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Separation and Purication Technology 24 (2001) 223 233 www.elsevier.


Accelerated plasticization of thin-lm composite membranes used in gas separation

M. Wessling a, M. Lidon Lopez b,*, H. Strathmann a

Membrane Technology Group, Uni6ersity of Twente, 7500 AE Enschede, The Netherlands b Dpt de Ciencias Experimentales, Uni6ersidad Jaime I, 12080 Castellon, Spain

Received 27 July 1998; received in revised form 24 January 2001; accepted 28 January 2001

Abstract Permeation experiments with He, N2, O2 and CO2, have been carried out with double layer composite membranes consisting of a silicone rubber support layer and a thin polyimide layer determining the permeation properties. The estimated thickness of the polyimide layer in the composite membranes was between 1.5 and 4 microns. This paper describes the phenomenon of accelerated plasticization of such thin polyimide layers used in gas separation membranes. The pressure-normalized uxes were determined at 5 bars for N2, O2 and in the range of 1 8 bars in the case of He and CO2. Helium permeation decreased with increasing feed pressure and no hysteresis behavior was found for successive increasing and decreasing feed pressure steps. For CO2, the pressure-normalized ux did not follow the typical behavior of glassy polymers but increased continuously with increasing feed pressure. Also, CO2 permeation showed a clear hysteresis effects resulting in an increasing permeability with time and an elevated magnitude in successive decreasing feed pressure steps. Hence, stronger plasticization effects in the composite membranes must be concluded in comparison with thick single lm membranes. The plasticization effects are signicantly pronounced as the polyimide concentration in the solution from which the membranes are cast become more dilute. The latter is interpreted as accelerated plasticization with decreasing lm thickness. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Gas separation; Permeation; Composite membrane; Plasticization

1. Introduction A well-known limitation in the design of commercial membranes for gas separation processes is the trade-off between permeability and permselec* Corresponding author. E -mail address: Lopez).



tivity, where an increase in selectivity is coupled with a decrease in permeability. In practice, a very selective material such as an aromatic polyimide has to have a low effective membrane thickness ( B 1 mm) in order to have high uxes. However, some recent work shows that the transport properties of a dense membrane depend on membrane thickness as the membranes become very thin [14]. A dependency of the diffusion coefcients

1383-5866/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 1 3 8 3 - 5 8 6 6 ( 0 1 ) 0 0 1 2 7 - 7


M. Wessling et al. / Separation /Purification Technology 24 (2001) 223 233

and the gas solubility on the membrane thickness has been reported [1]. Other related work focused on the dependence of physical aging and membrane thickness on gas properties of polymer membranes [2 4]. Related to the subject of thickness-dependent membrane properties, plasticization phenomena may become important in very thin membranes as well. Wessling [5] indicated for double layer composite membranes (polyimide on polydimethylsiloxane and polyimide on poly (1-trimethyl 1-silylpropyne) with a polyimide thickness of a few microns) that the permeability coefcient increases with increasing CO2 feed pressure. In contrast, for thick polyimide membranes the permeability coefcient decreases with pressure for feed pressures below the plasticization pressure [5]. Pinnau [6] found a similar behavior for asymmetric polysulfone membranes. Pfromm [4] showed that the decrease of the permeability coefcients with increasing pressure was lower in the case of very thin membranes. It is the purpose of this article to demonstrate that composite membranes with a thin glassy polymer layer show distinctly different permeation characteristics with gases inducing plasticization than thick lms.

2. Background Theoretical models for the permeability coefcients of gases through polymers distinguish between the behavior below and above the glass transition temperature [7]. Above the glass transition temperature the permeability coefcient of a (rubbery) polymer is constant for low pressures and increases eventually at elevated feed pressures. Below the glass transition temperature the situation is different due to micro-heterogeneities of the polymer matrix. Generally, for highly sorbing gases such as carbon dioxide, glassy polymers show a decrease in permeability with increasing feed pressure due to the predominant effect of the micro-heterogeneities, a typical example being polycarbonate [8]. However, when the carbon dioxide plasticizes the membrane, this being the case for many glassy polymer at sufciently high concentration [9], the permeability increases after going through a minimum when the plasticization effects are stronger than the decrease of the permeability due to the glassy state of the polymer. This phenomenon is visualized for a thick membrane (l = 31 mm) in Fig. 1 for the glassy polyimide Matrimid 5218 from Ciba Geigy used in this study. Above the plasticization pressure, the permeability is no longer constant

Fig. 1. Pressure-normalized CO2 ux as a function of the feed pressure for a thick single-layer polyimide membrane (thickness l = 31 mm).

