You are on page 1of 49

Journal of Membrane Science 279 (2006) 1–49

Review

Polymeric CO2/N2 gas separation membranes for the capture of carbon dioxide from power plant flue gases
Clem E. Powell, Greg G. Qiao ∗
Cooperative Research Centre for Greenhouse Gas Technologies, Department of Chemical and Biomolecular Engineering, University of Melbourne, Australia Received 15 July 2005; received in revised form 23 November 2005; accepted 23 December 2005 Available online 17 February 2006

Abstract Global warming has been identified as one of the world’s major environmental issues. While it is impossible to completely stop the effects of anthropological global warming, it is possible to mitigate these effects via a variety of options. One such option is the reduction of greenhouse gas emissions by the capture of carbon dioxide from flue gases followed by underground sequestration. For this technology to become widespread, new methods of capturing carbon dioxide must be devised. While capture of carbon dioxide with amine solvents is the most mature technology, another possible contender is gas separation membranes. This review will focus on novel materials for gas separation. In particular, polymeric gas separation membranes are examined. Possible design strategies, synthesis, fabrication and role of novel materials are discussed. © 2006 Elsevier B.V. All rights reserved.
Keywords: Geosequestration; Gas separation; Membranes; Polymeric; Carbon dioxide; Nitrogen; Polysulfones; Polyimides; Polycarbonates; Polyarylates; Polypyrrolones

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1. Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2. Carbon capture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Gas separation membranes for CO2 /N2 separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Synthetic strategies for polymeric gas separation membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Polymer structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1. Polyarylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2. Polycarbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3. Polyimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.4. Polypyrrolones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.5. Polysulfones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.6. Copolymers and polymer blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3. Pressure/temperature effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4. Cross-linking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5. Mixed-matrix membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6. Asymmetric membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Appendix A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.1. Polyacetylenes (Figs. A1–A3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.2. Poly(arylene ether) (Fig. A4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.3. Polyarylates (Figs. A5–A7) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2 4 5 5 6 9 9 10 11 13 14 17 19 20 22 23 24 24 25 26

2.

3.

Corresponding author. Tel.: +61 3 8344 8665; fax: +61 3 8344 4153. E-mail address: gregghq@unimelb.edu.au (G.G. Qiao).

0376-7388/$ – see front matter © 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2005.12.062

2

C.E. Powell, G.G. Qiao / Journal of Membrane Science 279 (2006) 1–49

A.4. Polycarbonates (Figs. A8–A10) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.5. Poly(ethylene oxide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.6. Polyimides (Figs. A11–A15) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.7. 6FDA-based polyimides (Fig. A16). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.8. Poly(phenylene oxide)s (Fig. A17) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.9. Poly(pyrrolone) (Fig. A18) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.10. Polysulfones (Figs. A19–A22) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.11. Others (Figs. A23–A27) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.12. Copolymers and polymer blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.13. Cross-linking polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

28 29 30 34 36 36 37 40 42 44 45

1. Introduction Anthropogenic climate change is rapidly becoming one of the major issues in environmental science. Global temperatures are projected to rise between 1.4 and 5.8 ◦ C by 2100 in the absence of climate change policies [1]. This increase in global temperatures is likely to cause a number of negative effects; including rising sea levels, changes in ecosystems, loss of biodiversity and reduction in crop yields [2]. These effects can be partially alleviated by reductions in emissions of greenhouse gases. Reduction of greenhouse gas emissions can occur in a number of ways; such as improvements in energy efficiency, increased use of non-fossil fuel power sources, improved soil management and the geological sequestration of carbon dioxide from significant greenhouse gas producing point sources [3]. Membranes have been investigated for over 150 years [4,5], and since 1980 gas separation membranes have been used commercially [6]. Gas separation membranes are used in a number of industrial processes; such as the production of oxygen enriched air, separation of CO2 and H2 O from natural gas, purification of H2 , and recovery of vapours from vent gases. A number of reviews examining gas separation membranes have been published [6–13]. Different strategies towards the construction of more efficient membranes have suggested by Koros and Mahajan [14]. Recent work has investigated the practicality of using gas separation membranes for the capture of carbon dioxide from power station flue gases. While cost effective carbon sequestration is a complex multi-faceted operation with many significant hurdles to overcome (such as the cooling and compression of the flue gases prior to separation), there is a need to summarise the capabilities of membranes for carbon capture. There are a number of roles where gas separation membranes can be used to reduce emissions of greenhouse gases; however, this review will concentrate on the capture of carbon dioxide from flue gases and therefore focus on the use of membranes for the separation of carbon dioxide/nitrogen mixtures. A recent paper by Carapellucci and Milazzo looks at the possible use of membranes for carbon dioxide separation from flue gases from an engineer’s perspective [15]. This review will adopt a chemist’s view, examining the gas permeation properties of membranes in the light of their chemical structure. For this reason, attention will focus on dense film membranes. Other membrane structures, such as hollow fibre

and flat asymmetric membranes will be discussed, but in less detail. A variant on polymeric membranes is a carbon membrane. These membranes are constructed by heating a polymeric membrane above its decomposition temperature. These membranes can give excellent performance, but tend to have significant problems such as brittleness and cost. Because the mechanism of gas transport is very different in carbon membranes compared with polymeric membranes, carbon membranes will not be considered in this review. A number of useful references on carbon membranes have been published [16–21]. 1.1. Theory What follows is a brief introduction to some terms required in the experimental characterization of gas transport properties of membranes; a more complete discussion can be found elsewhere [8,10]. Generally, gas molecules are transported through a polymeric membrane by a solution–diffusion mechanism (other mechanisms included a molecular sieve effect and Knudsen diffusion). The relationship between permeability, diffusivity and solubility can be described by the following equation: P = DS where P is the permeability coefficient (cm3 (STP) cm−2 s−1 cmHg−1 ; a measure of the flux of the membrane), D the diffusivity coefficient (cm2 s−1 ; a measure of the mobility of the molecules within the membrane) and S is the solubility coefficient (cm3 (STP) cmHg−1 ; a measure of the solubility of gas molecules within the membrane). The common measurement of P is the barrer (10−10 cm3 (STP) cm−2 s−1 cmHg−1 ). While P is a measure of a polymer’s permeability, a membranes permeance must also be measured. This is quantified using a term known as a gas permeation unit (GPU), commonly used to describe the gas transport of a membrane, as opposed to a membrane material. The GPU has a unit of 10−6 cm3 (STP) cm−2 s−1 cmHg−1 . Experimentally, P is determined via the following relationship: Q P = l A p where l is the effective thickness of the membrane, Q the measure of the gas permeation rate through the membrane, A the surface

C.E. Powell, G.G. Qiao / Journal of Membrane Science 279 (2006) 1–49

3

area of the membrane and p is the pressure difference across the membrane. The ideal selectivity of one gas A over another gas B, α, is defined as PA α= PB The dual mode sorption model provides another means of describing the sorption of gas molecules into a glassy membrane. The gas molecules are assumed to fit into two categories; molecules absorbed directly into the polymer matrix and molecules absorbed into micro-cavities within the polymer matrix. The concentration of molecules absorbed in the polymer matrix, CD , and the concentration of molecules absorbed into micro-cavities, CH , can be described by the following equations: CD = kD p, C bp CH = H 1 + bp

the molecular sieves. Mixed-matrix membranes are discussed further in Section 2.5. The upper bound can be described by the following equation: αA/B = βA/B λA/B PA

where βA/B and λA/B are constants for each gas pair. Freeman has suggested a theoretical model for this relationship [24]. From this model, βA/B and λA/B can be calculated from the following equations: λA/B = and βA/B = SA λA/B S exp −λA/B b − f SB A 1−a RT dB dA
2

−1

where kD is the Henry’s Law coefficient, CH the hole saturation constant, p the pressure and b is the hole affinity constant. Hence, the total concentration of absorbed molecules can be described as C = kD p + CH bp 1 + bp

An experimental investigation of the dual-sorption model has been recently published by Chung and co-workers [22]. There appears to be a trade-off between selectivity and permeability, for example a highly selective membrane tends to have a low permeability. Robeson has suggested that the permeability–selectivity trade-off possesses an upper bound [23]. Fig. 1 provides an example of this upper bound. Subsequent to the publication of Robeson’s paper, only a few examples of polymeric membranes have been published which exceed the upper bound. Koros and Mahajan have suggested that it may be possible to exceed the upper bound significantly by the use of “mixed-matrix membranes” [14]. These membranes consist of a polymeric membrane with a large volume of sub-micromolecular sieves. This approach could combine the processability of membranes with the high performance characteristics of

where d is the kinetic diameters of gases A and B, S the solubility coefficient of gases A and B, a the constant equal to 0.64, and b and f are the constants depending on the polymer. The constant b = 9.2 and 11.5 cm2 s−1 for rubbery and glassy polymers respectively. The value of f can vary by a very large degree, from 0 to 14,000 cal mol−1 . The fractional free volume (FFV) is a measure of the theoretical volume of the polymer divided by the actual volume of the polymer. The fractional free volume is usually defined as V − V0 V where V is the volume of the polymer per unit mass and V0 the volume per unit mass occupied by the polymer chains. Park and Paul have suggested a definition of FFV, one which assumes that the FFV is not constant for all gas types [25]: FFV = V − (V0 )n (FFV)n = , V
K

(V ) =
k=1

γnk (VW )k

where γ nk is a set of empirical factors which depend on gas n and substituent k. (VW )k is the van der Waals volume for substituent k. Using this revised FFV, the authors can get a good correlation between experimental permeabilities and permeabilities calculated with the following relationship: P = A exp − B FFV

Fig. 1. Oxygen–nitrogen selectivity vs. oxygen permeability (from Ref. [23]).

where A and B are the constants for the gas. For carbon dioxide at 35 ◦ C and 10 atm pressure, A = 1750 and B = 0.860. For nitrogen at 35 ◦ C and 2 atm pressure, A = 112 and B = 0.967 [25]. Some attempts have been made to model the passage of carbon dioxide through a polymeric membrane via a solution–diffusion mechanism [26–30]. Gases, in these models, tend to move through gaps in the polymeric structure—called the free volume. Because of movement of the polymer chains, a channel between gaps can be formed allowing gas molecules to “jump” from one gap to another. Through this jumping motion, gas molecules can effectively diffuse through the membrane structure. Selective transport of gases can be achieved by use of a

4

C.E. Powell, G.G. Qiao / Journal of Membrane Science 279 (2006) 1–49 Table 1 Examples of group contributions to permeabilities Group Volume ˚ 3) (A CO2 permeability (barrer) N2 permeability (barrer)

39.0

3.34

0.327

40.75 Fig. 2. Movement of CO2 through a 6FDA–PDA membrane (from Ref. [27]).

0.021

0.00139

polymer which forms channels of a certain size. Large channels will allow faster diffusion of gases through a membrane at the cost of less selectivity between different gases; smaller channels will allow a much greater selectivity at the cost of lower permeation rates. A more complete discussion of gas transport through polymeric membranes has been published by Maier [8] (Figs. 2 and 3). Pavel and Shanks have performed a molecular dynamics study of the diffusion of carbon dioxide and oxygen through a variety of polyesters [31]. A relationship between calculated density and calculated diffusion was not observed. There was a relationship between the calculated diffusion coefficient and the calculated Voronoi free volume. The gas molecules were observed to travel through transient cavities through the polymer structure. The distribution of these holes had a significant dependence on the conformation of the phenyl rings. The calculated diffusion coefficients followed a para > ortho > meta series. Another method to determine permeabilities theoretically is a group contribution approach [32,33]. The authors have used a number of literature polymers to calculate volume and permeability contributions for a large number of structural moieties commonly present in polymers used in the construction of gas separation membranes. The permeabilities can then be calculated using the following expression:
n

65.56

309.0

15.5

74.5

10.66

0.508

68.0

34.18

0.877

54.94

16.0

0.678

773.19 Data from Refs. [32,33].

278.7

27.5

ln P =
i=1

φi ln Pi

where φi is the volume fraction of group i, and Pi is the permeability contribution of group i.

One advantage of a group contribution approach is the ability to quickly examine the effects of structural alterations on permeabilities. Some examples of the volume and permeabilities of various groups are tabulated in Table 1. 1.2. Carbon capture Geological sequestration of carbon dioxide requires two separate steps: the first is the capture of carbon dioxide, and the second is the transport and sequestration of the captured carbon dioxide. This review will only concentrate on the first process; however, for an example of the sequestration aspect, a review of the Weyburn pilot project, located in Saskatchewan Canada, is informative [34]. A number of different techniques have been proposed for the capture of carbon dioxide. These include chemical absorption, physical absorption, pressure swing absorption,

Fig. 3. Movement of CO2 through the cavities of a 6FDA–ODA membrane (from Ref. [27]).

the report examines inorganic membranes in detail. Addi- Table 2 Typical non-nitrogen components of untreated flue gases from Eastern Low Sulfur Coal Species H2 O O2 CO2 Hg complexes CO Various hydrocarbons HCl SO2 SO3 NOx Data from Ref. O2 .E. Conversely. thermally and chemically robust. SO2 . Baker has pointed out that the compression and cooling of flue gases prior to a membrane separation require significant amounts of energy. have recently published a review on the geological sequestration of carbon dioxide. where the excess oxygen is kept to a minimum. which means that large quantities of gases will need to be processed. While the composition of flue gases varies greatly depending on the fuel source. such as the production of steel. One is their ability to permeate the gas . The significant difference between the power plants and steel works was the concentration of carbon dioxide in the waste gas stream. This review includes a brief discussion on the possibility of membrane separation of carbon dioxide. or these chemicals will need to be removed prior to the membrane separation step. There are a number of issues associated with the capture of carbon dioxide from flue gases which limit the use of membranes.G. the membranes will need to be chemically resistant to the harsh chemicals contained within flue gases. citing their low productivities. when high purity gas streams are not vital. have recently investigated the possible role of cardo polyimide membranes for the capture of carbon dioxide from flue gases [36]. so the gases need to be cooled to below 100 ◦ C. prior to membrane separation. Concentration 5–7% 3–4% 15–16% 1 ppb 20 ppm 10 ppm 100 ppm 800 ppm 10 ppm 500 ppm tionally.C. Powell. White et al. which in turn lowers the efficiency of the power plant [6]. For a membrane to be useful for the capture of carbon dioxide. oxygen in waste gases can significantly reduce the purity of the carbon dioxide gas stream because of the relatively high permeability of oxygen through membranes. Fuel gases are generally reducing with CO. untreated flue gas streams also contain considerable particulate matter. Membranes are a low cost means of separating gases. which will in turn lower the thermal efficiency of the power plant. the carbon dioxide can be separated from the hydrogen gas which is then used to produce energy. This technique works by reaction of hot steam and methane to form a carbon dioxide and hydrogen gas mixture. CO2 . [37]. G. The concentration of carbon dioxide in flue gases is low. this effect tended to decay with time. creating a pressure difference across the membrane will require significant amounts of power. Baker has suggested using N2 /O2 separation membranes to produce oxygen enriched air which can then be used for combustion of fossil fuels [6]. and able to be cheaply manufactured into different membrane modules. resistant to plasticisation. Kazama et al. It was found that polymeric gas separation membranes were less cost effective at capturing carbon dioxide than amine solvents from power plants. They conditioned the polymers with exposure to high pressure CO2 . Conversely. high carbon dioxide/nitrogen selectivity. [35]. NOx and HCl. cryogenic distillation and separation via membranes. power plant and prior treatment. A potential problem is identified. Likewise. 2. This can be avoided in external combustion plants. cost effective. The authors are unconvinced about the usefulness of polymeric membranes for the capture of carbon dioxide. Gas separation membranes for CO2 /N2 separation 2. The authors find that a multi-step polymeric membrane system can effectively separate out carbon dioxide from gas flues. a modelling study of polymeric membranes in gas turbine power plants by Carapellucci and Milazzo is more encouraging [15]. In addition to polymeric membranes. which caused a significant increase in the performance of the polyimide membrane. produce flue gases with a considerably higher CO2 concentration. some general statements can be made. Additionally. is the incorporation of membranes into a precombustion separation step. Sakellaropoulos and co-workers have investigated the use of polysulfone and polyimide membranes for separation of CO2 /N2 from flue gases [38]. however this was reversed when steel works were examined. it should posses a number of properties. Flue gases tend to be oxidising and generally consist of N2 . Similar concerns are expressed by White et al. Table 2 lists typical components of untreated flue gases from eastern low-sulfur bituminous coal [37]. however. CO2 can be separated from fuel gases prior to combustion. H2 O. At this stage. Qiao / Journal of Membrane Science 279 (2006) 1–49 5 temperature swing absorption. Both of these techniques are attempts to increase the concentration of CO2 and overcome one of the factors which disadvantage gas separation membranes. Other potential uses for membranes in the sequestration of carbon dioxide. Also recently published is a US Department of Energy report examining membrane separation of carbon dioxide for the purposes of geological sequestration [18].1. Synthetic strategies for polymeric gas separation membranes Polymers used for CO2 /N2 separation membranes have to meet certain criteria. namely: • • • • • • • high carbon dioxide permeability. The high temperatures of flue gases will rapidly destroy a membrane. CO2 and H2 S [35]. H2 O. H2 . resistant to aging. Some industrial processes. comprehensively covering both the capture and storage of carbon dioxide [35].

