectrometer (Kratos Analytical Ltd., England) using the monochromatized Al K X-ray source (1486.6 eV photons) at a constant dwell time of 100 ms and a pass energy of 40 eV. All core-level spectra were obtained at a photoelectron take-off angle of 90 with respect to the sample surface. TGA was performed using PerkinElmer TGA 7 in the nitrogen environment and the reection UV spectra were recorded in the range of 200800 nm with UV-3101 PC (Shimadzu). SEM-EDX was carried out by JEOL JSM-6360LA (analytical scanning electron microscope) with the 10 s coating time. The gel content of cross-linked polyimide membranes were measured by extracting the lms in dichloromethane for 24 h. The insoluble fractions were vacuum dried at 120 C for about 1 day. The weights of polyimide lms before and after extraction were measured and the gel content was calculated by % gel content = W1 100% W0 (1)

2.4. Measurements of gas transport properties The pure gas permeabilities were determined by a constant volume and variable pressure method. Detailed experimental design and procedures have been reported elsewhere [26]. The permeabilities were obtained in the sequence of He, H2 , O2 , N2 , CH4 and CO2 at 35 C. The gas permeability was determined from the rate of downstream-pressure increase (dp/dt) obtained when permeation reached steady state according to the following equation: P= 273 1010 VL 760 AT (p2 76/14.7) dp dt (2)

where P is the permeability of a membrane to a gas and its unit is in Barrer (1 Barrer = 1 1010 cm3 (STP) cm/cm2 s cmHg), V the volume of the downstream chamber (cm3 ) and L is the lm thickness (cm). A refers to the effective area of the membrane (cm2 ), T is the experimental temperature (K) and the pressure of the feed gas in the upstream chamber is given by p2 (psia). The ideal separation factor of a membrane for gas A to gas B was evaluated as follows: A/B = PA PB (3)

3. Results and discussion 3.1. Characterization of modied polyimide lms Fig. 2 shows FTIR-ATR spectra of 6FDA-durene membranes before and after CHBA cross-linking. The original 6FDA-durene is characterized by bands at around 1783 cm1 (attributed to C O asymmetric stretch of imide groups), 1718 cm1 (attributed to C O symmetric stretch of imide

where W1 and W0 are the insoluble fraction weight and original weight of the cross-linked polymer lms, respectively. The gas equilibrium isotherms for O2 , N2 , CH4 and CO2 gases were measured at 35 C using a Cahn D200 microbalance sorption cell. The microbalance was rst calibrated with every individual gas as a function of pressure. Then approximately 100 mg of polymeric lms were placed on the sample pan. The system was evacuated for 24 h prior to test. A chosen gas at a specic pressure was fed into the system and the polymer sample started to sorb the gas until the equilibrium was reached. From the weight gained, the amount of gas dissolved in the polymer was calculated after correction for buoyancy. Subsequent experiments at higher pressures were carried out by repeating the procedures of gas feeding from the reservoir to the sample cell and weight monitoring without vacuuming the system again.

Fig. 2. FTIR-ATR spectra of 6FDA-durene before and after cross-linking.

L. Shao et al. / Journal of Membrane Science 267 (2005) 7889

81

Fig. 3. FTIR-ATR spectra of CHBA-modied 6FDA-durene before and after thermal annealing.

groups), and 1351 cm1 (attributed to C N stretch of imide groups). After cross-linking, the C O stretch band at around 1647 cm1 of amide groups and the C N stretching of the C N H group at around 1521 cm1 were presented. The intensities of the characteristic imide peaks (1783 and 1718 cm1 ) decrease, and the intensities of the characteristic amide peak (1647 cm1 ) increases with immersion time (cross-linking time). This suggests that the degree of crosslinking increases with immersion time. When the crosslinking time is up to 2 days, the imide peaks almost disappear. Fig. 3 presents FTIR-ATR spectra of CHBA modied 6FDA-durene membranes before and after thermal annealing. According to Fig. 3a, the original 6FDA-durene shows the imide peaks at around 1783, 1718 and 1351 cm1 , and the cross-linked lms show amide peaks at around 1647 and 1521 cm1 . However, thermal annealing decreases the intensity of amide peaks and increases the intensity of imide peaks. The relative intensity of amide/imide peaks (1647 cm1 /1718 cm1 ) continuously decreases with the annealing temperature from 0.590 (30 min100 C) to 0.412 (30 min150 C), and further down to 0.240 (30 min200 C). It shows that the thermal annealing converts the amide groups into the imide groups. This phenomenon is more pronounced at higher wavenumbers (above 3100 cm1 ) in the FTIR-ATR spectra (as shown in Fig. 3b). The broad peak around 35003100 cm1 is attributed to the NH (or hydrogen bond), which arises from amide groups ( NH stretch) in the materials [34]. After cross-linking, the broad peak of NH/hydrogen bond shows up. Nevertheless, the broad peak decreases with the thermal annealing temperature, and it almost disappears when the annealing temperature reaches only up to 200 C. FTIR-ATR results illustrate that the chemical compositions of 6FDA-druene lms change with chemical crosslinking and thermal annealing. Based on FTIR-ATR results,