M. Wessling et al. / Separation /Purification Technology 24 (2001) 223 233 Table 1 PI layer thickness as a function of the initial polymer solution concentration determined by an optical thickness meter Polymer concentration (wt%) 0.6 0.4 0.15 Layer thickness (mm) 4 1.9 1.3 1.2


but increases in time [10]. For real applications with gas mixtures, Bos recently discussed the impact of plasticization on the gas separation process and its prevention by polymer material modication [11,12]. One major conclusion was that an increase in CO2 indicates signicant plasticization of the glassy polymer: as a result the permeability of the product to be rejected (methane) also increases resulting in undesired product loss thereof making the separation process less economic [12]. Moreover, plastization is not only observed with CO2 permeation but also during the permeation of condensable gases such as propane and propylene [13]. Considering the preliminary experiment [5] and the prior literature, there is evidence that thin glassy polymer layers generally suffer from this plasticization phenomenon requiring special measures to prevent it. This publication establishes experimental evidence that a decreasing membrane thickness to improve membrane productivity spoils selectivity performance.

3. Experimental

3.1. Membrane preparation

As glassy polymer, commercial polyimide Matrimid 5218, was kindly provided by Ciba

Geigy. Two-component silicone rubber, RTVA (90 wt%) and RTVB (10 wt%), were purchased from General Electric Silicones. The solvents used in this work, dichloromethane (for the polyimide) and n -hexane (for the polydimethylsiloxane) were reagent grade purchased from Merck and used without further purication. The polyimide thin lm was cast onto a glass plate pouring with a syringe 5 cc of a very diluted polyimide solution (0.6 0.075 wt%) in a casting glass ring of 10 cm diameter. Immediately after casting, the casting rings were placed in a box and the membrane was allowed to dry in an atmosphere of owing nitrogen for 1 h. Using an optical thickness meter from Leitz (resolution of 0.01 mm) the lm thickness of PI layers cast from polymer solutions having different concentrations were measured and the results are listed in Table 1. Due to the difculty to obtain defect-free membranes, free-standing thin lms of polyimide were coated while still sticking to the glass plate with a thicker layer of PDMS. The two polymers used to prepare the double layer composite membranes are signicantly different with respect to their physical properties and their permeation properties. Table 2 lists the gas permeabilities for various gases. The values given for the polyimide were obtained from a thick polyimide lm (thickness 31 mm) and the PDMS are taken from the literature [14,15]. Due to the predominating permeation properties of the polyimide one can assume in most cases that the performance of the double layer composite membrane is hardly inuenced by the supporting PDMS and that the membrane permeation properties are that of the thin glassy polymer layer. A large number of membranes were prepared out of which eight were thoroughly characterized. The membrane identication code, the total membrane thickness (PI + PDMS) as well as the polymer concentration of the PI solu-

Table 2 Permeabilities of silicone rubber and Matrimid polymide for different gases Gas permeability (Barrer) Silicon rubber Polyimide CO2 3250 8.7 He 350 24 O2 600 1.7 N2 280 0.23


M. Wessling et al. / Separation /Purification Technology 24 (2001) 223 233

Table 3 List of double layer membranes with membrane identication code (ID) showing the total thickness of the membrane and the polyimide concentration in the casting solution Membrane ID Thickness of double layer membrane (mm) Polymer concentration in polyimide casting solution (wt%) 0.3 0.075 0.6 0.3 0.3 0.3 0.3 0.3

oven at 150C for four days. (Note that differences concluded in later comparison of the thick and the composite membranes may be affected by differences in the preparation procedure.)