6. The high free volume means the better gas permeation. Another important variable is the casting solvent used to form the membrane. polyaniline [39–42]. The permeability tends to drop with increasing pressure. The third one is that the polymeric membrane needs to provide good thermal and mechanical properties. For this reason. These have been neglected in the interests of clarity. Examples of polymers used in the construction of gas separation membranes include polyacetylenes [9]. Additionally. relative to many other polymers. the soft block can be synthesised from a polymer with more flexible chains and that can form rubbery segments on the polymer chain. When a polymeric membrane formed by use of these copolymers. have investigated the effect of varying the casting solvent on the permeability of poly(4-methyl-1-pentene) [96]. whereas the nitrogen permeability dependence is considerably less. it led to a drop in permeability from 400 to 230 barrer [95]. If the hard block is formed by high temperature polymers such as polyimides. The second criterion is the separation of carbon dioxide from other gases. Synthetic strategy for polymer structure used as CO2 separation membranes. It should be noted that permeabilities can be altered considerably by conditioning. This introduces difficulties in comparing results which in turn reduces the utility of gas permeation tests as a tool for determining structure/activity relationships.54]. there is considerably more data on pure gas measurements. 4.56]. through the membrane. Usually the balance of the hard and soft block ratio provide the good separation without loss of permeability. The hard block can be synthesised by polymer with well-packed and more rigid structures. poly(ethylene oxide) [55. such as thermal annealing of the membrane. G. it can also provide better thermal resistance. poly(phenylene oxide)s [75–77]. The permeability of carbon dioxide frequently shows a strong dependence on the carbon dioxide partial pressure. the rubbery segments usually form continuous microdomains and the nature of the flexible chain structure allows the transportation of gas. While mixed gas data would give results more applicable to industrial applications.0 to 93.50. The displayed polymers have been selected from Appendix A and all have been measured at 35 ◦ C and the carbon dioxide permeability at 10 atm. the results presented here are from pure gas measurements. so a reasonable gas flux is achieved during separation. Examples of these polymers are displayed in Fig.2. The glass segments usually gave lower free volume while the rubbery segments provide higher free volumes. and then rise steeply with increased pressure. Polymer structure This section aims to detail different polymers and their CO2 and N2 gas transport properties. 6 displays the literature values carbon dioxide permeability versus carbon dioxide/nitrogen selectivity of a large number of polymers. polyetherimides [53. for example.95]. glassy polymer segments will form a structural frame and provide mechanical support. On the other hand. poly(pyrrolone)s [78–82] and polysulfones [48. hence provide a good permeability. Upon thermally annealing a 6FDA–durene membrane at 100 ◦ C for 7 h then 180 ◦ C for another 7 h. Powell. Chung and co-workers have performed a study on the effect of cast- . the permeability will reach a minimum. A clear upper bound is observed.8 barrer depending on the casting solvent (see Table 3 for more details). with values ranging from 400 to 456 barrer [65. Also missing are some of the extremely highly fractional free volume polymers. On the other hand. the carbon dioxide permeability of the polyimide 6FDA–durene has been determined by three different laboratories.71. this is particularly pronounced in glassy polymers. hence the separation can be conducted effectively and sometimes at elevated temperatures.E. for this reason. For example. 4. Attention has been focused primarily on glassy section or block of the polymers in the scientific literature recently.83–94]. polycarbonates [48–52]. 2. therefore it forms a glassy segment of the polymer chain. While the poly(imide ethylene oxide) and cross-linked poly(ethylene oxide)s can appear to give both very high permeabilities and selectivities. The above criteria are commonly met by synthesis of a block polymer system as shown in Fig. The copolymer usually processes a hard block and a soft block. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig. Mohr and Paul. There is an extensive body of literature on gas separation membranes. Both the classes of polymers are discussed later in the text. some polymers are covered in more detail at the expense of others. The carbon dioxide permeability was found to vary from 15. this may be due to the lower pressure at which they were measured. 5. these polymers are not displayed in Fig. polyarylates [44–47]. Mixed gas tests would result in different values. If the membrane is vulnerable to plasticisation. The high free volume can also by achieved by intruding bulky structures into the soft blocks. poly(arylene ether)s [43]. Fig. polyimides [57–74].6 C.G.

Pereira and Admassu have investigated the effect of impurities such as pump compressor oils on the performance of a number of gas separation membranes [98. Another important issue concerning gas separation membranes is the effect of impurities on the membranes. This is particularly pronounced in thin films.G. Powell.C. Huang and Paul have published a method of monitoring the aging effects on gas transport properties of glassy polymers [100]. G. 6. permeability of polymeric membranes. 5. . ing solvents on the permeabilities of a copolyimide membrane [97]. Qiao / Journal of Membrane Science 279 (2006) 1–49 7 Fig.E.99]. Glassy polymers are vulnerable to aging effects. Example of polymeric structures. Selectivity vs. Fig.

One disadvantage of a high solubility is that this tends to lead to increased rates of plasticisation. have investigated the effect of methyl substituents on the gas permeability and solubility coefficients of 6FDA-based polyimides [71]. a decrease in the carbon dioxide/nitrogen selectivity is also observed upon the addition of extra methyl groups. usually at the cost of selectivity. with reduced selectivities. at the cost of a slightly reduced permeability.5 6.6 7. however.8 17.8 C.1 2.4 12.E. • Modification of the regions of the polymer which form a gap between cavities. with a corresponding loss in selectivity.4 (hexafluroisopropylidene)diphthalic anhydride to give a range of polyimides. [96]. Tanaka et al.and meta-phenyl diamines have been reacted with 4. Gas transport properties are affected by the method by which the membrane is constructed. can in principle. changes in the polymer packing can significantly alter the permeabilities in a number of ways: • Incorporation of bulky side groups into the polymer’s backbone tends to lead to an increase in the permeabilities.000 barrer and a nitrogen permeability of 4970 barrer. Other preparation variables investigated include drying time.0 42. it is best to compare membranes that have been prepared with identical methodology. G. By altering the concentration of polymer in the casting solvent. This increased sorption was attributed to an increase in CH . The effect of incorporating bulky substituents into bisphenol A polycarbonate has been investigated by Muruganandam and Paul [52]. This effect can be counteracted by the addition of certain additives. nitrogen and various hydrocarbons in a variety of commercial rubbery polymer membranes has been conducted by Freeman and co-workers [104]. Materials for effective separation of gases can follow one of two overall strategies. • Para substituted phenyl rings tend to give. A series of methyl-containing para. As the heating was increased. The rate at which gases diffuse through a polymeric matrix depends on the amount and distribution of the free volume within the polymer. The authors found that heating the polycarbonate above Tg . Powell.0 α(CO2 /N2 ) 13. These permeabilities tend to decrease with time due to slow crystallisation of the polymer. Relative to bisphenol A polycarbonate. in many cases. Improving the solubility ratio of a membrane is. manipulation of the polymer structure can alter the barrier between cavities allowing carbon dioxide to diffuse through the polymer structure significantly faster than nitrogen. slight changes to the permeability are observed. Data from Ref. and then quenching the film would increase the CO2 sorption. • Closely packed polymer chains tend to give better selectivity.0 77. The introduction of mixed-matrix membranes may allow superior performance. For these reasons.G.8 83. A number of different polymers have been investigated for this effect. This polymer possesses a carbon dioxide permeability of 28.0 Permeabilities in barrer.7 P(N2 ) 1. relative to meta. This may be achieved by the synthesis of polymers which consist of alternating bulky and flat groups. As the number of methyl groups increases (from zero to four) a significant increase in the carbon dioxide permeability is observed (from 9. These very large permeabilities are associated with a very large fractional free volume. Yilmaz and co-workers have investigated the effect on gas transport properties by altering the preparation of a polycarbonate membrane [101]. to the synthetic strategy described earlier. much simpler than improving the diffusion selectivity. The synthetic polymer with the largest measured permeabilities is poly(1-trimethylsilylpropyne).4 6. Tetrabromobisphenol A polycarbonate exhibits better selectivities.7 1. pressure = 2 atm. be used to alter selectivity for different gas pairs. Unfortunately.6 27. allowing the addition of functional groups to interact with them and thus increase the solubility of carbon dioxide within the membrane. Another study by Tsujita and co-workers has examined the effect of thermal and pressure conditioning on the gas transport properties of polycarbonates [102]. As the gas molecules jump from one transient cavity to another. the loss of selectivity is slight compared with the increase in carbon dioxide permeability. conceptually. Further. Carbon dioxide is considerably more polarisable than nitrogen. However. leading to an increase in the permeabilities and a loss of selectivities. at the cost of permeability. This increase in permeabilities has been subscribed to an increase in the number of large free spaces.6 15. An investigation into the permeabilities and solubilities of carbon dioxide. As expected. increasing the rate of diffusion of carbon dioxide through the polymeric structure and increasing the solubility of carbon dioxide in the membrane.8 93. there is considerably less scope for the rational design of these membranes. tetramethyl.7 12.20 to 440 barrer). and annealing time. temperature = 35 ◦ C. significantly higher permeabilities. The insertion of bulky substituents into the peripheral polymer backbones should disrupt efficient packing of the polymeric chains.8 13. Increasing the solubility ratio of a polymer for carbon dioxide over nitrogen may allow the upper bound to be exceeded. the CO2 sorption capacity of the membranes likewise increased. Other polyacetylenes give lower. Qiao / Journal of Membrane Science 279 (2006) 1–49 Table 3 Effect of casting solvent on the gas transport properties of poly(4-methyl-1pentene) Casting solvent Chloroform p-Xylene cis-Decalin Cyclopentane Cyclohexane Carbon tetrachloride Crystallinity 57 62 65 41 51 56 P(CO2 ) 15. Koros and co-workers have also investigated the carbon dioxide permeability of various polycarbonates at high pressures [103]. Changes of a similar magnitude are also observed when dichloromethane is used instead of chloroform as the casting solvent.and tetrachloro-bisphenol A polycarbonate show greater permeabilities. A more complete discussion of this can be found elsewhere [8]. . Poly(ethylene oxide) is an example of a polymer with high carbon dioxide solubility. there is frequently a trade-off between selectivity and permeability.

Polyaniline which had been doped with HCl. Qiao / Journal of Membrane Science 279 (2006) 1–49 9 Fig. have found considerably lower selectivities. These polymers were synthesised by using a combination of various monomers. a small number possess permeabilities as high as 85. Polycarbonates A number of polycarbonates have been synthesised and their carbon dioxide/nitrogen gas transport properties studied. 7. but still substantial permeabilities.2. Polyarylates A large number of polyarylates have been synthesised and their gas transport properties studied. The structure of a common polyarylate is displayed in Fig. The sterically bulky polyarylate. with Hellgardt reporting a CO2 /N2 ideal selectivity of only 17 [42].40]. The carbon dioxide permeabilities and carbon dioxide/nitrogen selectivities for a number of polyarylates is graphed in Fig. Poly- Fig.G. and hence permeabilities is poly(dimethylsiloxane) which possesses a carbon dioxide and nitrogen permeabilities of 4550 and 351 barrer. A number of polymers types have shown good gas transport properties and considerable scope for structural variations. with an acid chloride to afford the desired polyarylate. dedoped with ammonia and finally redoped with HCl have been reported to give very high selectivities [39. 8. 7. 2. PA. it is unlikely that they will be useful for the capture of carbon dioxide. . for example. Most polyarylates possess carbon dioxide permeability less than 25 barrer. These polymers give very good combinations of carbon dioxide permeabilities and selectivities. a direct comparison of gas transport properties is difficult. The structure of these polymers is displayed in Fig. A recent communication by Budd et al. while the nitrogen permeabilities range from 92 to 42 barrer. ethylene oxide (EO). Polyaniline has been extensively studied in the literature [39–42]. Subsequent studies. such as bisphenol A. Another polymer with an extremely large fractional free volume. Because these gas transport properties of these materials were tested at different pressures and temperatures to the majority of the gas permeabil- ity literature. For example. expands the field of high fractional free volume gas separation membranes [105]. these polymers also incorporated reasonable solubility selectivities. reports a CO2 permeability of approximately 0.1. Yoshino et al. 9. Powell. The most common synthetic route involves reaction of a diol. G. Two aromatic rigid yet twisted polymers (denoted as polymers of intrinsic microporosity) have been synthesised and their permeabilities measured.C. The oxygen/nitrogen separation properties of polyarylates have been reviewed by Paul and Pixton [106].1 barrer [42]). The following describes the main polymer types which have been studied as CO2 separation membranes. Because of the low CO2 permeability of polyaniline membranes (Hellgardt. Unlike other high fractional free volume polymers.E. have examined a number of high molecular weight branched poly(ethylene oxide)-based polymers [56]. 8. TBHFBPA/tBIA. respectively. the structure of which is displayed in Fig.2. Examples of high free fractional volume polymers. with one example possessing a carbon dioxide permeability of 773 barrer and a carbon dioxide/nitrogen selectivity of 46. exhibits the highest carbon dioxide and carbon dioxide/nitrogen selectivity of 19. 2-(2methoxyethoxy)ethyl glycidyl ether (EM) and allylglycidyl ether (AGE). 2.2. The carbon dioxide permeabilities range from 1100 to 2300 barrer. 10. however. an ideal selectivity for CO2 /N2 of 1560 has been reported [39]. This reaction can be performed under a variety of conditions such as interfacial or a stepwise polycondensation.

A number of different diahydrides have been used in the synthesis of polyimides for gas separations.107]. Polyimides are generally synthesised by the reaction of a diamine with a diahydride in an aprotic solvent to form a polyamic acid. The structures of these starting materials are displayed in Fig. Polyimides Polyimides combine excellent thermal and chemical stability with a very wide range of carbon dioxide permeabilities. Carbon dioxide permeability vs.G. Carbon dioxide permeability vs. The chemical structures of these dianhydrides is displayed in Fig. Polyimides incorporating the group 6FDA have been the object of much research. selectivity for polycarbonates. 12.10 C. BPDA or 6FDA as the dianhydride. (c) the formation of charge-transfer complexes is reduced. a number of authors have synthesised novel dianhydrides for the use in the formation of novel polyimides [66. PI–TMMPA. selectivity for polyarylates. 9.2. The carbon dioxide permeability and carbon dioxide/nitrogen selectivities for a number of polycarbonates are graphed in Fig. 15). which in turn reduces the likelihood of effective chain packing [9. which possess a carbon dioxide permeability of 111 and a carbon dioxide/nitrogen selectivity of 15. While most polyimides are synthesised using either PMDA. An example of the synthesis of the polyimide 6FDA–pPDA is displayed in Scheme 1.0. 11. The polyimide.3. has been observed to give extremely high permeabilities. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig. 14. as they tend to combine both high selectivities and high permeabilities. Some polyimides. The structure of this polymer is displayed in Fig. particularly those incorporating the group 6FDA possess very high carbon dioxide permeability. 11. the ready availability of structural variants of bisphenol A has led to a large number of different polymers. Fig. Three reasons are commonly given for this behaviour: (a) the CF3 groups considerably increase the stiffness of the chain. carbonates are generally synthesised by reaction between a diol and phosgene under a variety of conditions. (b) effective chain packing is reduced by the large CF3 groups which leads to an increase in the permeability. Fig. 13. One notable exception to this is the polycarbonate TMHFPC. and selectivities range from 15 to over 25. An extensive review of the gas separation properties of polyimides was published in 1996 [13]. 10. This polymer then undergoes a polycondensation reaction (either thermally or chemically) to form the desired polyimide.E. 12. Most polycarbonates tend to have a carbon dioxide permeability of under 40 barrers. TBHFBPA/tBIA. Fig. These dianhydrides were then reacted with a range of diamines to give a number of polyimides. 2. . This result is unsurprising given the large steric bulky nature of the polymer (Fig.108]. G. TMHFPC. Like many polymeric materials used in the synthesis of gas separation membrane materials. these include PMDA. 6FDA and BTDA. allowing the membrane to more effectively separate molecules on the basis of steric bulk. Powell.