the reaction mechanisms during chemical cross-linking and thermal annealing may be proposed and illustrated in Fig. 4 [33]. To conrm the reaction mechanisms during diamino crosslinking and thermal annealing, XPS was carried out and the results are summarized in Table 1. Because the uorine element content remains constant in polyimides, the change in the ratio of nitrogen to uorine (N/F) can be used to study and analysis. The results show that the surfaces of 30 min CHBA cross-linked membranes have higher nitrogen content (N/F = 0.65) than that of the original ones (N/F = 0.31). However, the thermal annealing decreases the N/F ratio. After thermal annealing at 200 C, the N/F ratio drops back to 0.40. This phenomenon can be attributed to the release of CHBA at elevated temperatures and is consistent with the FTIR-ATR results which conrm our hypothesis of reaction mechanisms. Fig. 5 illustrates the change of gel content of cross-linked samples with annealing temperature. It demonstrates that after 5 min CHBA cross-linking, the gel content is up to about 90%, and the gel content is almost 100% when the cross-linking time reaches to the 30 min. For comparison, the un-heat-treated cross-linked samples (at 25 C) are used as controlled in this gure. It shows that the proposed crossTable 1 Elemental composition of modied 6FDA-durene surface determined by XPS Samples Original (theoretical) Original (experimental) CHBA30 min CHBA30 min annealed at 100 C 150 C 200 C F 1s 14.63 13.06 11.02 9.32 12.36 11.07 O 1s 9.76 12.67 9.69 11.65 10.90 12.41 N 1s 4.49 4.05 7.19 5.59 5.59 4.40 C 1s 70.73 70.22 72.10 73.43 71.15 72.11 N 1s/F 1s 0.31 0.31 0.65 0.60 0.45 0.40

82

L. Shao et al. / Journal of Membrane Science 267 (2005) 7889

Fig. 4. Possible reaction mechanisms during chemical cross-linking and thermal annealing.

linking method carried out in the CHBA/methanol solution not only affects the surface of membranes but also the bulky matrix. This is due to the fact that the methanol swells the membranes, which facilitate the diffusion of cross-link agents through the membranes to react with the bulky body [28,32]. The thermal annealing remarkably reduces the gel content of the CHBA cross-linked membranes, and the higher the annealing temperature the lower the gel content. This phenomenon can be attributed to the reversible nature of diamino cross-linking reaction as illustrated in Fig. 4. Because the FTIR-ATR and XPS for the chemical composition analysis are limited on the surface of the membranes, SEM-EDX is carried out on the cross-section of the membranes. However, the original 6FDA-durene and the cross-linked samples are too tough to prepare clean and

Fig. 5. Gel content vs. annealing temperature (the cross-linked samples (at 25 C) without thermal treatment are used as the control).

well fractured samples for the SEM-EDX test, so only the 200 C annealed sample was tested and shown in Fig. 6. It illustrates that the C and N elements homogenously distribute throughout the cross-section of membranes. There is no obvious difference between the surface and the body part of the membranes. It means that the thermal annealing almost homogeneously changes the chemical compositions and structures of the cross-linked polyimide matrix. After the thermal annealing, it is found that the membrane colors have signicantly changed from transparent to yellow. The higher the annealing temperature, the deeper the yellow color. The color change during thermal treatment is typically due to the formation of charge transfer complexes (CTCs) [21,35,36]. The alternating electron acceptor and donor endow the polyimides with the ability to form CTCs. However, CTCs in solid state polyimides are most likely in a non-equilibrium state [35]. It means that thermal treatment at higher temperatures may facilitate the formation of CTCs, which can cause the spectral red shifts of UV absorption bands by reducing the donoracceptor distance. The changes in UV wavelength and color are listed in Table 2. The data of thermal treated Matrimid published by Bos et al. [21] are also included in this table for comparison, although their thermal treatment temperature is greatly different from ours. Bos et al. [21] thermally treated Marimid at 350 C and found its color change increasing with the duration of thermal treatment, which was attributed to CTCs. In this study, the original 6FDA-durene membranes were

L. Shao et al. / Journal of Membrane Science 267 (2005) 7889

83

Fig. 6. SEM-EDX pictures of CHBA-cross-linked samples annealed at 200 C.