3.2. Permeation experiments

The experimental procedure used to determine the permeation coefcient was the constant volume/pressure variable method and the experimental set-up is comparable with the one described earlier [9]. All cells were double-walled and were thermostated using water pumped by a Colora thermostated bath. All the permeation experiments in this report were carried at 30C. The system was evacuated by means of three Edwards vacuum pumps. The pressure was measured using two Baratron Pressure transducers (one for the high-pressure chamber and other for the low-pressure chamber) connected to a PC. The permeability coefcient, P is given by P= Jl Dp VclVm = . (pf pp) Dt (pf pp)RTA (1)

1 2 3 4 5 6 7 8

52 22.5 58 51 55 41 31 29

tion are listed in Table 3. The overall thickness of the composite membrane was measured with a micrometer screw gauge (Mitutoyo). The accuracy of the micrometer was 1 mm. The exact procedure to prepare the double layer membranes was as follows: the rst step was to cast the polyimide layer using the procedure discussed above. When the rst step was nished a second layer was formed pouring 5 cc of a 10 wt% solution of PDMS in n -hexane in the same casting ring with a syringe. After another evaporation step of 1 h in a nitrogen atmosphere the membrane was dried in a nitrogen oven at 65C for 15 h to crosslink the PDMS layer. The double layer membrane was released from the glass plate with ultra pure water and further dried during four days in a vacuum oven at 30C to remove residual solvents. The membrane was transferred from the water bath to the petri dishes employed to dry it into the vacuum oven with the aid of a lter paper. For comparison, thick polyimide membranes (around 30 mm) were also prepared. A polymer solution of 20 wt% was cast onto a glass plate using a casting knife of 0.3 mm. The solutions were ltered with a 1 mm glass ber lter (Whatman) combined with a 5 mm metal lter (Bekaert Fibre Technologies). Immediately after casting the membrane was covered and dried in a nitrogen atmosphere. Then, the membrane was released with ultra pure water and dried into a vacuum

Where, J is the ux per unit of area and unit of time, l, the membrane thickness, (pi pf), the pressure difference between the feed and the permeate, (Dp /Dt ), the ratio of the pressure increase in the calibrated volume and the experimental time, after the steady-state was reached, Vc, the calibrated volume, R, the ideal gas constant, A, the membrane area, T, the temperature, and Vm, the molar volume at STP. The permeability is expressed in Barrer (10 10 cm3(STP) cm/(cm2 s cm Hg)). The pressure-normalized ux, P /l is given in cm3 (STP) cm/(cm2 s cm Hg).

4. Results and discussion

4.1. Helium permeation experiments

The rst experiments characterizing the permeation properties of the double layer membranes were carried out with helium. It is inert character resulting in a low gas solubility as well as its high diffusivity makes it a suitable gas to determine the virgin properties of the membrane and, later in

M. Wessling et al. / Separation /Purification Technology 24 (2001) 223 233


the sequence of characterization measurements, any alteration of properties due to physical aging or plasticization. Permeabilities were measured over a pressure range of 1 8 bar feed pressure. The procedure employed in all cases was the following: before permeation characterization, the membrane was evacuated at least for one night and the rst experiment was carried out at one bar feed pressure and vacuum on the permeate side. After a period of equilibration of 20 min, the experiment was performed. Then the feed pressure was increased by 1 bar to the next pressure and the permeability was measured again. In some cases after the measurement at the highest pressure (7 or 8 bars) the pressure was lowered and the permeability was measured again to identify any hysteresis effect. The composite membranes prepared (besides membrane 4) showed a decreasing permeance as can be seen in Fig. 2. In all the cases, except membrane c 4, the experiments were performed with the PI layer at the feed and PDMS at the permeate side. The permeability of membrane c 4 was more or less constant. The helium permeation does not show any hysteresis as can be concluded from Fig. 3. Prior to CO2 permeation, the thick membrane was also characterized by helium permeation showing a constant permeability with increasing and decreasing feed pressure.

When analyzing these Helium permeation data one should keep in mind that the resistance (l /P ) of the PDMS layer is of the same order than the PI resistance. Consequently, the helium permeance of the composite membranes may be affected by changes in the PDMS permeance. It can be found in literature that He permeability decreases with increasing pressure for PDMS [16]. The reason could be that the soft PDMS is compacted at high pressures. The compaction occurs when the PDMS layer facing the porous support, but not when the PDMS layer faces the feed (membrane c 4). Therefore, membrane c 4 showed comparable behavior as the thick PI membrane whereas and the permeability of the rest of membranes decreased due to PDMS compaction.

4.2. Layer thickness of double layer composite membranes

In the following section experimental results for the permeabilities of gases having a low solubility in the polymers (O2, N2 and He) are given (a) to determine the separation properties of the double layer membranes and (b) to calculate layer thickness of the double layer composite membranes. The experimental procedures for the measure-

Fig. 2. Pressure-normalized uxes of helium as a function of the feed pressure for double layer membranes. The numbers indicate the membrane numbers according to Table 3.