19 [79. however. as varying the proportion of the mers can vary the rigidity.G. Qiao / Journal of Membrane Science 279 (2006) 1–49 11 Scheme 1. the number of different polypyrrolones which have been studied is quite limited. 17 displays the carbon dioxide permeability and carbon dioxide/nitrogen selectivities of a variety of polyimides. The synthesis of the polypyrrolone 6FDA–TAB is displayed in Scheme 2. A study on the effect of cross-linking Matrimid 5218 is discussed in Section 2. Polypyrrolones Polypyrrolones are structurally similar to polyimides. leading to only a small decrease in the carbon dioxide/nitrogen selectivity [109]. The temperature dependence of these copolypyrrolones has also been studied [80]. despite this. The presence of the tetraamine groups required for reaction significantly limits the possible structural variations. 16. Matrimid 5218. 6FDA/PMDA–TAB. . Zimmerman and Koros have published a series of papers investigating copolymers of 6FDA/PMDA–TAD [79.80]. However.C. The results of these are discussed more fully in the copolymer section. Matrimid has been functionalised by brominations. The structures of these polymers are displayed in Fig. they are considerably more rigid. which can be greater than that of similar polyimides. Another target of considerable research is the commercial polyimide. Polypyrrolones are of interest because of their high thermal and chemical resistance. Polypyrrolones are generally synthesised by reaction of dianhydride and a tetraamine functionalised monomer.4. which is shown in Fig. Because of their high rigidity. 18. Zimmerman and Koros have performed an investigation into a copolypyrrolone. For this reason. Walker and Koros have investigated a polypyrrolone 6FDA–TADPO and compared it to a number of polymers [82]. a significant volume of the literature covers copolypyrrolones and copoly(imides pyrrolone).2. G. Fig. the carbon dioxide permeability decreases and the selectivity increases.E. Synthesis of 6FDA–pPDA. As the proportion of PMDA increases. Bromination tended to increase both the carbon dioxide and nitrogen permeabilities. it has been suggested that polypyrrolones can act as a molecular sieve. 2.4.80]. the structure of which is displayed in Fig. Powell.

Fig. 13. 15. 14. . Fig. Polypyrrolone structures. Powell.12 C. Common dianhydrides used in the synthesis of polyimides. Fig. G. Catechol-based dianhydrides. selectivity for polyimides. Carbon dioxide permeability vs. PI–TMMPA. 17. 16. Fig. Synthesis of 6FDA–TAB. Matrimid 5218.E. 18.G. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig. Fig. Scheme 2.

Some polysulfones have been functionalised by a bromination [110]. An extensive study of the gas transport properties of PSF has been performed by Paul and co-workers [54]. Naphthalene-based polysulfone membranes. 20 and 21. The structures of these polymers are displayed in Figs. ensuring that the final products were composed of a mixture of unreacted monomer. G. 19. Fig. 22). 22. Adamantane-based polysulfone membranes. because of their reasonable performance and low cost. 25) Fig.5. brominated monomer and alkylated monomer. Guiver and coworkers have abstracted the bromine atom with butyl lithium and subsequently performed a reaction with iodotrimethylsilane [85]. Aitken and Paul have likewise examined naphthalene-based polysulfone membranes [91]. Polysulfones are generally synthesised by a condensation reaction between a bisphenol and a dihalogenated diphenylsulfone. Pixton and Paul have investigated the transport of different adamantanebased polysulfone membranes [88]. The most extensively studied polysulfone is PSF. leading to the potential for more structural variation. The reaction site on the polymer can be altered by using a brominated polysulfone as a precursor. 20. Using this technique a number of novel polysulfones structurally related to PSF (Fig. Novel polysulfones-based off PSF. formed using bisphenol A.2. This increases the reactivity of the polymer. A number of different polymers were successfully synthesised with different degrees of bromination and alkylation. Fig. Both the bromination and alkylation steps were not carried out to completion. 23). large numbers of PSF derivatives have been synthesised. Two routes for the synthesis of PSF are displayed in Scheme 3. By substitution of bisphenol A with a different diol. 6FDA/PMDA–TAB.E. Polysulfones are already used in industrial gas separation processes [6]. . Qiao / Journal of Membrane Science 279 (2006) 1–49 13 Fig. These display a wide range of carbon dioxide permeabilities and selectivities. 21. Most other polysulfones are structurally related to this polymer.G. 2. Powell. have further reacted the polymers with a series of acetylenes utilising a PdII /CuI catalyst (Scheme 4) [87]. More exotic polysulfones have also been examined. PPSF (Fig. HFPSF (Fig. Bonfanti et al.C. Polysulfones Considerably amounts of research have been performed on the gas transport properties of polysulfones. 24) and TMPSF (Fig. A number of polysulfones have been modified by reaction with butyl-lithium followed by addition of a pendent group [83–86].

Powell.6. Fig.E. have been synthesised and their gas transport properties examined. A copolymer will tend to have permeabilities which are intermediate compared with the homopolymers which make it up. G. An NMR study of some polysulfones modified by addition of a trimethylsilyl group found a decrease in chain mobility when the Me3 Si group was ortho to the sulfone group through the ether linkage [111].G. Synthesis of PSF. Copolymers and polymer blends Copolymers offer the potential to fine tune permeabilities and reduce the costs of polymer synthesis. These copolymers generally gave both high selectivities and a high CO2 permeability. 27.2. The structure of these copolyimides is displayed in Fig. As the proportion of sulfonated groups increases. the carbon dioxide permeability drops dramatically. A series of copolyimides formed from reaction of NTDA with a mixture of sulfonated and non-sulfonated diamines was synthesised by Espuche and co-workers [63]. 26 displays the carbon dioxide permeability and carbon dioxide/nitrogen selectivity for a variety of polysulfones.14 C. polyamides and polyimides have been investigated by Okamoto and co-workers [112]. The CO2 /N2 gas separation properties of a large series of poly(ethylene oxide) segmented copolymers with polyurethanes. likely due to the high solubility of carbon dioxide into the . Qiao / Journal of Membrane Science 279 (2006) 1–49 Scheme 3. 2. Likewise an expensive and effective polymer can be significantly reduced price by the formation of a copolymer which incorporates cheaper monomers.

and function more like molecular sieves than polymeric membranes. A decrease in the permeabilities was observed with an increase in the amount of amidation. Dense films of 6FDA–durene and 6FDA–durene/mPDA (50:50) have also been reacted with N.E. As the naphthol concentration increases. Pure 6FDA–FDA has greater carbon dioxide and nitrogen permeabilities than pure 6FDA–HFBAPP. FDA and HFBAPP. The authors found that the effect of . the degree of amidation was also increased. While. The increase in permeabilities for certain copolyimides is greater than expected from the addition rule of the semi-logarithmic equation. Copolysulfones incorporating both bisphenol A and 1.1-bi2-naphthol have had their gas transport properties studied [114]. The structure of this copolymer is displayed in Fig.N-dimethylaminoethyleneamine in hexane to perform an amidation on the group ring [58]. Sakellaropoulos and co-workers have investigated the gas transport properties of a series of polysulfone–polyimide polymer blends [116. 6FDA has been reacted with various ratios of two diamines. Similarly. This combination of both high selectivities and permeabilities may be related to the low pressures used during the determination of the gas transport properties. 6FDA–TAB/DAM has been examined by Burns and Koros [115].C. to give a number of copolyimides. This unexpected increase is due to a greater increase in the solubility coefficients than antcipitated. Similarly 6FDA copolyimides have been synthesised [61. As the weight fraction of FDA increases. 28) which exhibits a CO2 permeability of 238 barrer and a CO2 /N2 selectivity of 49.113]. a decrease in the permeabilities is observed. a series of three component polyimides have been synthesised and their gas permeabilities tested [68]. the permeabilities increase. 29. are extremely rigid. the paper contains an interesting discussion on the relationship between entropy and permeability. The oxygen/nitrogen separation properties of 6FDA–TAB and the copolymer 6FDA/PMDA–TAB has been examined by Zimmerman and Koros [78].G. Powell. Increasing the proportion of DAM leads to an increase in the permeability and a decrease in the selectivity. G. A copoly(imide pyrrolone). The reaction is displayed in Scheme 5.117]. Qiao / Journal of Membrane Science 279 (2006) 1–49 15 Scheme 4. Of particular note is the polymer PMDA-pDDS/PEO4(80) (Fig. the authors do not investigate carbon dioxide transport. Synthesis of alkynylated PSF. By increasing the reaction time. both the carbon dioxide and nitrogen permeabilities decrease. As the proportion of 6FDA–pPDA increases. Chung and co-workers have synthesised and determined the gas transport properties of a series of copolyimides incorporating the 6FDA–durene and 6FDA–pPDA subunits [65]. The polypyrrolones studied in the paper. poly(ethylene oxide) segments.

The membranes were synthesised by mixing a polyamic acid with a mixture of tetraethyl orthosilicate. . The synthesis of these network membranes is displayed in Scheme 6. Powell. G. These cores were then reacted with a variety of poly(ethylene oxide) chains. and their gas transport properties determined [119]. could be altered. however. Silica-polyimide membranes have likewise been prepared by Morooka and co-workers [120]. These poly(ethylene oxide) molecules varied in both molecular weight (2000. The authors suggest that this could be due to interactions between the carbon dioxide and polyimide or densification and consolidation of the membrane induced by the presence of high pressure carbon dioxide. Tris(4-aminophenyl)amine was reacted with 6FDA to give a mixture of hyper-branched polyimide cores.E. Novel polysulfones-based off HFPSF. 23. is lower for the polymer blends than what would be expected if it follows a similar relationship. 3-glycidyloxypropyltrimethoxysiland and a coupling agent. Nanocomposite membranes incorporating polyacetylenes have also been synthesised by Peinemann and co-workers [121]. Okamoto and co-workers have investigated a series of star polymers incorporating a 6FDA-based polyimide core and poly(ethylene oxide) arms [118]. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig. The permeability of carbon dioxide. The membranes could then be doped with a variety of ions. The presence of the silica increased the carbon dioxide permeability at the cost of selectivity. 2840 or 5000) and terminal groups (amino or hydroxyl). The amic acid precursors were cast and then heat to form both the imide and siloxane bonds.G. A series of poly(imide siloxane) copolymers have been synthesised by Smaihi et al. The solution was then cast onto alumina support tubes which were then heated at 350 ◦ C to form the networked membrane. PPSF and novel polysulfones-based off PPSF.16 C. Marand and co-workers have likewise investigated the gas permentation properties of thermally annealed polyimide-organosilicate hybrid membranes [59]. 24. increasing the proportion of polyimide on the transport properties of gases which do not interact significantly with the polymer matrix can be described by a simple relationship. By varying the ratio of 6FDA to tris(4aminophenyl)amine the composition of the polyimide cores Fig. The nitrogen and carbon dioxide gas transport properties of the hybrid membranes was tested at both 90 and 190 ◦ C.

26. EP and ED the activation energies for permeation and diffusion. 6FDA–TAB/DAM.E. Fig. 27. PMDA–pDDS/PEO4(80). Fig. D = D0 exp − ED RT . Carbon dioxide permeability vs. Pressure/temperature effects The relationship between temperature and gas transport properties can be expressed with the following equations: P = P0 exp − S = S0 exp − EP RT Hs RT . Powell. NTDA–BDSA/ODA. 25. G. 2.G. selectivity for polysulfones. 29. Novel polysulfones-based off TMPSF. Qiao / Journal of Membrane Science 279 (2006) 1–49 17 Fig.3. respectively Fig. .C. Fig. where P0 . 28. D0 and S0 are the initial conditions.

This implies that increasing the temperature should lead to an increase in the permeability and a decrease in the selectivity of a membrane. Powell. Of particular interest. The permeabilities of both carbon dioxide and nitrogen were measured at 25.42 −76. G.95 −32. Lin and Freeman have investigated the gas transport properties of poly(ethylene oxide) for a large number of gases at different temperatures [55].101 0.71 −55.E. indicating plasticisation of the membrane. as expected from the dual-mode sorption model.N-dimethylaminoethyleneamine and 6FDA–durene.15 −22. however.0 barrer and m = 34 ± 10 atm−1 . Stern and co-workers have investigated the gas transport properties of a series of 6FDA–polyimide membranes [72]. Qiao / Journal of Membrane Science 279 (2006) 1–49 Scheme 5.02 barrer and m = −10 ± 7 atm−1 . and Hs is the heat of sorption. whereas NO2 PA.61 Scheme 6. Table 4 Pressure dependence of permeabilities Polymer CO2 n 6FDA–mPDA 6FDA–mMPDA 6FDA–DATr 6FDA–DBTF 0. Synthesis of poly(imide siloxane) copolymers. p2 the upstream pressure and p is the pressure difference across the membrane. . n and m have been determined (Table 4). By fitting experimental data to this equation.512 1. whereas the glassy polymer was unaffected by pressure changes. Data from Ref.97 N2 n −0.0 = 0.0 (1 + mp2 ) where PA. The permeability of carbon dioxide increases with pressure. From this they determine that for CO2 PA. Villaluenga and Tabe-Mohammadi have examined the effect of pressure variations on both glassy and rubbery polymers [122]. whereas nitrogen permeability decreases slightly with increased pressure.098 m (×105 ) −10.412 m (×105 ) −70.13 −71.19 15. The authors applied the following empirical model to these results: PA = PA (1 + m p) = PA.18 C.25 ± 0. The effect of changing the upstream pressure was also investigated.344 0.700 1. The permeabilities of both gases increased dramatically upon heating. 35 and 45 ◦ C. [72]. However. an empirical relationship between pressure and permeability was developed: log P = n + m p where n and m are the constants.G. The effect of altering the pressure was much more significant when the rubbery polymer was examined. m an adjustable constant.0 = 12 ± 1. Reaction of N.427 0.986 1.0 is the permeability at an infinitely small pressure difference. the CO2 /N2 selectivity suffered a significant loss.

azo containing compounds and hydrosilylation reactions.5 CO2 /N2 selectivity 6.9 16. Cross-linking Cross-linking offers the potential to improve the mechanical and thermal properties of a membrane.0 14. Costello and Koros have similarly examined 6FDA–6FpDA and 6FDA–6FmDA over a large temperature range (35–325 ◦ C) and have suggested that 6FDA–6FpDA would be a candidate for incorporation into a high temperature application. Methacrylate terminated monomers incorporating poly(ethylene oxide) of various lengths (Fig. Koros and co-workers have investigated the effect of carbon dioxide plasticisation in a small number of polyimide membranes [123]. was kept constant at 5%).8 kcal mol−1 . The selectivity increases with the ethylene oxide concentration. [126].1 g/100 g polymer 2 g/100 g polymer 5 g/100 g polymer CO2 permeability 15. 30) were photo polymerised. the activation energies are 2. All of the polymers gave good CO2 /N2 selectivities. has demonstrated excellent CO2 /N2 properties for cross-linked various poly(ethylene oxide) polymers [127].28 and 3.0 × 101 and 2. The activation energies.4. have investigated the effects of cross-linking poly(ethylene oxide) on the carbon dioxide and nitrogen gas transport properties [126]. Above 150 ◦ C.E.G. A patent published by Kita et al. Hirayama et al. The authors have also published a useful paper on material selection for solubility selective polymers which possess good carbon dioxide permeabilities while still possessing excellent carbon dioxide/light gas selectivity [130].3 1. 2. such as carbon dioxide. the glassy polymers are expected to be less susceptible to pressures changes. These polymers were prepared by the polymerization of various oxirane compounds. and most exhibited large CO2 permeabilities at temperatures up to 100 ◦ C. The 6FDA–TADPO membranes were heated from 35 to 200 ◦ C. 30. The effect of increasing the proportion of cross-linking agent is tabulated in Table 5.C. Cross-linking was achieved via a variety of methods. Recently a large volume of research on cross-linked poly(ethylene oxide) has been published by Freeman and co-workers [128. Koros and Mahajan have suggested that cross-linking can be used to increase membrane stability in the presence of aggressive feed gases and to simultaneously reduce plasticisation of the membrane [14]. Data from Ref. respectively. An unsuccessful attempt at improving gas transport properties by cross-linking a polyarylate has been performed by Wright and Paul [131].1 kcal mol−1 for carbon dioxide and nitrogen. Koros and co-workers have performed an in-depth study of the temperature effects on the gas transport properties of the polypyrrolone 6FDA–TADPO [124]. EP are listed as 0.1 N2 permeability 2.129]. Qiao / Journal of Membrane Science 279 (2006) 1–49 19 as the authors did not use a highly condensable gas.0 × 103 barrers. The authors synthesised a copolyary- Fig. Increasing ethylene oxide concentration causes a dramatic decrease in the selectivity. [125].0 0. 6FDA–TADPO possesses a P0 of 5. The effect of increasing the proportion of ethylene oxide on the carbon dioxide–nitrogen selectivity was also examined (K-bismuththiol Table 5 Effect on increasing proportion of K-bismuththiol on gas transport properties of poly(ethylene oxide-co-epichlorohydrin) Cross-linking agent 1. Powell. Copolymers of poly(ethylene oxide-co-epichlorohydrin) have been cross-linked with various concentrations of Kbismuththiol [125]. including reaction with peroxides. the P0 is better expressed as 9. Above 150 ◦ C.0 × 102 barrers for carbon dioxide and nitrogen. Monomers used by Hirayama et al. At this concentration the selectivity is 63. They investigated the effects of increasing the temperature on the gas transport properties of two polyimides: 6FDA–DAF and 6FDA–IPDA [73].7 and 5. G. peaking at 93 mol%.0. Both the preexponential factor P0 and the activation energy EP have been determined. respectively.5 15 32 Permeabilities measured at 25 ◦ C.3 × 102 and 5. .