pre-treated at 250 C in vacuum, but still kept transparent. This demonstrates that thermal treatment up to 250 C has no inuences on the formation of CTCs in unmodied 6FDA-durene membranes. The cross-linked membranes still remain transparent and only show a small red shift of about 9 nm in the UV absorption band compared with that of the original one. Interestingly, the thermal treatment on modied 6FDA-durene membranes causes a surprising increase in red shift. In addition, the higher the annealing temperature the larger the red shift. At 200 C annealing, the red shift is up to 326 nm, which is much larger than that of Matrimid (the maximum of its red shift is 21 nm) even though Matrimid is treated at a higher temperature (350 C). The strong ability to form the CTCs in the cross-linked membranes arises from the nature of this novel cross-linking agent and the coupling effects of cross-linking and thermal annealing. The diamino chemical cross-linking opens the main chains in the solid state polyimides, which modies the polymer chains to be relatively exible. When the therTable 2 UV wavelength and color properties of modied 6FDA-durene and thermal treated Matrimid Materials 6FDA-durene Original CHBA30 min CHBA30 min100 C CHBA30 min150 C CHBA30 min200 C Matrimid [21] Untreated 15 min350 C 30 min350 C 45 min350 C Color (UV) (nm) 433.5 442.5 524 552.5 759.5 391 394 406 412 (UV shift) (nm) 0 9 90.5 119 326 0 3 15 21

Transparent Transparent Light yellow Yellow Dark yellow Light yellow Darker Darker Darker

mal treatment is applied, the relatively exible chains are thermodynamically easier to achieve the congurational rearrangement and form CTCs, especially at higher temperatures (such as 200 C in this study). As a result, thermal annealing facilitates the formation of CTCs in the cross-linked membranes. Although the thermal treatment regenerates imide groups from amide groups in the cross-linked networks, the micro-structures of the polyimide membranes exhibit irreversible changes and the formation of CTCs displays significant inuences on gas transport properties (discussed later). The conceptual modeling of CTCs in 6FDA-durene is shown in Fig. 7. It should be pointed out that both the intra- and intermolecular CT interactions happen and contribute to the coloration and the micro-structure changes [3537]. Nevertheless, in the solid state polyimides, the CTCs dominate over intermolecular CTCs via -bonding overlap between donors and acceptors [37]. TGA was carried out to characterize the stability of the modied 6FDA-durene membranes. The degradation temperature (Td ) is determined at the 5% weight loss. According to Fig. 8a, the Td of chemically cross-linked 6FDA-durene membranes decreases with the cross-linking duration. This may be due to the thermal instability of CHBA moiety at high temperatures. As shown in Fig. 8b, the thermal annealing improves the thermal stability and increases the Td of the cross-linked membranes. This is consistent with the previous discussion and the proposed reaction mechanisms, which suggesting the removal of CHBA moiety and forming of CTCs during the heat treatment. 3.2. Gas sorption Gas sorption experiments were performed on the original and modied polyimide lms. Fig. 9 shows the gas sorption isotherms in polyimide lms at 35 C. Since the plasticization

84

L. Shao et al. / Journal of Membrane Science 267 (2005) 7889

Fig. 7. Charge transfer complex model of 6FDA-durene polyimides.

study (discussed later) suggests that the cross-linked 6FDAdurene lm may plasticize at pressures above 110 psia, the CO2 sorption isotherm was conducted only up to 100 psia for the tting comparison of dual mode sorption parameters. For other gases (O2 , N2 and CH4 ), the applied pressures were up to 225 psia. The solubility isotherms of gases are concaved to the pressure axis and can be well described by the dual

sorption model of gas sorption in glassy polymers as follows [38]: C = C D + C H = kD p + CH bp 1 + bp (4)

where C is the total absorbed gas concentration in the bulky polymer, CD and CH are the gas concentrations in Henry (the

Fig. 8. TGA results of membranes: (a) the effects of cross-linking duration; (b) the effect of thermal annealing.

L. Shao et al. / Journal of Membrane Science 267 (2005) 7889

85

Fig. 9. Sorption isotherms of membranes at 35 C.

dissolution mode in the densied region) and Langmuir (the hole lling mode in the unrelaxed volume) environments separately; kD , CH and b are the Henry law constant, Langmuir capacity constant and Langmuir afnity constant (the ratio of the rate constants of gas adsorption and desorption in the microcavities or defects), respectively. According to Fig. 9a, the solubility of different gases follows the order: N2 < O2 < CH4 < CO2 , which is consistent with the order of gases critical temperatures (N2 : 118.6 C < O2 : 146.9 C < CH4 : 82.6 C < CO2 : 31.0 C). The highest CO2 sorption arises from the highest inherent condensability and the strongest polymerpenetrant interactions. The chemical cross-linked and thermal annealed 6FDA-durene membranes show the same trends for different gas sorption as that of the original sample. Fig. 9b shows the CH4 sorption isotherms in the original and modied 6FDA-durene lms. Comparing different modied membranes, the sorption concentration follows the order: original > CHBA30 min > CHBA30 min100 C > CHBA30 min200 C. This indicates that the cross-linking decreases gas sorption, and the thermal annealing of the