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Fig. 3. Pressure-normalized helium uxes as a function of the feed pressure for double layer membranes. The numbers indicate the membrane numbers according to Table 3. The open circle indicates a successive increasing feed pressure. The solid dots indicate a successive decreasing feed pressure. Table 4 Gas permeation properties of double layer membranes Membrane ID 1 2 3 4 5 6 7 8 Ideal selectivity O2/N2 P /l O2 (106 cm3(STP)/cm2 s cm Hg) 5.3 6.3 6 6.9 5.2 5.9 5.3 0.75 1.2 0.42 0.66 0.49 1.3 1.2 1.1 P /l He (106 cm3(STP)/cm2 s cm Hg) 4.11 5.62 2.64 4.00 3.02 6.04 5.46 5.38

ments of the O2 and N2 permeability were the same as in the case of He. The measurements were carried out at the feed pressure of 5 bars. At least 4 h of vacuum were applied between the measurements of O2 and N2. All permeation experiments with He, N2 and O2 were determined before the permeation experiments with CO2 to exclude any membrane conditioning effects on the inert gas permeation experiments. Table 4 lists the permeability values measured for O2 and He and the ideal selectivity of membranes for O2/N2 for all the membranes. Membrane 1 broke after the O2 measurement, therefore no permeation data for N2 and CO2 is available. As in the case of He all membranes,

except membrane 4, were in the permeation cell with the polyimide facing the feed and the silicone rubber facing the permeate. Using the resistance model [17] and the permeation data from single gas experiments, one can determine parameters characterizing the membrane morphology. The model was originally developed for integrally skinned gas separation membranes having a dense separating layer coated with a silicone rubber layer. The model is supposed to describe the performance of the double layer membranes as well and may be used to determine the skin thickness and number of defects of the glassy polyimide layer.

M. Wessling et al. / Separation /Purification Technology 24 (2001) 223 233 Table 5 Membrane morphology parameters estimated by the resistance model assuming defects in the PI layer Membrane ID Estimated thickness of the PI layer (mm) He/O2 1 2 3 4 5 6 7 8 4.7 3.0 5.2 2.7 4.3 1.1 2.5 2.6 O2/N2 1.6 4.1 2.6 3.4 1.4 1.5 1.7 He/N2 3.0 5.5 2.7 4.3 1.2 2.5 2.7 Estimated thickness of the PDMS layer (mm) He/O2 17.8 19.5 52.8 48.3 50.7 39.9 28.5 27.4 O2/N2 20.9 53.9 48.3 51.6 39.6 29.5 27.3 He/N2 19.5 52.5 48.3 50.7 39.8 28.5 26.3 Estimated porosity of PI layer (%) He/O2 0.32 0.3 0.09 0.03 0.08 B0 2.4 2.4 O2/N2 0.05 0.04 0.02 0.05 0.05 0.03 0.05



0.02 0.05 0.03 0.03 0.03 0.1 0.12

P l lPI J = PDMS + = PPDMS mPPDMS + (1 m )PPI l (pf pp)

(2) Eq. (2) represents the model for the composite membrane consisting of a thin glassy polyimide layer having a certain porosity m, coated and plugged with a PDMS layer. P is the permeability of the composite membrane, l, the total thickness of the composite membrane as specied in Table 3, PPI, the permeability of the polyimide, lPI, the thickness of the polyimide layer, PPDMS, the permeability of the silicone rubber and lPDMS, the PDMS layer thickness. Knowing the total membrane thickness, the permeabilities and the pressure-normalized uxes for two single gases, one can determine the thickness of the separate layers and the porosity of the PI layer. The results of the calculations are given in Table 5 for the possible combination of the three gases measured. It shows that the calculated PI layer thickness obtained from the combinations of He/O2 and He/N2 agree with each other whereas all values from the O2/N2 gas pair are consistently lower. Considering the PI layer thickness as a function of initial polymer solution concentration listed in Table 1, the values of the pairs He/O2 and He/N2 overestimate the PI layer thickness. The estimated porosity of the PI layer were low, normally below 0.1%. The disagreement of the optically measured PI layer thickness and the calculated one according to Eq. (2) leads to the question whether one may even assume defects that were plugged with PDMS.