the effects of cross-linking on gas permeabilities did not begin to become significant until after a week of exposure to the pxylenediamine/methanol solution. possibly due to reduced diffusion of the cross-linking agent into the membrane. Similar work has been performed on 6FDA–durene and a PAMAM dendrimer [136].137–139]. 31. Improvements in the selectivities for some gas pairs were noted upon irradiation induced cross-linking. When other gas systems (such as He/N2 and O2 /N2 ) were investigated. increasing the proportion of 6FDA–DIA did lower both the carbon dioxide and nitrogen permeabilities.64]. Mixed-matrix membranes Mixed-matrix membranes refer the incorporation of solid particles within a membrane. Membranes formed from the polyimide 6FDA–durene can be cross-linked by reaction with a diaminobutane dendrimer in methanol solution [135]. The change in the Matrimid 5218 membranes carbon dioxide permeability over exposure time is graphed in Fig. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig.5. G. results for carbon dioxide/nitrogen separations. . Thermal decomposition of the polymer was observed during the cross-linking stage. Powell. with a corresponding large increase in the CO2 /N2 selectivity. Increased cross-linking generally leads to increase in the carbon dioxide/nitrogen selectivities at the cost of carbon dioxide permeability. it is likely that they will give similar results for CO2 /N2 separations. Both the carbon dioxide and nitrogen permeabilities decreased significantly with increased cross-linking.35 barrer). p-xylenediamine/methanol solution exposure time. Nakagawa and co-workers have incorporated a photosensitiser into a polyimide membrane and irradiated with UV light to induce cross-linking [133]. The carbon dioxide/nitrogen selectivity is also observed to decrease upon exposure to the solution. FBP/XTA-C110/tBIA. 32. Exposure of 6FDA–durene to the p-xylenediamine/methanol solution quickly causes a reduction in the permeabilities (the magnitude of the reduction depends on the exposure time). the cyclobutene group can cause cross-linking by linear addition and cycloaddition.G. an increase in the selectivities was observed. N2 permeability increases from 2.E.17 to 2. The cross-linking is thought to occur between the benzophenone moiety and an alkyl substitute on the diamine section of the polyimide. Upon heating to 350 ◦ C. Rezac et al. In both cases.20 C. The use of diamines to cross-link polyimides has been a topic of considerable interest in the literature since 2001. and exposed it to 350 ◦ C to induce cross-linking. The copolyarylate is displayed in Fig. although slower. Crosslinking the polymers did not significantly alter the gas permeabilities. Cross-linking can then be achieved by heating the membrane to 340 ◦ C under vacuum. a small increase in the permeability of the copolyarylate was observed (CO2 permeability increases from 33 to 37 barrer. Upon heating. Koros and co-workers have synthesised carboxylic containing polyimide membranes which can then be cross-linked by either a transesterification reaction or reaction with a metal ion [123. Generally the presence of particles can Fig. 2. As the dendrimer generation number increased. there was a significant drop in the CO2 permeability. late. Carbon dioxide permeability vs. The methanol causes the membrane to swell. The authors suggest that changes in the gas transport properties are due to degradation reactions. however. FBP/XTA-C110/tBIA. have blended 6FDA–IPDA with a diacetylene containing oligomer 6FDA–DIA [132]. Matrimid 5218 gives similar. A patent by Hayes has investigated photochemical crosslinking of copolyimides which include a benzophenone functional group [140]. Chung and co-workers have cross-linked 6FDA–durene and Matrimid 5218 dense membranes by soaking the membranes in a solution of p-xylenediamine in methanol [57. the speed at which cross-linking occurred decreased. The use of diamines to cross-link polyimides was patented in 1991 [134]. have investigated the effects of surface modification of polyimide (Matrimid 5218) and polysulfone (PSF) membranes by an ion beam [141]. however. Longer reaction times led to a larger degree of cross-linking. 32. Won et al. 31. These membranes have been investigated for their usage in CO2 /natural gas separations. Cross-linking decreased the solubility of the membranes in dichloromethane and N-methylpyrrolidone dramatically. while the p-xylenediamine reacts with two carbonyl groups cross-linking the polyimide. however.

6 11.51 2. and priming the particles with small amounts of the polymer can increase polymer–particle interactions. Whereas. Koros has suggested experimental procedures to minimise these issues.0 11. [144].5 17. but have significant problems with their processability.0 13. it would exhibit different behaviour to a gas molecule which is forced to take a discontinuous path through both the polymeric material and the solid particles. 33.143]. The authors suggest that the fullerene is causing rigidification of the polymer matrix.C.44 10. leading to a decrease in the diffusion coefficient. The authors used a modified version of the Maxwell equation to account for this and obtained a much close correlation with the experimental results (Table 6).23 13. If the mixed-matrix material acts as in a continuous fashion then the permeability can be modelled as Peff = P1 Φ1 + P2 Φ2 where Pn is the permeability and Φn is the volume fraction of component n. In principle. sonication and decantation of smaller solid particles can increase the viscosity of the casting solution reducing both aggregation.2 12. have formed mixed-matrix membranes from Matrimid 5218 and a benzylamine-modified fullerene [147]. Effective medium theory (EMT) has likewise been used to model mixed-matrix membranes [142]. Maxwell and Bruggeman (Table 6). polysulfones and 6FDA polyimides) formed on silicon dioxide impregnated ceramic = 1 − Φd Considerable differences between the calculated and experimental permeabilities were observed. The Bruggeman model uses the following equation when examining a random dispersion of spherical particles: (Peff /Pc ) − (Pd /Pc ) 1 − (Pd /Pc ) Peff Pc −1/3 tion of particles.33 2. as well as the formation of spaces between the solid particle and the polymeric material. Koros and co-workers have investigated a number of different polymeric membranes (polycarbonate. A number of articles providing an overview of mixed-matrix membranes have been previously published [142.5 12.1 13.21 2. Powell. Three potential problems with the formation of effective mixed-matrix membranes are the aggregation and sedimenta- Fig.2 2.8 2. For a dilute suspension of spheres in a matrix: Peff = Pc where Pd and Pc refer to the permeabilities of the dispersed and continuous phase. Addition of the fullerene appears to lower the permeabilities of all of the examined gases. 33 displays the carbon dioxide and nitrogen permeabilities versus increased fullerene content.48 Data from Ref. The authors investigated two models. . Chung et al. Effect of increased proportion of benzylamine modified fullerene in Matrimid 5218 mixed-matrix membranes gas transport properties. they can act as molecular sieves altering the permeabilities. and will tend towards continuous behaviour when the concentration of the solid particles is high.90 4.6 2.0 17. Qiao / Journal of Membrane Science 279 (2006) 1–49 21 have three effects on the permeabilities. This can allow the gases to flow non-selectively around the solid particles. as can reducing the rate of evaporation of the casting solution [145]. The authors suggested that this was due to rigidification of the polymer where it was in close proximity to a CMS particle. they can disrupt the polymeric structure increasing permeabilities and they can act as barrier reducing permeabilities.G. The behaviour of gases within a mixed-matrix will vary depending on the spatial relationship of the particles within the matrix. This was particular in the case of Matrimid 5218.40 3. If a gas molecule can make a continuous path through the particles without significant transport through the polymeric material. if the material acts in a discontinuous fashion.59 4.5 17. then the permeability can be described as Peff = P1 P2 Φ 1 P2 + Φ 2 P1 Pd + 2Pc − 2Φd (Pc − Pd ) Pd + 2Pc + Φd (Pc − Pd ) Table 6 Theoretical and experimental CO2 permeabilities of mixed-matrix membranes Carbon dioxide permeability (barrer) Bruggeman model Matrimid 5218 17% CMS 19% CMS 33% CMS 36% CMS Ultem® 1000 16% CMS 20% CMS 35% CMS Maxwell model Modified Maxwell model 11.1 12.3 Experimental 13.3 10.3 16. The Maxwell equation can be used to model the gas transport properties of mixed-matrix membranes [142]. have tried to avoid these problems by synthesising zeolite containing polymeric hybrid materials using covalent bonding of the zeolite to the polymer matrix [146]. Often these molecular sieves possess superior gas transport properties. G. Thompson et al. respectively. sedimentation. Koros and co-workers have compared theoretical permeabilities with experimental derived permeabilities of Matrimid 5218 and Ultem® 1000 mixed with carbon molecular sieves (CMS) [144]. a mixed-matrix membrane will exhibit discontinuous behaviour when the concentration of solid particles is low.E. Fig. Generally the literature has focused on the incorporation of molecular sieves into a polymer matrix.

Asymmetric membranes For membranes to be used in practical applications. when PMDA–ODA was mixed with poly(styrene-co-4-vinylprydine) nanoparticles in certain proportions an increase in both the carbon dioxide permeability and carbon dioxide/nitrogen selectivity was observed [60]. Dense membranes are generally synthesised by casting a solution of solvent and polymer onto a flat surface. polyimides [166–168]. Interestingly. such as collision of hyperthermal protons with absorbed organic precursors [152].155]. Hollow fibre membranes have been constructed using a number of different polymeric materials. Flat sheet asymmetric membranes have been constructed from a number of different polymeric materials. Khulbe et al. Most studies on the gas transport properties of polymers are performed on dense homogeneous membranes. it is important that the gas flux of the substructure be considerably greater than the flux through the selective layer [153]. Both the nitrogen and carbon dioxide permeabilities increase as the concentration of polypyrrole is increased. polyetherimide [156. it is necessary for them to be constructed into a useful morphology. including polysulfones [159–162]. Fig. However. including polysulfones [154. polyimide–poly(ethylene oxide) copolymers[169] and polymer blends [170]. polyetherimide [165]. This gives a membrane with two components: a defect free selection layer (similar to that found on a dense film membrane) and a porous support layer (Fig. and then allowing the solvent to evaporate. polyethersulfones [163]. their permeability has a close relationship to the intrinsic permeability of the polymer. Qiao / Journal of Membrane Science 279 (2006) 1–49 substrates [148]. These membranes can be manufactured as either flat sheets or hollow fibres (Fig. . For an asymmetric membrane to have similar selectivities to the intrinsic selectivity of the material.G. Other mixed-matrix membranes using polymeric particles have been examined [60]. These studies allow the efficiency of a material to be evaluated. as well an increase in the permeabilities. [155]). A series of mixed-matrix membranes incorporating powdered polypyrrole and polycarbonate have been synthesised and their gas transport properties determined by Yilmaz and coworkers [149]. G. Recent patents include useful details about the synthesis of various asymmetric membranes [171. This leads to dense membranes possessing considerably lower gas fluxes than alternative membrane structures. Spontak and co-workers have formed mixed-matrix membranes from cross-linked poly(ethylene oxide) and various nanoparticles [150. What follows is a brief introduction into this field. the construction of a gas separation module requires a more complex membrane structure to be used. Lin and Chung have investigated the effect of aging on the performance of hollow fibre membranes constructed with 6FDA–durene [173]. as far as experimental margins of error permit. Conceptually. some CO2 /N2 data was collected. As such. Fig. polycarbonates. 34). have carried out atomic force microscopy and contact angle goniometery studies on a polyethersulfone–polyimide blend hollow fibre membrane [174]. Dense membranes tend to be significantly thicker than the selective layer of asymmetric membranes. An extensive review of membrane structures is beyond the scope of this review.172]. 35. polyphenylene oxide [164]. SEM pictures of a hollow fibre membrane (from Ref.6. The authors observed an increase in the selectivities compared with dense membranes of the polymers. Powell.22 C.157] and polyimides [158]. 34. [175]). 35). 2. Structure of a typical asymmetric membrane (from Ref. Ultra thin membranes have also be constructed by more exotic techniques.151]. the simplest type of asymmetric membrane is one formed via a Loeb-Sourirajan phase separation process.E. While these membranes were examined primarily for their CO2 /H2 separation performance.

Often an expensive selective layer is combined with a cheaper layer which provides structural support. For example. Also of interest are polymers with a high fractional free volume. there are a number of different point sources which produce large CO2 emissions (steel foundries. the gas transport properties for the CO2 /N2 gas pairs were worse than polysulfone. such as polycarbonates. The carbon dioxide and nitrogen gas transport properties of a number of polymeric membranes have been discussed. With all fillers. Chung and co-workers have constructed dual-layer hollow fibre membranes using polyimide and a poly(ether sulfone) to construct each layer [179]. The introduction of VGCFs caused a reduction in the CO2 permeability and an increase in the N2 permeability. it is equally important to ensure that membranes are physically durable and resistant to both chemical attack and plasticisation. Composite membranes can take a number of different morphologies. G. A number of composite membranes have been constructed from a number of different polymeric materials. sulfonated poly(phenylene oxide) [75]. The membrane was then cross-linked by soaking the hollow fibres in a solution of p-xylenediamine in methanol. The new selectivity was 28.2. The carbon dioxide gas flux. one such role is the development of novel polymeric materials for the separation of carbon dioxide from nitrogen in power plant gas flues. carbon membranes can offer excellent gas transport properties. Mixedmatrix membranes offer a realistic technique to combine the gas transport properties of carbon membranes with the practicability of polymeric membranes. such as hollow fibre. leading to a change in selectivity from 42 to 14. combine good performance while possessing considerable scope for structural variation. The carbon dioxide/nitrogen selectivity of a hollow fibre membrane system consisting of cardo polyimides has been dramatically increased (from 35 to 81) by the incorporation of an inner layer consisting of a zero-generation polyamidoamine dendrimer. potential structural variations and ease of membrane formation. 5 and 10% (w/w). however their fragility. While this review concentrates on flue gas CO2 /N2 separation. it is expected that future research will concentrate on improving these properties through techniques such as crosslinking after manufacture into appropriate membrane morphology. the class of polymer with the largest volume of research are polyimides. does however. Some types of polymers. In addition to the power generation industry. while gas transport properties are important. The introduction of 2% CB led to only minor changes for the permeability of both gases. mechanical and gas transport properties of silicon coated polysulfone hollow fibre membranes has been investigated by Shilton and coworkers [180]. . the polyimide/polyethylene oxide polymers described in Section 2.6 have excellent gas separation properties and are further of future research. The authors postulated that the fillers increased the fractional free volume. CO2 can also be separated from fuel gases leading to lower CO2 emissions. Chemists can play an important role in the development of this technology. which can be used in combustion. Conclusions Geosquestration of carbon dioxide is an emerging technology used to reduce the impact of fossil fuel combustion. vapour grown carbon fibres (VGCF) and TiO2 were all trialled as fillers. The concentration of VGCF and TiO2 was 5%.G. while still being flexible enough for manufacture into various membrane types. whereas CB was trialled at 2.E. One possible strategy towards the synthesis of high performance gas separation membranes is the construction of polymers consisting of both hard and soft sections. polysulfones and polyimides. 3. Powell.183] and polysulfones. Likewise. difficulty of manufacture and high cost impose significant limitations on their utility. however. Another type of asymmetric membrane is the composite membrane. It is expected that this trend towards increased research on polyimides will continue in the near future. Pinnau and co-workers have published an interesting discussion of composite membranes [181]. there are a number of different locations where membranes can play a significant role. Composite membranes can be constructed by a variety of techniques including dip coating [184] and chemical vapour deposition [185]. Carbon black (CB). Qiao / Journal of Membrane Science 279 (2006) 1–49 23 A number of recent studies have been carried out on the effect of preparation variables and aging of hollow fibre membranes [175–178]. the CO2 permeability was essentially unchanged. This is due to their gas transport properties. however. good physical properties. While many polymers have been described here. including poly(ethylene oxide) containing polyimides [169]. the carboncontaining fillers interacted with the carbon dioxide leading to a reduction in its permeability. The addition of the fillers (with the exception of VGCF) did lead to an increase in the bursting pressures of the membranes. 10% CB reversed this trend and led to a selectivity of 33. to get concentrated CO2 flue gases. While most of polymers offer very high permeabilities and modest selectivities. polyimides [182. A number of different classes of polymers have been surveyed for their utility as materials for effective gas separation membranes. Composite membranes utilise two or more different polymeric materials in their construction. particularly polyimides which incorporate 6FDA. Frequently a three layer system is synthesised by the addition of a protective layer above the selective layer. TiO2 also induced an increase in the N2 permeability. whereas 5% CB led to a small increase in the N2 permeability and a small decrease in the CO2 permeability. The high solubility of carbon dioxide in certain polymers will ensure that polymers with high carbon dioxide/nitrogen solubility selectivity will increase in interest. some recent advances which also have moderate solubility selectivities have lead to excellent gas transport properties. etc). For reason. Additionally. The effect of filling agents on the structural. N2 /O2 separation membranes can be used to create oxygen enriched air.C. drop by almost 50% [36].