cross-linked lms further reduces gas sorption. During crosslinking, the reduction in sorption concentration of 6FDAdurene membranes may be explainable because of the crosslinking network [23] and the hole lling effect by the diamino cross-linking agent [32], both diminish the gas sorption in Langmuir sites. According to the shift in UV wavelength, the thermal annealing facilitates the formation of CTCs in the cross-linked polyimide membranes and densies the membrane structures [35]. As a result, the gas sorption further decreases during the thermal annealing process. Table 3 listed the dual model parameters (kD , CH and b), which were calculated by a non-linear least squares t of the sorption data. It can be seen that kD and b increase in the order of N2 < O2 < CH4 < CO2 . kD is related to the enthalpy of dissolution ( HD ) and b is related to the apparent enthalpy of hole-lling, which are dependent on the nature of polymerpenetrant interaction [39]. As a result, polar molecular CO2 have the highest values of kD and b due to the strongest polymerpenetrant interactions. To illustrate the cross-linking and annealing effects on the polyimide membranes, a comparison of dual mode param-

Table 3 Dual mode sorption parameters of membranes at 35 C Samples Original Gas O2 N2 O2 N2 kD (cm3 (STP)/ cm3 polymer atm) 0.384 0.257 0.335 0.273 CH (cm3 (STP)/ cm3 polymer) 28.12 27.48 18.84 16.35 b (atm1 ) 0.052 0.045 0.059 0.058 Gas CH4 CO2 CH4 CO2 kD (cm3 (STP)/ cm3 polymer atm) 0.800 2.656 0.804 3.028 CH (cm3 (STP)/ cm3 polymer) 33.98 52.43 23.50 41.62 b (atm1 ) 0.146 0.741 0.176 0.885

CHBA30 min

CHBA30 min annealed at 100 C O2 N2 200 C O2 N2

0.220 0.171 0.250 0.178

16.65 15.08 14.48 14.35

0.056 0.051 0.050 0.043

CH4 CO2 CH4 CO2

0.722 2.330 0.728 1.925

20.39 37.75 18.22 31.82

0.216 0.807 0.161 0.717

86

L. Shao et al. / Journal of Membrane Science 267 (2005) 7889

eters are carried out for different membranes. As shown in Table 3, CH continuously decreases with the cross-linking and annealing. Because CH is the Langmuir capacity constant which reects the gas sorption capacity of microcavities and defects in the unrelaxed polymer at certain temperatures, it is reasonable to believe that the volume percentage of microcavity and defects decrease continuously. This decrease may initially come from the hole-ling effect of the cross-linking agent and the tightening effect induced by cross-linking [32], which is coherent with the decrease in the permeability after cross-linking (discussed later). After thermal annealing, the decrease of CH is mainly due to the effect of forming charge transfer complexes (CTCs) [21,35,36], which results in more densied membranes. In other words, the unrelaxed volume (excess free volume) further decreases after thermal annealing. Besides, the micro-structure of the cross-linked membranes during thermal annealing is modied, which may affect the fractional free volume (FFV) and its distribution in the membranes. 3.3. Gas transport properties of modied lms The effects of chemical cross-linking and thermal annealing on the gas transport properties of the modied membranes may be summarized as follows from two aspects: (1) chemical aspect: the membranes chemical compositions and material polarity have been modied [40]; (2) physical aspect: the membranes micro-structure has been modied because of the hole lling effects by the cross-linking agent and the formation of CTCs. Table 4 shows the gas transport properties of crosslinked and thermal annealed 6FDA-durene membranes. The gas permeability of the original 6FDA-durene membranes < N2 follows the sequence: CH4 (kinetic diameter: 3.80 A) < O2 (3.46 A) < He (2.6 A) < CO2 (3.30 A) < H2 (3.64 A) Except for CO2 and H2 gases, the order of different (2.89 A). gas permeability corresponds well with their kinetic diameter, and the smaller the kinetic diameter of the gas molecules the larger the permeability. Because the permeability is a product of the solubility and the diffusivity, He has poor interactions (less solubility) with the polymer; therefore, its permeability is lower than that of H2 [41]. In the CO2 case, the deviation may be resulted from the higher polymerpenetrant interactions of the polar CO2 compared with that of He,
Table 4 Gas transport properties of membranes Samples Permeability (Barrera ) He Original 490 CHBA30 min 138 CHBA30 min annealed at 100 C 114 150 C 126 200 C 126
a