Instead one also may only consider two single resistances in series. Assuming that the polyimide layer is defect free (m = 0) Eq. (2) reduces to Eq. (3) where the resistance is the sum of the resistances in series, P J lPDMS lPI = = + l (pf pp) PPDMS PPI


Table 6 lists the membrane thickness when the simple model of resistances in series is applied to permeation data for O2, N2, and He. Still there is some discrepancy between the calculated values and the optical values, however the magnitude of each value agrees much better with optically determined one. Considering the literature cited, it is also questionable whether one may use the permeTable 6 Membrane morphology parameters estimated by the resistance model assuming a defect-free PI layer ID Calculated PI layer thickness (mm) O2 1 2 3 4 5 6 7 8 2.1 1.4 3.9 2.4 3.3 1.2 1.4 1.5 N2 1.0 3.4 2.1 3.2 0.89 1.1 1.1 He 2.4 2.9 5.5 2.7 4.5 1.3 2.4 2.7


M. Wessling et al. / Separation /Purification Technology 24 (2001) 223 233

Table 7 Pressure-normalized uxes of helium before and after permeation of with carbon dioxide Membrane ID P /l (He)106 (cm3(STP)/cm2 s cm Hg) Before CO2 permeation 2 6 8 6.8 6.5 5.2 After CO2 permeation 6.9 6.9 5.4

ability values measured with thick lms to perform the described analysis. Therefore, the values listed have to be assumed to estimate the PI layer thickness, but they do not give an exact value.

4.3. Carbon dioxide permeation experiments

After permeation characterization with gases He, O2 and N2, the permeation behavior of the double layer membranes was determined for CO2 as a gas that readily dissolves in polymers and may cause plasticization altering the separation properties of the membranes. The experiments aim is to verify the phenomenon that thin-lm membranes made from glassy polymer show a

very different plasticization behavior than thicklm membranes. The experimental procedure was as follows: after one night evacuation of the membrane, the rst permeation experiment was carried out at 1 bar feed pressure. After one period of equilibration of 20 min the permeability was measured. This protocol was followed and the feed pressure was increased up to 8 bars in feed pressure steps of 1 bar. The membrane was kept at the highest pressure for 2 h to check whether the permeability increased with time. In some cases, after the measurement at the highest pressure (8 bars) the pressure was lowered stepwise and measured again to identify any hysteresis effects. Finally, to monitor membrane integrity, again He permeation experiments were carried out for some of the membranes. Permeation exchange experiments with thick Matrimid lms have shown that the permeability of He returns to almost the same value (slightly higher) after a membrane was exposed to signicant plasticization during the permeation of CO2. Hence the permeation exchange experiment is a good measure to monitor the integrity of the membranes after the sequence of characterization experiments. The results for three membranes characterized are listed in Table 7 and indicate no integrity loss.

Fig. 4. Pressure-normalized CO2 uxes as a function of the feed pressure for the membranes studied in this project. The numbers indicate the membrane ID as listed in Table 3.

M. Wessling et al. / Separation /Purification Technology 24 (2001) 223 233


Fig. 5. Hysteresis in pressure-normalized CO2 uxes as a function of the feed pressure for membrane c 2.

Fig. 6. Pressure-normalized CO2 uxes, normalized for the initial value at p = 1 atm, as a function of the feed pressure. The numbers indicate the membrane ID. The weight percentage given indicates the concentration of the polyimide in the original casting solution.

The CO2 permeation results for composite membranes are shown in Fig. 4, clearly demonstrating that most of the membranes do not show a distinct minimum but an immediate increase in the pressure-normalized ux. This reconrms the behavior found earlier [5]. Fig. 5 shows the results for membrane c 2 of increasing and subsequent decreasing the feed pressure. In contrast to the helium experiments, the gure shows signicant

hysteresis, again suggesting signicant plasticization at very low feed pressures. Also, at a constant pressure of 8 bars, the permeability is not constant but increases in time as previously described in the literature [10]. From the absolute values of the CO2 permeances and its absolute increase, no conclusion can be drawn with respect to the magnitude of plasticization. Therefore, the permeance at 1 bar feed


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pressure was used to normalize the permance. Fig. 6 shows the normalized CO2 permeance as a function of feed pressure. None of the values for the composite membranes lies below the ones of a thick lm. Some of the membranes still have a slight minimum, but most of them show an immediate increase of the pressure-normalized ux with increasing feed pressure. There appears to be a relationship between the concentration of the polymer solution concentration and the magnitude of the permeance increase. The less polymer in the initial casting solution (the thinner the PI layer) the stronger is the plasticization effect. The physical reasons for this phenomenon are not clear today and it requires much more experimental effort to systematically characterize material properties as a function of membrane thickness.

cant and may not be neglected in the analysis of membrane gas separation processes in plasticizing environments.