24 C.G. Chemical structures of some polyacetylenes used in the formation of gas separation membranes.1. A. Qiao / Journal of Membrane Science 279 (2006) 1–49 Appendix A What follows is a listing of polymers with their structures and their carbon dioxide/nitrogen gas separation properties. A1. Chemical structures of some polyacetylenes used in the formation of gas separation membranes. A2. Fig. Polyacetylenes (Figs.E. A1–A3) Fig. . G. Powell.

G. Name Poly(trimethyl-prop-1-ynyl-silane) Poly(3.2.E. Chemical structures of some polyacetylenes used in the formation of gas separation membranes.0 1.7 23.3 2.9 8.8 11.53 29. G.8 18.7 12. Qiao / Journal of Membrane Science 279 (2006) 1–49 25 Fig. Name 6FPT–6FBPA 6FPT–BPA 6FPPy–6FBPA 6FPPy–BPA Feed pressure (atm) 1.0 1.18 1.5 13.2 4.3-dimethyl-but-1-yne) Poly(1-(dimethyl-trimethylsilanylmethyl-silanyl)-propyne) Poly(1-[dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propyne) Poly(trimethyl-(2-prop-1-ynyl-phenyl)-silane) Poly(1-prop-1-ynyl-2-trifluoromethyl-benzene) Poly(dec-2-yne) Poly(1-chloro-dec-1-yne) Poly(1-chloro-oct-1-yne) Poly(1-chloro-hex-1-yne) Poly(hexyl-dimethyl-prop-1-ynyl-silane) Poly(trimethyl-(1-pentyl-prop-2-ynyl)-silane) Poly(hexyl-dimethyl-(1-propyl-prop-2-ynyl)-silane) Poly(prop-1-ynyl-benzene) Poly(but-1-ynyl-benzene) Poly(oct-1-ynyl-benzene) Poly(chloroethynyl-benzene) Poly(1-ethynyl-2-methyl-benzene) Poly(dimethyl-phenyl-(1-propyl-prop-2-ynyl)-silane) Temperature (◦ C) 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 P(CO2 ) (barrer) 19000 560 310 150 290 130 130 170 130 180 71 120 70 25 40 48 23 15 54 P(N2 ) (barrer) 1800 43 21 14 24 7.0 21.39 1.6 13.37 2. Poly(arylene ether) (Fig.3 14 16 11 10 4.8 9. A4) Carbon dioxide and nitrogen gas permeability data for poly(arylene ether) dense films.44 P(N2 ) (barrer) 2.7 6.0 2.5 α(CO2 /N2 ) 10.6 Reference [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] A.4 8.8 10.6 Reference [43] [43] [43] [43] .1 11.1 17.5 12.5 1.0 3.0 16.46 21.29 18.3 10.C.0 Temperature (◦ C) 35 35 35 35 P(CO2 ) (barrer) 25.3 8.5 5. Powell.6 13. Carbon dioxide and nitrogen gas permeability data for poly(acetylene) dense films.0 14. A3.6 11.32 12.0 1.70 α(CO2 /N2 ) 11.0 5.

8 12.7 19.E. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig. A5–A7) Carbon dioxide and nitrogen gas permeability data for polyarylate dense films.1 5.5 20.1 8.2 21. G.90 1.20 1.7 20.4 36.7 17.16 16. Polyarylates (Figs. A4. Name BPA/IA BPA/tBIA HFBPA/IA HFBPA/tBIA PhTh/IA PhTh/tBIA FBP/IA FBP/tBIA TBBPA/IA TBBPA/tBIA TBHFBPA/IA TBHFBPA/tBIA TBPhTh/IA TBPhTh/tBIA TBFBP/IA TBFBP/tBIA DMBPA/IA DMBPA/tBIA TMBPA/IA TMBPA/tBIA DiisoBPA/IA DiisoBPA/tBIA DBDMBPA/IA PhAnth/IA PhAnth/tBIA FBP/IA FBP/tBIA Feed pressure (atm) 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 Temperature (◦ C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 5.22 0.08 0.28 1.52 0.07 4.93 21.5 25.1 56.93 α(CO2 /N2 ) 22.G.9 12.5 1.9 19.47 0.94 0.6 19.36 1.39 0. Fluoro-containing novel poly(arylene ether).0 28.8 P(N2 ) (barrer) 0.2 14.7 24.1 23.0 25.6 5.4 23.0 12.24 8.57 1.0 44.8 25 19.4 24.29 1.8 4.4 19.09 0.4 36.1 21.5 20. A.3.6 20.9 29.28 0.27 1.9 24.26 C.88 0.063 0.8 23.4 69.11 3.2 17.2 19.8 12.34 30.58 2.8 19.9 6.1 14.1 Reference [45] [45] [45] [45] [45] [45] [45] [45] [46] [46] [46] [46] [46] [46] [46] [46] [44] [44] [44] [44] [44] [44] [44] [47] [47] [47] [47] .6 85.93 0.35 0.1 27.74 23. Powell.70 2.18 0.45 9.24 1.9 23.57 1.

Powell. Fig. A5. Structures of asymmetric polyarylates used by Pixton and Paul [44].C. G. A6. .G. Qiao / Journal of Membrane Science 279 (2006) 1–49 27 Fig. Structures of symmetric polyarylates used by Pixton and Paul [44–46].E.

G.0 15. Name PC PC PC TMPC TMPC TCPC TBPC HFPC TMHFPC NBPC PCZ PC–AP FBPC Feed pressure (atm) 10/5 1 10 1 10 1 1 10 10 10/2 10/2 2 2 Temperature (◦ C) 35 35 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 6.105 0. Powell.0 19.4 21. Structures of anthrone-based polyarylates studied by Pixton and Paul [47].33 0.2 15.0 26.0 6.361 0.2 9.592 α(CO2 /N2 ) 19. A.7 21 21 16.1 2.4 0.48 15.5 6.6 18.36 0.5 23. G.23 24 111 9.182 1.6 6.E.47 0.58 18.289 0.66 4.3 25.0 0.32 1. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig.28 C.8 17.6 7. Polycarbonates (Figs. A7. A8–A10) Carbon dioxide and nitrogen gas permeability data for dense films incorporating polycarbonates.1 P(N2 ) (barrer) 0.09 1.4.1 18.5 Reference [50] [52] [51] [52] [51] [52] [52] [51] [51] [49] [49] [48] [48] .

99 1. Poly(ethylene oxide) Carbon dioxide and nitrogen gas permeability data for poly(ethylene oxide) dense films. A.8 14.07 0.3) EO/EM/AGE (96/4/2.4 7. Powell.0 16.8 15.24 0.8 14.6 4. A8. Structures of some polycarbonates.5) Feed pressure (atm) 7.G.4 7.0 1.8 4.6 Not reported Not reported Not reported Temperature (◦ C) 25 35 35 35 45 45 45 35 35 35 P(CO2 ) (barrer) 8.22 0.5 12. Name PEO PEO PEO PEO PEO PEO PEO EO/EM/AGE (80/20/2) EO/EM/AGE (77/23/2.E. Qiao / Journal of Membrane Science 279 (2006) 1–49 29 Fig.5.1 α(CO2 /N2 ) 140 55 63 79 40 48 52 46 44 48 Reference [55] [55] [55] [55] [55] [55] [55] [56] [56] [56] .24 0.1 13 15 17 40 46 52 773 680 580 P(N2 ) (barrer) 0. G.C.

8 26.3 -ODA PMDA–4.145 0.8 10/2 10/2 10 Temperature (◦ C) 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 11.8 6.4 -ODA PMDA–3.3 27. A11–A15) Carbon dioxide and nitrogen gas permeability data for dense films incorporating polyimides.12 1.18 3.66 0.03 P(N2 ) (barrer) 0. Fig.018 0. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig.1 23.20 α(CO2 /N2 ) 17.4 -ODA PMDA–4.4 -ODA PMDA–3. A.10 0.8 10 6.29 0. A10.14 2. Polyimides (Figs.3 -ODA PMDA–MDA Feed pressure (atm) 6. Name PMDA–BAPHF PMDA–3BAPHF PMDA–4.8 6. G.049 0. Structures of some polycarbonates.E.G. Structures of some aromatic halogenated polycarbonates. Powell.55 4.50 1.8 21.1 27.0 24.2 Reference [74] [74] [74] [186] [74] [70] [70] [186] .0454 0. A9.8 6.71 0.6.5 20.30 C.

00 27 20 63 71 67 200 22 63 110 39 95 6.25 α(CO2 /N2 ) 19.7 16.8 25.6 4.59 2.45 1.370 0.7 33 34 31 28 27 25 34 29 30 33 19 32 28 19.1 0.7 17.3 19.65 2.1 30.2 4.1 10.1 25.5 8.943 1.37 6.4 18.0236 0.4 -ODA BTDA–BAPHF BTDA–BATPHF BTDA–BAHF BTDA–mTrMPD BTDA–BAFL PI oMeCat–durene mMeCat–durene DMeCat–durene mtBuCat–durene oMeptBuCat–durene TMeCat–durene mMetCat–MDA mtBuCat–MDA TMeCat–MDA TMeCat–TMB DBuCat–TMB mtBuCat–DMOB TMeCat–6FiPDA 6F TMMPD IMDDM ODA Matrimid 5218 Feed pressure (atm) 10 10/2 10/2 10/2 10/2 10/2 1 10/2 10/2 10/2 10/2 10/2 10/2 1 10 1 1 1 1 1 1 1 1 1 1 1 1 1 3 3 3 3 10 Temperature (◦ C) 35 35 35 35 35 35 25 35 35 35 35 35 35 25 35 30 30 30 30 30 30 30 30 30 30 30 30 30 Not reported Not reported Not reported Not reported 35 P(CO2 ) (barrer) 29.563 1.61 8.6 17.15 27.8 0.7 16. Qiao / Journal of Membrane Science 279 (2006) 1–49 31 Name PMDA–IPDA PMDA–BAPHF PMDA–BATPHF BPDA–BAPHF BPDA–BATPHF BPDA–BAHF BPDA–BAFL BPDA–mTrMPD BTDA–4.21 1.9 0.G.063 0.94 10.9 5.39 0.195 0.4 19.E.2 16.245 0.97 0.55 0.39 0.5 22.8 22. A11.5 P(N2 ) (barrer) 1.83 0.42 0.7 54 114 600 196 25 6.9 37.1 18. .9 38. Common polyimide moieties. G.625 4.55 2.8 18.2 3.7 23 137 0.9 15 2.50 0.8 1.3 26.6 24.8 35.6 Reference [186] [70] [70] [70] [70] [70] [187] [71] [70] [70] [70] [70] [71] [187] [60] [66] [66] [66] [66] [66] [66] [66] [66] [66] [66] [66] [66] [66] [107] [107] [107] [107] [57] Fig.5 31.95 9.05 2. Powell.50 0.4 20.C.

G. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig. Some diamine repeating units.32 C. Powell.E. A12. .G.

Fig. Catechol-based polyimides synthesised by Kricheldorf and co-workers [66]. A13. .E. Qiao / Journal of Membrane Science 279 (2006) 1–49 33 Fig.G. G. Powell.C. Some diamine repeating units. A14.

5 1.88 2.8 6.67 35.20 8.8 6. Powell.12 31.4 27.068 0.0 12.8 6. A16) Carbon dioxide and nitrogen gas permeability data for dense films incorporating the polyimide 6FDA.64 8.8 6.255 0.3 42.981 1. Structures of some bulky novel polyimides.1 α(CO2 /N2 ) 19.086 0.447 0.0 25.7 16.41 6.12 16.7.733 0.85 20.6 21.099 0.7 440 456 9.52 431 28.30 3. 6FDA-based polyimides (Fig.181 0. A.8 19.8 10 10 10 10 10 10 10 Temperature (◦ C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 15.11 10.50 1.1 13.34 C.24 2.8 10 6.91 13.23 40.8 6.4 ODA 6FDA–APAP 6FDA–pp ODA 6FDA–BAPHF 6FDA–BATPHF 6FDA–BAHF 6FDA–1.94 2.6 22.6 1.31 1.80 2.9 18.E.59 15. G.05 4.7 19.63 21.5 16.36 2.4 12.9 20.G.8 6.50 1.1 42.0 23.6 22. A15.5-NDA Feed pressure (atm) 10 10 10 10 10 6.7 17.5 21 Reference [71] [71] [71] [65] [72] [72] [72] [72] [72] [72] [72] [69] [69] [69] [69] [69] [69] [69] [70] [70] [70] [70] [70] [70] [62] .5 17.4 26.12 0.6 22.11 1. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig.50 0.8 6.8 10 6.3 22.1 22. Name 6FDA–pPDA 6FDA–pDiMPDA 6FDA–durene 6FDA–durene 6FDA–mPDA 6FDA–mPDA 6FDA–mMPDA 6FDA–mMPDA 6FDA–mTrMPDA 6FDA–DATr 6FDA–DBTF 6FDA–PHDoeP 6FDA–PPDoeP 6FDA–PMDoeP 6FDA–PEPE 6FDA–PBEPE 6FDA–PTEPE 6FDA–PMeaP 6FDA–3.8 6.473 0.78 6.2 23 P(N2 ) (barrer) 0.8 51.17 4.60 35.6 28.259 0.

38 19.5 22.27 2.4 23.94 2.7 24.0 36.1 kg/cm2 10 6.9 21.2 21.33 5.24 0.10 0.81 0.7 Reference [58] [58] [58] [58] [58] [58] [58] [68] [186] [74] [186] [74] [74] [74] [73] [73] [73] [73] [73] [73] [67] [67] [67] [67] [187] Fig.3 3.18 3.0 19 19 2.6 27.15 1.3 32 360 62 190 98 P(N2 ) (barrer) 1.9 49.3 -ODA 6FDA–3BDAF 6FDA–IPDA 6FDA–IPDA 6FDA–IPDA 6FDA–DAF 6FDA–DAF 6FDA–DAF PI-1 PI-3 PI-4 PI-5 6FDA–BAFL Feed pressure (atm) 10 10 10 10 10 10 10 1.81 0.5 17.94 0.G.39 0.4 16.75 16.6 54.9 0.0 29.87 1.09 1.8 23.83 0.8 6. G.5 19.5 20.9 23.38 3.3 18.4 19.8 6.3 27.0 24.C.4 7.4 27.8 10 6.0 15.3 24.0 23 22.3 25.1 6. A16.1 21.8 10 10 10 10 10 10 1 1 1 1 1 Temperature (◦ C) Not Reported Not Reported Not Reported Not Reported Not Reported Not Reported Not Reported 30 35 35 35 35 35 35 35 45 55 35 45 55 30 30 30 30 25 P(CO2 ) (barrer) 11.4-ODA 6FDA–MDA 6FDA–4BDAF 6FDA–3. Qiao / Journal of Membrane Science 279 (2006) 1–49 35 Name 6FDA–durene 24 h amidation 6FDA–durene/mPDA (50/50) 6FDA–durene/mPDA (50/50) 4 h amidation 6FDA–durene/mPDA (50/50) 6 h amidation 6FDA–durene/mPDA (50/50) 12 h amidation 6FDA–durene/mPDA (50/50) 24 h amidation 6FDA–durene/mPDA (50/50) 48 h amidation 6FDA–FDA/HFBAPP (1/1) 6FDA–ODA 6FDA–4.2 15.4 21 26.3 α(CO2 /N2 ) 8.1 46.5 465.06 1.7 23.E.4 16.6 84. 6FDA–terphenylene polyimides synthesised by Fritsch and co-workers [66]. Powell.5 2.6 17.5 19.95 1.8 25.98 0. .8 26.