and the possibility of differing orientations of its anisometric molecules during the diffusion comparison [42]. However, after cross-linking and then thermal annealing, the order of gas permeability follows a new order as: CH4 < N2 (3.64 A) < O2 (3.46 A) < CO2 (kinetic diameter: 3.80 A) < He (2.6 A) < H2 (2.89 A), in which the CO2 gas has (3.30 A) changed the order and demonstrates a lower permeability than that of He gas. This may due to the chain tightening effects caused by the novel chemical cross-linking reaction [32] and by the thermal-induced CTCs formation. The effects of thermal annealing on permeability combine the effects of the formation of CTCs and the release of CHBA on gas transport. Thermal annealing applied at 100 C slightly decreases the permeability of cross-linked membranes, which may be attributed to: (1) the tendency toward thermodynamic equilibrium of chain packing of 6FDA-durene, (2) CHBA moieties in the interstitial space of the cross-linking structure and (3) the initiation of CTCs formation. An increase in the degree of cross-linking during the annealing may also be the cause [23,24]. However, permeability surprisingly increases slightly if the annealing is taken place at 150 C. This is mainly due to the heavy release of the cross-linking agents and the redistribution of FFV during the conversion of amide into imide groups, which cannot fully be compensated by the densifying effect of the CTCs formation. Therefore, the permeability becomes relatively constant after annealing at 200 C, which is a result of the balance between the release of the cross-linking agents and the formation of CTCs. The discrepancy between permeability and gas sorption trend of CHBA cross-linked membranes with thermal treatment should arise from the diffusivity, which is affected by the complex structure evolution and CTC formations. A comparison of selectivity shows that all modied membranes have higher H2 /CO2 , O2 /N2 and CO2 /CH4 selectivity than that of the original 6FDA-durene membranes. The O2 /N2 selectivity of annealed samples does not change much with annealing temperature. On the other hand, the H2 /CO2 and CO2 /CH4 selectivity of the annealed samples show the larger changes with annealing temperature. Interestingly, the CO2 /CH4 selectivity increases with annealing temperature. However, the H2 /CO2 selectivity initially increases after annealing at 100 C and then decreases with an increase in annealing temperature. At 100 C annealing, the rearrangement of polymeric chains and the possible further cross-

Selectivity O2 186 20.2 14.6 17.1 17.4 N2 55.4 4.33 3.01 3.74 3.70 CH4 45.1 2.86 1.87 2.40 2.28 CO2 612 55.2 37.2 54.5 59.8 H2 /CO2 1.28 2.93 3.41 2.62 2.36 O2 /N2 3.36 4.67 4.85 4.57 4.70 CO2 /CH4 13.6 19.3 19.9 22.7 26.2

H2 786 162 127 143 141

1 Barrer = 1 1010 cm3 (STP) cm/cm2 s cmHg.

L. Shao et al. / Journal of Membrane Science 267 (2005) 7889

87

linking may be the driving forces to yield higher H2 /CO2 and CO2 /CH4 selectivity. Further increase in anneal temperature favors the CTCs formation and decreases polymerpenetrant (CO2 ) interactions by changing the chemical composition of the membranes. As a result, the selectivity of H2 /CO2 decreases, while the selectivity of CO2 /CH4 increases with increasing annealing temperature. It implies that the thermal annealing can effectively improve the CO2 /CH4 selectivity of cross-linked 6FDA-durene membranes without much reduction in permeability (as shown in Table 4) because of the optimized free volume distribution during the membrane structure evolution driven by cross-linking and thermal annealing. Interestingly, the FTIR, XPS and TGA show that the 6FDA-durene almost regenerates its original chemical composition and thermal stability after 200 C annealing. However, Table 4 indicates that the gas transport properties of the sample annealed at 200 C become much different from that of the original sample. The former has a lower permeability and higher selectivity. This phenomenon may be attributed to the combined effects of the chemical cross-linking modication and thermal annealing on the membrane. The formation of CTCs, the release of CHBA, and the redistribution of FFV all play an important role on gas transport properties of modied membranes. 3.4. The effects of thermal annealing on the CO2 plasticization resistance Plasticization phenomena are observed in many glassy polymers such as PSF, PMMA and polyimide (PI) [4346]. The dual mode sorption model illustrates that the permeability decreases with an increase in pressure [2,14,2127,38]. Because the condensable gases such as CO2 have the strong polymerpenetrant interactions, it can swell up the glassy polymer and loose the polymer matrix when the pressure is above the critical plasticization pressure. Consequently, the permeability increases and selectivity decreases with increasing pressure when the plasticization happens. Therefore, the plasticization resistance should be achieved to keep the membranes satisfactorily performance in the aggression environments [7]. According to Bos et al.s work [21], the formation of CTCs may be a reason for the improvement of plasticization resistance in thermally treated Matrimid membranes. Most recently, Krol et al. [22] thermally treated the Matrimid hollow bers and found that the formation of CTCs restricts the chain mobility and suppresses the plasticization in propane/propylene environments. Therefore, it would be interesting to investigate the plasticization phenomena after the cross-linking or/and thermal annealing. Fig. 10 demonstrates the relationship between the relative CO2 permeability versus the feed pressure as a function of various post-treatment conditions. The original 6FDA-durene exhibits an increase in the relative CO2 permeability when the pressure is above approximate 300 psia. After cross-linking, the cross-linked sample becomes more easily plasticized