Acknowledgements One of the authors, M.L. Lo pez is indebted to the Conseller a de Educacio i Cie ` ncia de la Generalitat Valenciana, for a postdoctoral grant during her stay at the University of Twente.

[1] S.M. Shishastskii, Y.P. Yampolskii, K.V. Peinemann, Effects of lm thickness on density and gas permeation parameters of glassy polymers, J. Membr. Sci. 112 (1996) 275. [2] M.E. Rezac, P.H. Pfromm, L.M. Costello, W.J. Koros, Aging of thin polyimide-ceramic and polycarbonate-ceramic composite membranes, Ind. Eng. Chem. Res. 32 (1993) 1921. [3] P.H. Pfromm, W.J. Koros, Accelerated physical ageing of thin glassy polymer lms: evidence from gas transport measurements, Polymer 36 (1995) 2379. [4] P.H. Pfromm, Gas transport properties and aging of thin and thick lms made from amorphous glassy polymers, Ph.D. Dissertation, University of Texas at Austin, 1994. [5] M. Wessling, Relaxation phenomena in dense gas separation membranes. Ph.D. Dissertation, Twente University, 1992. [6] P. Pfromm, I. Pinnau, W. Koros, Gas transport through integral asymmetric membranes: a comparison to isotropic lm transport properties, J. Appl. Polymer Sci. 48 (1993) 2161. [7] J.H. Petropoulos, Plasticization effects on the gas permeability and permselectivity of polymer membranes, J. Membr. Sci. 75 (1992) 47. [8] E.S. Sanders, Penetrant induced plasticization and gas permeation in glassy polymers, J. Membr. Sci. 37 (1988) 63. [9] A. Bos, I. Punt, M. Wessling, H. Strathmann, CO2-induced plasticization phenomena in glassy polymers, J. Membr. Sci. 155 (1999) 67. [10] M. Wessling, I. Huisman, Th. Van den Boomgaard, C.A. Smolders, Time-dependent permeation of carbon dioxide through a polyimide membrane above the plasticization pressure, J. Appl. Polym. Sci. 58 (1995) 1959 1966. [11] A. Bos, I.G.M. Pu nt, M. Wessling, H. Strathmann, Suppression of CO2 plasticization by semi-interpenetrating polymer network formation, J. Polym. Sci. Polym. Phys. 36 (1998) 1547.

5. Conclusions Thin lm composite double layer membranes consisting of a glassy polyimide layer performing the gas separation and a dense support layer from PDMS have been prepared and characterized by gas permeation experiments. The purpose of this work was to elucidate if thin lms (used in industrial separation) show different plasticization performance than thick lms (used in laboratory experiments for characterization purposes). The polyimide separation layer had a thickness ranging from 1.5 to 4 mm and the support PDMS layer thickness ranged from 20 to 50 mm. In CO2 permeation experiments, thicker membranes show initially a decrease of the permeability with increasing feed pressure due to its glassy character. With increasing concentration of CO2 due to an increased applied feed pressure, plasticization sets in and the permeability goes through a minimum and increases for even higher pressures. In sharp contrast, thin lms do not show a minimum but the permeability increases immediately with increasing feed pressure. This veries that thin lms not only show a signicant aging behavior as described in literature by other authors, but they also show a signicant difference in performance in an plasticizing environment. The impact on membrane performance is signi-

M. Wessling et al. / Separation /Purification Technology 24 (2001) 223 233 [12] A. Bos, I.G.M. Pu nt, M. Wessling, H. Strathmann, Plasticization-resistant glassy polyimide membranes for CO2/ CH4 separations, Sep. Purif. Techn. 14 (1998) 27. [13] K. Okamoto, K. Noborio, J. Hao, K. Tanaka, H. Kita, Permeation and separation properties of polyimide membranes to 1,3-butadiene and n -butane, J. Membr. Sci. 134 (1997) 171. [14] M. Mulder, Basic Principle of Membrane Technology, Kluwer, Dordrecht, 1996.


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