5 689. Poly(pyrrolone) (Fig.6 26.5 3.6 1.2 20.9 P(N2 ) (barrer) 0.0 Reference [77] [77] [77] [76] [76] [76] [76] A.0 93.1 kPa Temperature (◦ C) 35 35 35 22 22 22 22 P(CO2 ) (barrer) 1. A.12 P(N2 ) (barrer) 2.2 0. A17) Carbon dioxide and nitrogen gas permeability data for poly(phenylene oxide) dense films.046 3.8. A17.3 Reference [79] [82] [81] .1 kPa 689.E.7 3. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig. Poly(phenylene oxide)s (Fig.7 8.5 1.0 27. Name PPS PDMPO PDPPO PDMPO PDMPO (20.0 46.0% brominated) Feed pressure (atm) 1.5 1.8 23.1 kPa 689.60 65.36 C.6 0. G.3 24.5 1.9.5 39.1 kPa 689.G.1 159.8 18.4% brominated) PDMPO (60.6 97.7 26. Powell.9 90.0% brominated) PDMPO (37. Structures of some poly(phenylene oxide) derivates.0026 α(CO2 /N2 ) 20. A18) Carbon dioxide and nitrogen gas permeability data for polypyrrole dense films. Name 6FDA–TAB 6FDA–TADPO BBL Feed pressure (atm) 10/3 10/3 10/3 Temperature (◦ C) 35 35 35 P(CO2 ) (barrer) 54.6 24.8 3.0 α(CO2 /N2 ) 34.

5 7.E.1 25.G.3-ADM PSF 2. Polysulfones (Figs.67 4.2 1.051 0.4 8.5 P(N2 ) (barrer) 0. Qiao / Journal of Membrane Science 279 (2006) 1–49 37 Fig. A18.5-NPSF 2.11 0. G.2 23.0 10 1.25 0.2 9.3 28.57 0.6 29.5 25.5 4.9 18 22.0 40 22.4 -PSF 1.20 0.33 0.3 9.24 1.61 0.6 17. 92% C CSiMe3 ) Feed pressure (atm) 10/5 10/>5 10/5 10/5 10/5 10/5 10/5 10/1 10/5 10/1 10/2 10/2 10/2 10/2 10/2 10/5 10/2 10/5 2 2 1 10/1 1 1 10/2 10/2 1 Temperature (◦ C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 25 35 35 35 35 P(CO2 ) (barrer) 5.5 21.4 Reference [93] [50] [93] [94] [92] [94] [94] [90] [92] [90] [89] [89] [91] [91] [91] [93] [89] [93] [48] [48] [90] [90] [187] [90] [88] [88] [87] .5 19.057 0.6 31.0 23.0 0.2-ADM PSF PSF (6% Br.278 0.8 1.6 1.484 0. A.8 5.9 21 12 72 4.5 36.28 0.6-NPSF 2.12 13. Structures of some poly(pyrrolone)s.25 0.8 7.32 0.5 13.3 24.091 1.2 28.2 0.8 2.8 2.5 25.7-NPSF DMPSF HMBIPSF DMPSF-Z PSF-AP FBPSF PSF-M TMPSF-M PSF-BPFL 3.5 1.20 0.1 α(CO2 /N2 ) 22.066 0. Powell.10.057 0.5 21.6 4.1 29.C. A19–A22) Carbon dioxide and nitrogen gas permeability data for dense films incorporating polysulfones. Name PSF PSF TMPSF HFPSF TMHFPSF PSF-F PSF-O PSF-P TMPSF-F TMPSF-P BIPSF TMBIPSF 1.5 1.7 21.074 0.8 20.3 23.4 24.4 24.3 6.06 0.3 26.46 2.1 23.8 17.21 0.2 5.

36 α(CO2 /N2 ) 14.4 22. 77% C CCMe3 ) PSF (5% Br.2 4.38 C. Qiao / Journal of Membrane Science 279 (2006) 1–49 Name PSF (3% Br.6 21 70 18 29 6.2 21.9 0.6 18.61 0.2 16.7 6.6 21. .7 0.8 18 10 5.4 5.1 3. G.60 0. Structures of PSF and some related methylated polymers.38 0.G.4 Reference [87] [87] [87] [84] [84] [84] [84] [86] [86] [86] [86] [86] [86] [86] [86] [86] [86] [84] [84] [83] [83] [83] [83] [83] [85] [85] [85] Fig.67 5.9 12. 47% C CSiMe3 ) PSF (21% Br.29 0.07 3. A19.3 72 P(N2 ) (barrer) 1.2 22.0 5.3 21.6 20 18 18 18 19 21.9 18.9 22 26 30 23 26 30 32 14 11 11 17.24 0.0 105 41 84 110 72 96 32 66.16 0.25 0. Powell.3 18.63 2.9 0.2 27 6.3 0.0) SM1 PPSF RM3 RM2 RM1 HFPSF HFPSF-o-HBTMS HFPSF-s-TMS HFPSF-o-TMS HFPSF-TMS TM6FPSF TM6FPSF-s-TMS TMPSF-TMS TMPSF-s-TMS TMPSF-HBTMS Feed pressure (atm) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Temperature (◦ C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 18.5 28.10 1.0) SM3 (degree of substitution = 1.3 4.96 3.9 16.77 0.95 1. 45% C CCMe3 ) PSF PSF-s-HBTMS PSF-o-HBTMS PSF-CH2 -TMS EM3 EM2 EM1 SM3 (degree of substitution = 2.51 3.E.17 0.7 6.2 1.0 4.24 1.

Fig. Qiao / Journal of Membrane Science 279 (2006) 1–49 39 Fig. A20.C. Some polysulfone structures incorporating bisphenol Z.G. G. .E. Powell. A21. Some polysulfone structures.

44 0.042 α(CO2 /N2 ) 37.598 1.42 0.9 12.10 1. A23–A27) Carbon dioxide and nitrogen gas permeability data for other polymeric dense films. Others (Figs.111 0. .5 21.0 25. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig.26 4.8 34.4 29. G.015 0.2 17.292 0.3 21. Powell.9 19.92 0.8 29.4 14.76 0.016 0.11 0. PEI structure.11.75 P(N2 ) (barrer) 0.47 0.18 2.E. A22.6 8.G.3 45.18 4.7 14.027 0.6 8.70 0.4 15.683 2.21 0.160 0.0 34 18 Reference [53] [53] [53] [53] [53] [53] [53] [53] [189] [189] [189] [189] [188] [188] [188] [190] [190] Fig.3 3.37 2.13 0.5 16. Polysulfone structures incorporating aromatic substituted bisphenols.034 0. Name HQDPA–PDA HQDPA–PDA HQDPA–DBA HQDPA–DBA HQDPA–MDBA HQDPA–MDBA HQDPA–EDBA HQDPA–EDBA 12H 6H6F 6F6H 12F PBK PBK-S PBSF PPES PPESK Feed pressure (atm) 7 7 7 7 7 7 7 7 5 5 5 5 10/2 10/2 10/2 Not reported Not reported Temperature (◦ C) 30 100 30 100 30 100 30 100 35 35 35 35 35 35 35 25 25 P(CO2 ) (barrer) 0.8 0.125 0. A23.077 0.27 10. A.40 C.7 23.9 3.

C. G.G. Powell. Some poly(ether ketone) structures. PEI studied by Li and co-workers.E. A25. Fig. Qiao / Journal of Membrane Science 279 (2006) 1–49 41 Fig. . A24.

E.7 155 370 187 144 88.098 0. Fig. Qiao / Journal of Membrane Science 279 (2006) 1–49 Fig.0 16.12.5 16.6 31.13 1. A27. Name 6FDA–TAB 6FDA/PMDA–TAB (50:50) 6FDA/PMDA–TAB (25:75) 6FDA/PMDA–TAB (10/90) 6FDA–TAB/DAM (75/25) 6FDA–TAB/DAM (50/50) 6FDA–DAM 6FDA/PMDA(1:6)–TMMDA (CH2 Cl2 cast) 6FDA/PMDA(1:6)–TMMDA (NMP cast) 6FDA/PMDA(1:6)–TMMDA (DMF cast) MDI–BPA/PEG(75) Feed pressure (atm) 10/3 10/3 10/3 10/3 3 3 3 10 10 10 2 Temperature (◦ C) 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 54.76 5. Structure of poly(phthalazinone ether ketone) (PPEK) and poly(phthalazinone ether sulfone) (PPES).036 3.7 8.1 6.8 0.6 31 P(N2 ) (barrer) 2.5 11.8 3.70 0. A. A26.0 15.9 30. Copolymers and polymer blends Carbon dioxide and nitrogen gas permeability data for copolymers and polymer blend dense films.8 23.4 17.6 29. G.70 α(CO2 /N2 ) 19.11 73.5 12. Poly(arylether bissulfone)s and poly(arylether bisketone) studied by Paul and co-workers [188].2 44 Reference [79] [79] [79] [79] [115] [115] [115] [97] [97] [97] [112] . Powell.3 22.42 C.G.16 0.8 23.

90 4.0 1.0% PTMOS) 6FDA–6FpDA–DABA-12.58 3.73 1. Qiao / Journal of Membrane Science 279 (2006) 1–49 43 Name MDI–BPA/PEG(80) MDI–BPA/PEG(85) L/TDI(20)–BPA/PEG(90) L/TDI(40)–BPA/PEG(85) IPA–ODA/PEO3(80) BPDA–ODA/DABA/PEO1(75) BPDA–mDDS/PEO1(80) BPDA–ODA/DABA/PEO2(70) BPDA–ODA/DABA/PEO2(80) BPDA–ODA/PEO3(75) BPDA–mDDS/PEO3(75) BPDA–mPD/PEO4(80) BPDA–ODA/PEO4(80) PMDA–ODA/DABA/PEO1(80) PMDA–ODA/PEO2(75) PMDA–mPD/PEO3(80) PMDA–APPS/PEO3(80) PMDA–APPS/PEO4(70) PMDA–mPD/PEO4(80) PMDA–ODA/PEO4(80) PMDA–pDDS/PEO4(80) PMDA/BTDA–BAFL (50:50) PMDA/BTDA–BAFL (90:10) BPDA–BAFL/HMDA (50:50) PPES PPES/PPEK (3:1) PPES/PPEK (1:1) PPES/PPEK (1:3) PPES/PPEK (1:4) PPEK HQDPA–DPA/MDPA HQDPA–DPA/MDPA HQDPA–DPA/EDPA HQDPA–DPA/EDPA PI PI/10PS PI/15PS PI/20PS PI/25PS PI/10PSVP PI/15PSVP PI/20PSVP PI/25PSVP NTDA–BDSA(30)/CARDO/ODA NTDA–BDSA(30)/CARDO NTDA–BDSA(30)/BAPHF NTDA–BDSA(30)/ODA 6FDA–FDA/HFBAPP (1/1) 6FDA–durene/pPDA (80/20) 6FDA–durene/pPDA (50/50) 6FDA–durene/pPDA (20/80) 6FDA–durene/3.50 1.25 0.08 2.2 4.147 0.53 7.09 14.7 19.32 2.00 2.29 3.75 0.9 16.3 -DDS (25/75) 6FDA–3.4 16.7 18.3 0.01 4.26 84.3 -DDS (75/25) 6FDA–durene/3.085 0.8 0.9 37.7 27.066 0.0% PTMOS) annealed 6FDA–6FpDA–DABA-12.E.5 (22.5 (15.34 1.59 1.92 2.07 1.20 0. G.3 91.77 0.5 (15.5 2.7 3.957 2.94 4.6 15.12 2.9 16.26 0.0 110 32.91 1.81 5.4 26.042 0.8 14 36 75 72 81 117 14 40 99 159 136 151 167 238 43 130 0.2 465.3 -DDS 6FDA–6FpDA-DABA-12.026 0.074 0.88 7.2 19.84 34.5 annealed 6FDA–6FpDA–DABA-12.13 0.64 0.91 0.9 47.74 2.052 0.8 3.74 2.27 0.090 0.2 15.089 0.1 19.1 17.027 0.4 1.31 41 36 36 52 23.33 2.28 21.6 44.25 2.12 1.0% MTMOS) 6FDA–6FpDA–DABA-12.5 (15.91 0.65 6.06 1.1 kg/cm2 10 10 10 10 10 10 10 4 4 4 4 4 4 4 4 4 Temperature (◦ C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 25 25 25 25 25 25 25 25 25 30 100 30 100 35 35 35 35 35 35 35 35 35 30 30 30 30 30 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 48 59 47 35 58 2.71 5.5 6FDA–6FpDA–DABA-12.3 -DDS (50/50) 6FDA–durene/3.C.5 (22.7 4.88 α(CO2 /N2 ) 47 49 51 48 53 56 58 57 56 52 53 54 51 52 54 50 51 53 52 52 49 33 34 39 34 40 46 39 34 18 41.3 3.15 1.16 2.5 (15.0 3.7 P(N2 ) (barrer) 1.8 30.0% MTMOS) annealed 6FDA–6FpDA–DABA-12.014 0.063 0.5 0.80 5.207 0.7 31.5% TMOS) annealed 6FDA–6FpDA–DABA-12.036 0.62 16.5% PTMOS) Feed pressure (atm) 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 1 1 Not reported Not reported Not reported Not reported Not reported Not reported 7 7 7 7 10 10 10 10 10 10 10 10 10 3 3 3 3 1.4 4.4 25.1 2.19 4.0 70.8 5.G.4 13.9 15.7 22.64 1.55 70 164 23 5.6 17.9 1.34 3.5 38.4 15.8 30.09 0.4 1.5 (22.14 0.5% TMOS) 6FDA–6FpDA–DABA-12.9 3.0 230 126 59.71 28.3 18. Powell.2 15.1 0.3 Reference [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [187] [187] [187] [190] [190] [190] [190] [190] [190] [53] [53] [53] [53] [60] [60] [60] [60] [60] [60] [60] [60] [60] [63] [63] [63] [63] [68] [65] [65] [65] [61] [61] [61] [61] [59] [59] [59] [59] [59] [59] [59] [59] [59] .023 0.92 0.048 0.54 0.6 2.55 1.7 16.70 3.