Fig. 10. Effect of pressure on the relative CO2 permeability of CHBA crosslinked and thermal annealed membranes.

compared with the original one, and the plasticization happens when the pressure is just over 110 psia. Instinctively, this phenomenon may be contrary to the common concept that the cross-linking can improve the plasticization resistance in the polymer matrix [7,21,23,24]. However, after close examination, one may attribute the disparity to the different methods of cross-linking and different cross-linking mechanisms. Conventional cross-linking reactions may take place on the side chains of the polymer, while its rigid main chains remain intact. However, the rigid main-chain structure of 6FDA-durene polyimide is modied by our cross-linking method; the imide ring is opened by the cross-linking reaction (as shown in Fig. 4). As a result, the cross-linked polymer has relatively exible main chains and is therefore more vulnerable to be plasticized by condensable gases when compared with that of the original samples. The other reason may arise from the fact that the methanol immersion during the crosslinking modication may loose the chain package [30,32]. Therefore, the CO2 gas is relatively easier to swell and loose the cross-linked polymer matrix. Surprisingly, the thermal annealing effectively improves the plasticization resistance of the cross-linked membranes. Even though at 100 C thermal annealing, the plasticization resistance of the cross-linked 6FDA-duren membranes is improved to be almost equal to that of the original one. The higher the thermal annealing temperature, the better the plasticization resistance. After thermal annealing at 200 C, the improvement is greatly achieved and the treated membranes do not show plasticization up to around 50 atm (720 psia), which is much higher than the plasticization pressure around 110 psia for the as-cross-linked sample and 300 psia for the original one. This enhancement of anti-plasticization characteristics is attributed not only to the regeneration of chemical composition from amide groups to imide groups driven by the thermal annealing, but also to the formation of the CTCs and the changes in the membrane micro-structure. In order others, the formation of CTCs can restrict the mobility of polymer chains and improve the plasticization resistance of

88

L. Shao et al. / Journal of Membrane Science 267 (2005) 7889

membranes. This is coherent with the Krol et al.s study [22]. Compared with Krol et al.s work, our method seems to be more powerful and effective to form the CTCs because the exible cross-linked membranes have the strong ability to undergo thermodynamically rearrangement of the conguration of polymer chains and form the CTCs at elevated temperatures. Consequently, the great improvement in the plasticization resistance is achieved by the coupling effects of chemical cross-linking and thermal annealing.