9 32.83 0.8 16.4 2.3 14.7 kPa 96.0% MTMOS) 6FDA–6FpDA–DABA-25 (15.5 16.7 kPa 96.9 9.7 kPa 96.44 C.62 P(N2 ) (barrer) 5.9 15.9 Reference [59] [59] [59] [59] [59] [59] [59] [59] [59] [59] [59] [59] [59] [114] [114] A.6 Reference [125] [125] [125] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [57] .7 27 240 510 98 400 240 420 250 6.7 kPa 96.7 kPa 96.7 kPa 10 Temperature (◦ C) 25 25 25 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 35 P(CO2 ) (barrer) 15.7 4.5% TMOS) annealed 6FDA–6FpDA–DABA-25 (15.6 0.9 16.1 7.8 16.7 kPa 96.19 0.4 3.3 77.7 kPa 96.06 4.5 16.7 kPa 96.3 1.7 kPa 96.7 kPa 96.6 60.90 3.2 12.7 19.87 1.5 (22.5% PTMOS) annealed Poly(5:5 BPA/BN) Poly(7:3 BPA/BN) Feed pressure (atm) 4 4 4 4 4 4 4 4 4 4 4 4 4 5 5 Temperature (◦ C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 90.1% Poly(ethylene oxide-co-epichlorohydrin) (1:1) 2% Poly(ethylene oxide-co-epichlorohydrin) (1:1) 5% DM14/MM9 (100/0) DM14/MM9 (100/0) DM14/MM9 (90/10) DM14/MM9 (90/10) DM14/MM9 (70/30) DM14/MM9 (70/30) DM14/MM9 (50/50) DM14/MM9 (50/50) DM14/MM9 (30/70) DM14/MM9 (30/70) DB30/MM9 (100/0) DB30/MM9 (100/0) DB30/MM9 (90/10) DB30/MM9 (90/10) DB30/MM9 (70/30) DB30/MM9 (70/30) DB30/MM9 (50/50) DB30/MM9 (50/50) DB30/MM9 (30/70) DB30/MM9 (30/70) DM9/MM9 (90/10) DM9/MM9 (90/10) DM23/MM9 (90/10) DM23/MM9 (90/10) DB10/MM9 (90/10) DB10/MM9 (90/10) DB69/MM9 (90/10) (cooling) DB69/MM9 (90/10) (cooling) DB69/MM9 (90/10) (heating) DB69/MM9 (90/10) (heating) DM14/MM23 (30/70) (cooling) DM14/MM23 (30/70) (cooling) DM14/MM23 (30/70) (heating) Matrimid 5218 Feed pressure (atm) 3 × 105 Pa 3 × 105 Pa 3 × 105 Pa 96.71 4.3 1.2 7.2 1.7 kPa 96.G.25 0.7 kPa 96.25 0.7 kPa 96.1 16.5 5.94 6.7 kPa 96.0% MTMOS) annealed 6FDA–6FpDA–DABA-25 (22.5 16.0 0. G.1 45 107 62 133 96 195 144 260 210 350 93 200 105 210 141 270 179 330 250 410 18.5 P(N2 ) (barrer) 2.7 kPa 96.7 kPa 96.87 1.7 kPa 96.07 1.7 kPa 96.9 20.7 kPa 96.7 kPa 96.0% PTMOS) annealed 6FDA–6FpDA–DABA-25 (22.6 81.79 4.7 kPa 96. Name Poly(ethylene oxide-co-epichlorohydrin) (1:1) 1.7 kPa 96.7 kPa 96.5% MTMOS) annealed 6FDA–6FpDA–DABA-25 (15.7 2.7 kPa 96.0% PTMOS) 6FDA–6FpDA–DABA-25 (15.7 kPa 96.4 1.66 2.16 α(CO2 /N2 ) 15.5% PTMOS) annealed 6FDA–6FpDA–DABA-25 6FDA–6FpDA–DABA-25 annealed 6FDA–6FpDA–DABA-25 (22.8 0.4 0.1 18.98 6.7 kPa 96.1 104 5.3 2.6 30.4 104 19.5 5.5% MTMOS) 6FDA–6FpDA–DABA-25 (22.07 5.7 kPa 96.7 kPa 96.7 kPa 96.3 51 145 290 6.2 68 38 69 39 66 36 64 36 63 33 63 35 64 36 67 35 62 34 60 33 68 38 66 38 61 34 56 36 62 35 62 35 62 25.E.3 10.9 12 4.7 kPa 96.6 5.3 15.20 4.9 14.5 0.11 0.8 2.7 kPa 96.6 19.7 1.7 kPa 96.6 1.4 15.85 1.52 14. Cross-linking polymers Carbon dioxide and nitrogen gas permeability data for cross-linked membranes dense films.25 7.0 14.5 15.0 0.13.0 15.1 28.5% PTMOS) 6FDA–6FpDA–DABA-25 (22. Powell.7 79.6 16.6 11.25 α(CO2 /N2 ) 6.5% TMOS) 6FDA–6FpDA–DABA-25 (22.07 3.2 3. Qiao / Journal of Membrane Science 279 (2006) 1–49 Name 6FDA–6FpDA–DABA-12.

M. Chem.G. [33] L. and Vulnerability. Group contribution modelling of Gas transport in polymeric membranes. Carbon 42 (2004) 241. Macromol. 238 (2004) 93. Membr. 193 (2001) 1. Klijnstra. Davis. K. 60 min cross-linked Feed pressure (atm) 10 10 10 10 10 10 10 10 10 10 10 Temperature (◦ C) 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 7. Canziani.-S.K. Wessling. Polymeric materials for gas separations. Hirsche. [16] S. Membr. 125 (1997) 23.W. Boca Raton.R. 229 (2004) 117. J. 14 days cross-linking Matrimid 5218. 32 days cross-linking 6FDA–durene. D. Smolders. J. Sci. [23] L. 226 (2003) 145. Park. Molecular dynamics simulation of diffusion of O2 and CO2 in amorphous poly(ethylene terephthalate) and related aromatic polyesters. Polyimides for gas separation. 73 (1992) 247. H. K. T. 30 min cross-linked 6FDA–durene. Jacobson. D.M. White. Yamada.K. . Socolow. S. Milazzo. Relationship between chemical structure of aromatic polyimides and gas permeation properties of their carbon molecular sieve membranes. Robeson. Granite. Membrane-based gas separation. Molecular modelling of polyimide membranes for gas separation. M. Carbo polyimide membranes for CO2 capture from flue gases. Granite. Separation and capture of CO2 from large stationary sources and sequestration in gelogical formations—coalbeds and deep saline aquifers. Ind.D. D. 94 (1994) 1.D. Rubin. Robeson. Sci. G. Dokken.P. Fabrication of carbon membranes for gas separation—a review.29 0. B. Morimoto. H. A. [14] W. H. J. Barsema.7 3. 36 (1996) 697. Takeuchi. Modelling of the diffusion of carbon dioxide in polyimide matrices by computer simulation. J. H. Greenhouse gas sequestration in abandoned oil reservoirs: the International Energy Agency Weyburn pilot project. Y. Cambridge University Press. G. Pinnau. Membr. Cambridge University Press.9 136 91. Houghton. 2004. Alb´ erola. Ed. D. Mech.0 5. 3 days cross-linking Matrimid 5218. B.24 0.J. Pavel. Climate Change 2001: The Scientific Basis. G. ACS Symp. Membr. Gas separation with polymer membranes. [31] D. Brown. Basis of permeability/selectivity tradefoff relations in polymeric gas separation membranes. Assoc.J. [4] T. [29] S. Bas. Macromolecules 35 (2002) 10198. Robeson. Adaptation.D. Inst. Cambridge. E. [37] E. J. Membr. [12] B. Stabilization wedges: solving the climate problem for the next 50 years with current technologies.A. A jump motion of small molecules in glassy polymers: a molecular dynamics simulation. I.K. UK. S. Mercier. Park. [19] J. Ismail. J. Neyertz. J. Membr. 41 (2002) 5470. J. Sci. Chem. Burrowes.1 4. Plastics Eng. 2001. GSA Today 14 (2004) 4. Baker.E. Cao. Yampol’skii. Sci.V. Lee. Membr. Future directions of membrane gas separation technology.R. [8] G. [15] R. Heuchel.W. Paul. Proc. Membr. Eng.A.6 25. L. Haraya. Whittaker. ACS Symp. Air Waste Manage. [20] H. 100 (1995) 9. Gilboy (Eds. A review of Carbon Dioxide Selective Membranes. [27] E.W. Polym. [24] B. D. H. Intermediate polymer to carbon gas separation membranes based on Matrimid PI. Wang. 62 (1991) 165. Pennline.05 2. C. Polymers for gas separations: the next decade. Sci. Climate Change 2001: Impacts. T.3 14. J. J.M. [21] Y. Karrenbeld. Res.A. [3] S. Keith. J.D. Power Energy 217 (2003) 505. J.8 70. Pushing the limits on possibilities for large scale gas separation: which strategies. Luebke. Z.J. Membr.6 24. Cambridge. C. Gas separation membranes: needs for combined materials science and processing approaches. C. 175 (2000) 181. Laciak. A. Lee.40 α(CO2 /N2 ) 25. 2003. Lee. A group contribution approach to predict permeability and permselectivity of aromatic polymers. L. Notice of the singular inflation of a bladder. Paul.3 2. Sci. Freeman. 188 (2002) 13.0 30. [7] W. Shanks. Sci. Stern. Yashima. Park. Rostron.J. A review on the latest development of carbon membranes for gas separation. Hajnal. [6] R.1 6. G. Kim.W. Sci. Chemical influence of the dianhydride and diamine structure on a series of compolyimides studied by molecular dynamics simulations. Angew.4 6. [30] M. [25] J. 93 (1990) 2062. Chung. Balster. Strazisar. Y. H.F. [17] A. D. Y. [11] W. Langsam. Smith.N. 15 min cross-linked 6FDA–durene. Freeman. Phys. van Eerden.B. Koros.J.M.6 5.Y. Koros. [5] T.S. Carbon molecular sieve membranes derived from metal-substituted sulfonated polyimide and their gas separation properties. Pacala. Series 733 (1999) 151.M. J.H. Maier.H. van der Vegt. Fleming. Graham. S. Sci.4 1. Lee. Membr. [36] S. 5 (1994) 724. I. J.0 12. D. Membr. 2001.B. S. Mulder. [10] D. Y. J.). 132 (1997) 33. McCarthy. Correlation of separation factor versus permeability for polymeric membranes.35 Reference [57] [57] [57] [57] [57] [57] [64] [64] [64] [64] [64] References [1] J. in: E.T. Int. Smith. J. David. Membr. [22] R.F. Chem. Leary.F. Tanaka. Sci.C. S. [2] J.A. [32] D. 21 days cross-linking Matrimid 5218. Technol. White. Feil. Polymeric Gas Separation Membranes. Res. Sci. Sci.S. [9] S. Pinel. C. Koops. T.J. 100 (1995) 17. Hutcheon.15 0. CRC Press.W.21 0. 37 (1998) 2960. K. On the law of the diffusion of gases. [35] C. Macromolecules 32 (1999) 375.53 6.F.S. [26] H. Membr. [18] D. Membr. Molecular modeling studies of polymeric gas separation and barrier materials: structure and transport mechanisms. Ismail. 10 min cross-linked 6FDA–durene. Photochemical removal of mercury from flue gas. Qiao / Journal of Membrane Science 279 (2006) 1–49 45 Name Matrimid 5218. Science 305 (2004) 968. O.Y. Carapellucci.V. [13] M. 1 day cross-linking Matrimid 5218.I. 53 (2003) 645. Eng. J. [28] E. J. M. 41 (2002) 1393. Hofmann. C.R.19 0. DOE/NETL-2003/1200. Mahajan. Chem. Mano. S.F.14 P(N2 ) (barrer) 0. 198 (2002) 259. Koros. E. Symp. Sci. R. [34] D. N.H.1 22. Langsam. R.1 11.M. Eng. C.B. Saufi. J. Hoffman.2 15. Desalination 144 (2002) 67. White.D. Powell. 1994.J. Polymer 44 (2003) 6713. R. Smit. Pennline. Adv. Membrane Systems for CO2 capture and their integration with gas turbine planes. Shekhawat. Majer.13 11. A critical review on diffusivity and the characterization of diffusivity of 6FDA–6FpDA polyimide membranes for gas separation. Kim. 7 days cross-linking Matrimid 5218. Ind. Department of Energy. Series 733 (1999) 1. D. 83 (1993) 1. Sci. National Energy Technology Laboratory.6 10. Part A: J.2 24.H. Kazama. Cheltenham. J.R. Pennline. Graham. Correlation and prediction of gas permeability in glassy polymer membrane materials via a modified free volume based group contribution method.J. Proceedings of Seventh International Conference on Greenhouse Gas Control Technologies. R. 5 min cross-linked 6FDA–durene. N.87 0. K.

-I. Chung. J. Shindo. S. Part B: Polym. Phys. Membr. D. M. [44] M. Koros. J. Polym. Chng. Kang. H. Jpn. [39] R. Pineri.R. Membr. L. [70] K.-K. 202 (2002) 27. Koros.R.J. Polymer 36 (1995) 2745. 42 (1989) 69. W. Sci.R. Koros. Coal Sci. Al-Masei. Sci. Phys. Phys. J. Xu. Dai.J. US Patent 5. T. Entropic selectivity analysis of a series of polypyrrolones for gas separation membranes. K. G. Xu. Mattes.J. [64] Y. Membr. 199 (2002) 191. 214 (2003) 83. A. Koros. Xu. G. S. Tin. Structural comparison of gas transport and sorption properties. Guiver. . [80] C. Effect of doping treatment of gas permeation properties and separation factors on polyaniline membranes. Al-Masei. [43] Z. Transport characterization of a polypyrrolone for gas separations. Aguilar-Vega. K. Sci. Sci. T. Sci. [76] F. [58] Y. Gas separation properties of aromatic polyetherimides from 1. [65] W. G. Polypyrrolones for membrane gas separations. G. Phys. J. [72] H. W. Polymer membrane conditioning and design for enhanced CO2 –N2 separation. Sci. W. Paul. Wang. G. St. Hamad.J. Liu. Phys. J. Itatani.R.M.S. Gas permeability of a three-component polyimide series. Sci. Husk. Part B: Polym. [57] P. Y.J. Wang. Okamoto. Polyimides derived from substituted catechol bis(etherphthalic anhydrides)s. Sci.-I. Polym. Desalination 148 (2002) 369. II.-S. I.Y. 2.J.4-dicarboxyphenoxy)benzene dianhydride and 3. 37 (1999) 1251. 46 (1989) 43. K.D. Escoubes. 46 (1989) 93.J. [59] C.E. Kaldis. Sakellaropoulos.R. Membr. Yamamoto. C. Walker. Kapantaidakis. Chemical cross-linking modification of polyimide membranes for gas separation.586 1992. Sci.R. Koros.W. Okano. J. The gas separation effects of annealing polyimide–organosilicate hybrid membranes. T.K. 27 (1989) 1887. G.R. Sci. Ishizu. Phys. Sci.P. Y. Appl.J. New polyimides for gas separation.B. Liu. Sci. Liu. Membr.G. Mi. Membr. Phys. Macromolecules 32 (1999) 7853. Phys. B. [69] S. J. Effect of metal cations on the gas separation performance of sulfonated poly (phenylene oxide) membranes. M. Sci. Stern. R. G.A. Part B: Polym.J. Polymeric membranes based on bisphenol-A for gas separations. J. W.S. Gas transport properties of poly(1. Kricheldorf. T. Hellums. 27 (2002) 419. Sci. Phys. Pineri. W. G.-H.J. M.-S.2 -bis(3. J. J.C.-H. M. Khulbe. [79] C.A. Lin. Qiao / Journal of Membrane Science 279 (2006) 1–49 [63] F. J. Gas transport properties of polyarylates: substituent size and symmetry effects. Polym. R. Koros.P. Applications to the separation of gas mixtures. Sci. [47] M.R.-W. Robertson.5-diaminobenzic acid or its esters. Conjugated polymer films for gas separation. Koros. W. B. Phys. J. Hellgardt. Phys. Dai. Soc. Liu. Haraya.R. Polym. 63 (1997) 1. Kita. Sci.A.A.K. Part B: Polym. Sulfonated copolyimides: influence of structural parameters on gas separation properties. Feld. Yoshino. M. [51] M. Paul. W. D. D.J. Vora. Clair. Sci.R. Kaner. [41] L. Piroux. Husk.096. Sci.4-phthalic) hexafluoropropane) diimide (6FDA–1. Paul. 32 (1994) 1009. Sci. 57 (1995) 1595.B. Polym. Anderson.M. Gas transport in polymers based on bisphenol-A. Effect of diamine composition on the gas transport properties in 6FDA/3. Wang. Paul. J. R.H. J. H. Membr. Zimmerman.4-bis(3. [52] N.R. Tabuchi. [74] S. G. W. Gas transport properties of polyarylates based on 9.M. D. Espuche. Part B: Polym. Activation energies and heats of sorption. Structure/permeability relationships of polyimide membranes II.R. J. 33 (1995) 1353. Temperature effects on gas permselection properties in hexafluoro aromatic polyimides. Mercier. Part II. Pixton. Liu. 205 (2002) 23. [73] T.A. Polym. 239 (2004) 105. D. Tanaka. T. 211 (2003) 25.J. 189 (2001) 231. McHattie. D. 225 (2003) 77.H. Kita. Polym.-S. H. T. Tetrabromination of the bisphenol. Paul. Y. Appl. Barbari. D. Koros. A. Muruganandam. Zimmerman. [54] T. Liu. H. C. Sci. Sci. Effects of amidation on gas permeation properties of polyimide membranes. Okamoto. Mi. Sci. E. CO2 /N2 gas separation properties of poly(ethylene oxide) containing polymer membranes. Tanaka.C. 26 (1988) 709. Phys. Desalination 145 (2002) 371. J. Sci. [60] Z. 31 (1993) 939. Chung. Li. Paul. J. Membr. Polypyrrolones for membrane gas separations.R. [82] D. Stern. Springer. Cornelius. M. Xiao. Jho. Effect of isopropylidene replacement on gas transport properties of polycarbonates. Part B: Polym. 37 (1999) 1235. J. Mater. Sci. Guiver. Sakai. E. Gas solubility.9-bis(4-hydroxyphenyl)anthrone.5-naphthalene-2. Part B: Polym. Permeability and permselectivity of gases in fluorinated and non-fluorinated polyimides. Part B: Polym. Phys. K. Trans. J. R. H. K. Kita. Maier. [45] M. Paul. J. Stern. [81] C. [67] M. J. J. Chung. Sci. Zimmerman. D.R. Wang. K. J. R. Y. 28 (1990) 2291. Preparation and characterization of polysulfones containing both hexafluoroisopropylidene and trimethylsilyl groups as gas separation membrane materials. Yamamoto.46 C. J.D. Evaluation of substituted polycarbonates and a blend with polystyrene as gas separation membranes. Membr. R. Res.R. Rebattet. Okamoto. Gas transport properties of polyphenylene ethers. W. Aguilar-Vega. J. Gas transport properties of polyarylates. Novel poly(arylene ether) as membranes for gas separation. Marand. Paul. J. [50] T. [78] C. Matsuura. 1.R. H.R. Clair. [61] S. S. Membr. M.S. Membr. Polym. Freeman. 55 (1991) 99. W. [77] M.S. Structure/permeability relationships of polyimides with branched or extended diamine moieties. H.-S. M. [56] M. H. R. [55] H. [46] M.R. Part B: Polym. diffusivity and permeability in poly(ethylene oxide). Kang. Sci. Chung. Macromolecules 32 (1999) 3341.L. Powell. D. Sci. J. Hamad. Gas separation properties of PMDA/ODA polyimide membranes filling with polymeric nanoparticles. Kaner.-L. Chowdhury. Y. Polymer 40 (1999) 5655. K. Desalination 145 (2002) 365. Polym.-I. Anderson. Effect of methyl substituents on permeability and permselectivity of gases in polyimides prepared from methyl-substituted phenylenediamines. Toshino. M.L.5-NDA) dense membranes. St. [42] G. J. Polym. D.L. Characterization of gas separation membranes prepared from brominated poly (phenylene oxide) by infrared spectroscopy. E. Polym. Lee. R. K. H.R. 38 (2000) 2703. Fluorinated polycarbonates for gas separation applications. J. Membr. 31 (1993) 1599. Part B: Polym. Lee. Polymer 33 (1992) 585. Part B: Polym. Y. Koros. Genies. [75] F. Y.L. Science 252 (1991) 1412. Kim. Pixton. [53] Y. Paul.R. T. Part B: Polym. Chun.D. Liu.3 diaminodiphenyl sulfone copolyimides. Reiss. J. Y. Wang. [66] M. Polym. Structure/permeability relationships of polyimide membranes. C. K. Macromolecules 33 (2000) 7127. Sci. 34 (1987) 185. W. M. Effect of cross-linking modification on gas separation performance of Matrimid membranes. New polyimides for gas separation. Pramoda. J. Gas transport properties of 6FDA–durene/1. 202 (2002) 165.-K. [40] R. H.B. [62] R. Lin. Wang. 30 (1992) 907. Kricheldorf. Paul. Sci. Phys.P. Macromolecules 37 (2004) 1403. Koros. D. Springer. D. Banerjee. Pixton. D. Hibshman.J. J. Wakeman. Okano. Comparision of gas transport and sorption in the ladder polymer BBL and some semi-ladder polymers. J. Enhancement in the gas permeabilities of novel polysulfones with pen- [38] S. Zimmerman. Polym. Mattes. Ding. T. Fritsch. Sci. Pixton. Macromolecules 28 (1995) 8277.J. Part B: Polym.S. [49] J. Chung. R.P. Chan. A. 33 (1995) 1135. Polym. T. Reiss. Characterization. Gas transport properties of polycarbonates and polysulfones with aromatic substitutions on the bisphenol connector group. Y. Paul. 31 (1993) 1577. Polym.P. R. Membranes having selective permeability. Membr. [83] Y.4 -(hexafluoroisopropylidene)diphthalic anhydride. Chung. Membr. Vora. Barbari. J. M. 184 (2001) 69. J.M. S.-S. Fritsch.4-phenylenediamine (pDA) copolyimides. Chng.R. [48] M. [71] K. Part B: Polym. B. Polyimides dervived from substituted terphenylenes and 4. Dannenberg. Robertson.-S. Jungbauer. Matsuura. [68] B. Polym.A. [84] Y. (1995) 1927. Preparation and characterisation of polyaniline based membranes for gas separation. Illing. Gas transport properties of polyarylates part I: connector and pendant group effects. J.R. Liu. Sci. 29 (1991) 731. Membr.