References
[1] P.H. Abelson, Synthetic membranes, Science 244 (1989) 4911. [2] D.R. Paul, Y.P. Yampolskii, Polymeric Gas Separation Membranes, CRC Press, 1994. [3] C. Liu, C.R. Martin, Composite membranes from photochemical synthesis of ultrathin polymer lms, Nature 352 (1991) 50. [4] S.A. Stern, Polymers for gas separations: the next decade, J. Membrane Sci. 94 (1994) 1. [5] H. Ohya, V.V. Kudryavtsev, S.I. Semenova, Polyimide Membranes Applications, Fabrications, and Properties, Gordon and Breach Publishers, Tokyo, 1996. [6] Y. Seo, S.U. Hong, B.S. Lee, Overcoming the upper bound in polymeric gas-separation membranes, Angew. Chem. Int. Ed. 42 (2003) 1145. [7] W.J. Koros, R. Mahajan, Pushing the limits on possibilities for large scale gas separation: which strategies? J. Membrane Sci. 175 (2000) 181. [8] J.H. Fang, H. Kita, K. Okamoto, Hyperbranched polyimides for gas separation applications. 1. Synthesis and characterization, Macromolecules 33 (2000) 4639. [9] H.B. Park, J.K. Kim, S.Y. Nam, Y.M. Lee, Imide-siloxane block copolymer/silica hybride membranes: preparation, characterization and gas separation properties, J. Membrane Sci. 200 (2003) 59. [10] K.C. Khulbe, C. Feng, T. Matsuura, G.C. Kapantaidakis, M. Wessling, G.H. Koops, Characterization of polyethersulfonepolyimide hollow ber membranes by atomic force microscopy and contact angle goniometry, J. Membrane Sci. 226 (2003) 63. [11] K. Xu, C. Dannenberg, J. Springer, G. Banerjee, G. Maier, Gas separation properties of polymers containing uorine moieties, Chem. Mater. 14 (2002) 3271. [12] M. Al-Masri, D. Fritsch, H.R. Kricheldorf, New polyimides for gas separation. 2. Polyimides derived from substituted catechol bis(etherphthalic andydirde)s, Macromolecules 33 (2000) 7127. [13] Y. Hirayama, T. Yoshinaga, Y. Kusuki, K. Ninomiya, T. Sakakibara, T. Tamari, Relation of gas permeability with structure of aromatic polyimides I, J. Membrane Sci. 111 (1996) 169. [14] M.R. Coleman, W.J. Koros, Conditioning of uorine-containing polyimides. 2. Effect of conditioning protocol at 8% volume dilation on gas-transport properties, Macromolecules 32 (1999) 3106. [15] T.S. Chung, R.E. Kafchinski, The effects of spinning conditions on asymmetric 6FDA/6FDAM polyimide hollow bers for air separation, J. Appl. Polym. Sci. 65 (1997) 1555. [16] M.R. Coleman, W.J. Koros, Isomeric polyimides based on uorinated dianhydrides and diamines for gas separation applications, J. Membrane Sci. 50 (1990) 285. [17] J. Kurdi, A.Y. Tremblay, Improvement in polyetherimide gas separation membranes through the incorporation of nanostructured metal complexes, Polymer 44 (2003) 4533. [18] A. Bos, I. Punt, H. Strathmann, M. Wessling, Suppression of gas separation membrane plasticization by homogeneous polymer blending, AIChE J. 47 (2001) 1088. [19] H. Kita, T. Inada, K. Tanaka, K. Okamoto, Effect of photocrosslinking on permeability and permselectivity of gases through benzophenone-containing polyimide, J. Membrane Sci. 87 (1994) 139. [20] Y. Liu, C. Pan, M.X. Ding, J.P. Xu, Gas permeability and permselectivity of photochemically crosslinked copolyimides, J. Appl. Polym. Sci. 73 (1999) 521. [21] A. Bos, I.G.M. Punt, M. Wessling, H. Strathmann, Plasticizationresistant glassy polyimide membranes for CO2 /CH4 separations, Sep. Purif. Technol. 14 (1998) 27. [22] J.J. Krol, M. Boerrigter, G.H. Koops, Polyimide hollow ber gas separation membranes: preparation and the suppression of plasticization on propane/propylene environments, J. Membrane Sci. 184 (2001) 275.

4. Conclusion The follow conclusions can be made in this study: 1. The coupling effects of diamino cross-linking and thermal annealing on polyimide membranes are characterized by FTIR-ATR, XPS, gel content, UV, SEM-EDX and TGA. The possible reaction mechanisms during crosslinking and thermal annealing are proposed based on the experimental results. It is found that the coupling effects facilitates the formation of CTCs and signicantly modies the micro-structure in the polyimide membranes. 2. According to gas sorption test, the solubility of different gases follows the order: N2 < O2 < CH4 < CO2 , which is consistent with the order of gases critical temperatures (N2 : 118.6 C < O2 : 146.9 C < CH4 : 82.6 C < CO2 : 31.0 C). The sorption concentration of different modied membranes follows the order: original > CHBA30 min > CHBA30 min100 C > CHBA 30 min200 C. 3. It is found that the thermal annealing can effectively improve the CO2 /CH4 selectivity of cross-linked 6FDA-durene membranes without much reduction in permeability. 4. The combined effects of diamino cross-linking and thermal annealing are effective to form the CTCs because the exible cross-linked polymeric chains have the strong ability to undergo thermodynamically rearrangement and form the CTCs during the thermal annealing. As a result, a great improvement in plasticization resistance is achieved by the proposed diamino cross-linking modication and the subsequent thermal annealing. 5. Based on experimental results, a novel strategy to enhance the plasticization resistance of polyimide membranes by means of diamino cross-linking and followed by thermal annealing is proposed.

Acknowledgements The authors would like to thank A*Star and NUS for funding this research with the grant numbers of R-279-000113-304 and R-279-000-165-112, respectively. The authors are grateful to Ms. Doreen Lai for help on SEM-EDX experiments and Dr. Cao Chun for valuable discussions.

L. Shao et al. / Journal of Membrane Science 267 (2005) 7889 [23] J.D. Wind, C. Staudt-Bickel, D.R. Paul, W.J. Koros, Solid-state covalent cross-linking of polyimide membranes for carbon dioxide plasticization reduction, Macromolecules 36 (2003) 1882. [24] J.D. Wind, D.R. Paul, W.J. Koros, Natural gas permeation in polyimide membranes, J. Membrane Sci. 228 (2004) 227. [25] J.D. Wind, S.M. Sirard, D.R. Paul, P.F. Green, K.P. Johnston, W.J. Koros, Carbon dioxide-induced plasticization of polyimide membranes: pseudo-equilibrium relationships of diffusion, sorption and swelling, Macromolecules 36 (2003) 6433. [26] Y. Liu, R. Wang, T.S. Chung, Chemical cross-linking modication of polyimide membranes for gas separation, J. Membrane Sci. 189 (2001) 231. [27] C. Cao, T.S. Chung, Y. Liu, R. Wong, K.P. Pramoda, Chemical crosslinking modication of 6FDA-2,6-DAT hollow ber membranes for natural gas separation, J. Membrane Sci. 216 (2003) 257. [28] P.S. Tin, T.S. Chung, Y. Liu, R. Wang, S.L. Liu, K.P. Pramoda, Effects of cross-linking modication on polyimide Matrimid membranes, J. Membrane Sci. 225 (2003) 77. [29] J.Z. Ren, R. Wang, T.S. Chung, D.F. Li, Y. Liu, The effects of chemical modications on morphology and performance of 6FDAODA/NDA hollow ber membranes for CO2 /CH4 separation, J. Membrane Sci. 222 (2003) 133. [30] Y.C. Xiao, T.S. Chung, M.L. Chng, Surface characterization, modication chemistry and separation performance of polyimide and polyamidoamine dendrimer composite lms, Langumir 20 (2004) 8230. [31] T.S. Chung, M.L. Chng, K.P. Pramoda, Y.C. Xiao, PAMAM dendrimer induced cross-linking modication of polyimide membranes, Langumir 20 (2004) 2966. [32] L. Shao, T.S. Chung, S.H. Goh, K.P. Pramoda, Transport properties of cross-linked polyimide membranes induced by different generations of diaminobutane (DAB) dendrimers, J. Membrane Sci. 238 (2004) 153. [33] H.K. Yun, K. Cho, J.K. Kim, C.E. Park, Adhesion improvement of epoxy resin/polyimide joints by amine treatment of polyimide surface, Polymer 38 (1997) 827.

89

[34] J.A. Mikroyannidis, Soluble and fusible polyamides and polyimides containing pyrazoline moieties and their crosslinking to heat resistant resins, J. Polym. Sci. A: Chem. 35 (1997) 1353. [35] M. Hasegawa, K. Horie, Photophysics, photochemistry and optical properties of polyimides, Prog. Polym. Sci. 26 (2001) 259. [36] D. Wilson, H.D. Stenzenberger, P.M. Hergenrother, Polyimides, Blackie, Glasgow, 1990. [37] J.M. Salley, C.W. Frank, Charge transfer in aromatic polyimides, in: M.K. Ghosh, K.L. Mittal (Eds.), Polyimides: Fundamentals and Applications, Marcel Dekker, New York, 1996. [38] W.J. Koros, Sorption and transport of gases in glassy polymers, Ph.D. Dissertation, University of Texas, Austin, TX, 1977. [39] W.R. Vieth, Membrane Systems: Analysis and Design, Oxford University Press, 1988. [40] M.Q. Zhao, Y.L. Liu, R.M. Crooks, D.E. Bergbreiter, Preparation of highly impermeable hyperbranched polymer thin-lm coatings using dendrimers rst as building blocks and then as in situ thermosetting agents, J. Am. Chem. Soc. 121 (1999) 923. [41] J.J. Shieh, T.S. Chung, Gas permeability, diffusivity, and solubility of poly(4-vinylpyridine) lm, J. Polym. Sci. B: Phys. 37 (1999) 2851. [42] A.S. Michaels, H.J. Bixler, Flow of gases through polyethylene, J. Polym. Sci. 50 (413) (1961) 113. [43] A.Y. Houde, S.S. Kulkarni, M.G. Kulkarni, Sorption, transport and history effects in phenolphthalein-based polysulfone, J. Membrane Sci. 95 (1994) 147. [44] E.S. Sander, S.M. Jordan, R. Subramanian, Penetrant-plasticized permeation in polymethylmethacrylate, J. Membrane Sci. 74 (1992) 29. [45] A.F. Ismail, W. Lorna, Penetrant-induced plasticization phenomenon in glassy polymers for gas separation membrane, Sep. Purif. Technol. 27 (2002) 173. [46] J.D. Wind, C. Staudt-Bickel, D.R. Paul, W.J. Koros, The effects of crosslinking chemistry on CO2 plasticization of polyimide gas separation membranes, Ind. Eng. Chem. Res. 41 (2002) 6139.