Won. Ruiz-Trevino. T. Ichiki. Phys. Y. Sci.D. L. J. Aitken. Permeability of carbon dioxide at elevated pressures in substituted polycarbonates. Mohr. J. Koros.P.J. Pereira. Qiao / Journal of Membrane Science 279 (2006) 1–49 dant 4-trimethylsilyl-␣-hydroxylbenzyl substituents. 31 (1992) 1061. Lee. Gas transport properties and molecular motions of 6FDA copolyimides.P. Morooka. W. Schrotter. Modified polysulfones. R. J.Y. K. H.-I.R. Membr. Macromol. Molecular design of high-performance polyimide membranes for gas separations. Symp. 64 (1997) 1987. 251 (2005) 263.J.4-trifluoro-5-trifluoromethoxy-1. Guiver. Gas separation membranes from polymers of intrinsic microporosity. Polym. A. Floudas. Powell. Kita. J. Polymer 32 (1991) 840. T. K.M. Y.P. T. Koros. Hacarlioglu.R. Eng.A. Geertsema.D. Paul. [117] G. 85 (2001) 91. J. 160 (1999) 87. Budd.R. Y. Lesimple. Ghanem. C. Yilmaz. Y. sorption. Eng. K. Polym. C. Datwani. Effect of structural symmetry on gas transport properties of polysulfones. Bilodeau.-S. Burns. L. Polym. Yoshino. Hirayama. Gas transport properties of polysulphones. Tabe-Mohammadi. Effects of hard-segment polymers on CO2 /N2 gas-separation properties of poly(ethylene oxide)segmented copolymers. de la Campa.P. M. W. J. T. 3.-I. Y. Comparison of tertramethyl-substituted bisphenols. Symp. J. J. I. J.A. Gramain. Synthesis and permselectivity properties of polysolfones based on bisphenol A and 1. D. Kase. Aitken. A. Sci. B. Bilodeau. Shao.G. Bonfanti. Gas permeation through PSF-PI miscible blend membranes. 28 (1990) 2305. Smaihi. D. Freeman. Dai. 36 (2001) 177. Gas transport properties in polycarbonate films with various unrelaxed volumes. Experimental methods for tracking physical aging of thin glassy polymer films by gas separation. 3 (1996) 11.S.-W. G. Sci. Macromol. J. S. Jho. Sci.J. J. P. 161 (1999) 157. 2. Polym.Y. Kim. Membr. J. Charmette. Guiver. J. P. N. G. Role of symmetry of methyl group placement on bisphenol rings. Gas transport in modified polysulfones with trimethylsilyl groups: effect of substitution site. G. Membr. J. Kita. Membr. H. K. Johnston. Green. Booker.J. S. Interrelation between phase state and gas permeation in polysulfone/polyimide blend membranes. 244 (2004) 167. Effect of preparation parameters on performance of dense homogeneous polycarbonate gas separation membranes. D. Polymer 36 (1995) 3165. J. W. Polym. J. J. Okamoto. Huang. Villaluenga. Sakellaropoulos. J. J. Part B: Polym.-C. Sci. J. D. . H.V. Sci. Sci. Macromolecules 36 (2003) 6433. Membr. D.M. D. Robertson. Robertson. Sci. Kang. Part B: Polym.E.J. P.L. I. W. Phys. W. McKeown. McHattie. Polymer 32 (1991) 1236. Paul.J. Gas separation properties of polysulfone membranes treated with molecular bromine. McHattie. S.1 bi-2-naphthol. Koros. P. 90 (1994) 117. Polym. Phys. D. Kinoshita. Lee.Y.M. Polyarylate gas separation membranes. M.P. Guizard. Membr. Part A: Polym. B. [124] L. D. Macromolecules 36 (2003) 2374. J. M. 199 (2003) 293. F. 90 (2003) 776. Chem.C.G. Paul. Toppare. Permeation properties to CO2 and N2 of poly(ethylene oxide)containing and crosslinked polymer films. Sci. S. [119] M. J. D. Polymer 43 (2002) 5369. B. 107 (1995) 263. D. Yin. Koros. [118] Y. X. H. Mau. N.252 B2 (2003). [113] M.R. Gas separation properties of hybrid imide–siloxane copolymers with various silica contents. K. Sep. Valentini. Roman. Preparation and characterization of silica–polyimide composite membranes coated on porous tubes for CO2 separation. Nagai. Admassu.S. Membr. Maeda. Polymer 32 (1991) 2382. K. Polymer separation membrane.G.J. Sci. Kentish.J. Gas permeation properties of polyimide/epoxy composite materials.L. J. 118 (1997) 401. L. Sci. Part B: Polym.J. Sep. Effect of casting solvent on the permeability of poly(4-methyl-1-pentene). Guiver.B.2.D.E. Tanihara.-i. 163 (1999) 167. Nagaoka. Membranes for gas separation based on poly(1-trimethylsilyl-1-propyne)–silica nanocomposites. E. Effect of bisphenol connector groups. Y.R. K. Kapantaidakis. Structure-property relationships for poly(pyrrolone-imide) gas separation membranes. Structural characterization and gas-transport properties of brominated matrimid polyimide. J.C. Tech. J. Sci. J. Ito. Tech. Kusuki. Part B: Polym. W.P.P. H. C. Chung. W. Hachisuka.P. Gas transport properties of polysulfones based on dihydroxynaphthalene isomers. J. 246 (2004) 13. Wind. 36 (2004) 294. Paul. Membr. Mikawa. Polymer 32 (1991) 2618. Koros. J. US Patent 6. Robertson. Gas transport properties of polysulphones.R. Sisto. Fang. Poly(ethylene oxide-coepichlorohydrin) membranes for carbon dioxide separation. 5. G. Sakellaropoulos.R. Wensley. Effects of pressure ration and pressure difference on the gas permeation properties of rubbery and glassy membranes.J. K. D. Sci.C. M. Pixton. [112] M. Macromolecules 37 (2004) 7688. Sci. G. Jho. J. 42 (2004) 226. Phys.R. J.R. Msayib. [126] Y. Loppinet. Kita. 23 (2003) 209. Polym. Sumiyama. Kang. Appl. Dai. I. 36 (2001) 3121. McHattie. N. Functional ethynlsubstituted polysulfones by bromination–alkynylation suitable as gas permselective membranes. Mater. K. Costello. K. Lee. Sci.C. Lee. Okamoto. Kaldis.D. Dai. C. gas transport properties of a novel 6FDA/PMDA–TMMDA copolyimide membrane and its derived carbon membranes. K. S. Admassu. Jho. Y. S. 47 [85] [86] [87] [88] [89] [90] [91] [92] [93] [94] [95] [96] [97] [98] [99] [100] [101] [102] [103] [104] [105] [106] [107] J. Y. Gas and Vapour Sorption and permeation in poly(2. B. Nunes. Barbari.R.3-dioxoleco-tetrafluoroethylene).J. W. D. J. Pixton. Pramoda. Tanaka. [120] K. 37 (1999) 2788. Paul. S. J. J.J. Polymer 33 (1992) 1701. Membr. [123] J. C. Prevost.Y. J.D. 40 (2002) 4193. Gas transport properties of biphenol polysulfones. de Abajo.R. Analysis of a thermally stable polypyrrolone for high temperature membrane-based gas separations. Sci. Pereira. Macromolecules 25 (1992) 3424. Lanzini. Appl. Polym. Chira. G. Won. Park.P. J. Polym. 1. Macromolecules 36 (2003) 6807. M. Y. Prabhakar. [125] J. K. Membr. Paul. Goh. Jho. Takizawa. Walker.S. F. Synthesis and characterization of tetramethyl polysulfones containing trimethylsilyl groups and their gas transport properties.L. Polym. Synthesis and gas permeation properties of star-like poly(ethylene oxides)s using hyperbranched polyimide as central core. Paul. G. Gomes. Part B: Polym. J. Y.S. Won. Macromolecules 25 (1992) 3651. Espeso. C. Res. Garcia. Macromolecules 34 (20012908). Kang. Haraya. Y. C. D.M. Polym. G. Tattershall.E.S. S. C. Fleming.S.J.S. J. Effects of chemical impurities on gas permeation and diffusion in polymeric membranes. [109] M. Paul. Tabuchi.P.L. [108] Y. Dai. A. [122] J.F. Kang. F. Casting solvent effects on morphologies. Correlation between structure and gas transport properties of silyl-modified polysulfones and poly(phenyl sulfones)s. Yoshino. H. M. [127] H. 244 (2004) 77. W.J. Sci. Koros. R. Lozano. W. 110 (1996) 239.M. Aitken. Dabou. H. Sakai. Lagunas-Fuentes. T. Membr. K.R. B. S. Guiver. 205 (2002) 259. Stevens. Polym. Sci. Sci. G. J. Paul.S. Hirose.P.H.S. [111] K.656. Y. J. Carbon dioxide-induced plasticization of polyimide membranes: pseudo-equilibrium relationships of diffusion. K. [114] G. Kapantaidakis. Effects of chemical impurities on gas sorption in polymeric membranes. G. Sanchez. Mi. Kawakami. C. Paul. C. Kaldis. A. Gas transport properties of polysulphones. [121] D. J. Sci. Membr. Jordon. Tsujita. J. Gas transport properties of adamantane-based polysulfones. Phys. Membr. Hodgkin. G. Koros. Robertson.B. [115] R. [116] G. Koros. Takizawa. 212 (2003) 147. I. Reynolds.S.R. Polycarbonate and polysulfone. Designing aromatic polyamides and polyimides for gas separation membranes. J. Koros. Fritsch. and swelling. Sci. Hayashi.K. Kusakabe.J. 38 (2000) 1707. Y. Won.D. Sirard. [110] T. W. Peinemann.P.S. Sci. M. Paul.R. K. 115 (1996) 65. L. S.

191 (2001) 1. Gas transport properties of thin polymeric membranes in the presence of silicon dioxide particles. Sci. Fan.G. Zimmerman. Zheng. H. M.J. Koros. S. Series 733 (1999) 277. 2005. Teo. Toppare. W. Haas.W. Polym. Beckham.S. Koros. D. Polycarbonate–polypyrrole mixed matrix gas separation membranes. Kim. X. T. Staudt-Bickel. [171] I.J.H. Sci. C.J. [144] D. Qin. US Patent 6. Wessling. Membr.E. . Soc. K.C. T. Surface modification of polyimide and polysulfone membranes by ion beam for gas separation. Sci.S. News 13 (1988) 266. US 6.D. Polym.J. K. 137 (1997) 145. Tailoring mixed matrix composite membranes for gas separations. [161] A. Sturgill. Sci.717. 41 (2002) 6139. L. Shinbo. Xu. Kita. Vora. 139 (1998) 285. 82 (2001) 2166. B. Kim. A. T.J. Wind. Miller. Fritzsche. Choi. Teo. Wang. II. [128] H. I. C. Gas separation of asymmetric 6FDA polyimide membrane with oriented surface skin layer. Development of thinfilm composite hollow-fiber membranes from modified polyphenylene oxide for gas separation applications. US Patent 6.K. Shao. Polym. Membr.L. [173] W.R. A. [151] N. 167 (2000) 79. D. Membr. Koros. Effects of low molecular weight photosensitizer and UV irradiation on gas permeability and selectivity of polyimide membrane. Libby. Ultrathin polymer film formation by collision-induced cross-linking of adsorbed organic molecules with hyperthermal protons.W. T. Yilmaz. J. B.E. Membr. B. Freeman. K. 225 (2003) 51. Koros. Chowdhury. [152] Z.T. D. [160] A. W.Y. Ismail. 15 (2003) 729.J. Sci.H. Pramoda. Koros. Patel. Membr. Sci. S. W. 136 (1997) 249. Ismail.248.M. Deng. Sci. Bikson. Membr. H. Highly CO2 -permeable and selective polymer nanocomposite membranes. Ind.H.J. Li. Wind. [158] M. Sci. 211 (2003) 335.C. [172] J.J. Lin. [165] D.J. Membr. Wright. Macheras. Kumar. Tucker. Spontak. Gas and vapor solubility in cross-linked poly(ethylene glycol diacrylate). Preparation and characterization of gas separation hollow fiber membranes based on polyethersulfone–polyimide miscible blends. Blanc. Xiao. Matsui. Wessling.R.497 1991. Sci. [150] N. Characterization of polyethersulfone–polyimide hollow fiber membranes by atomic force microscopy and contact angle goniometery. Formation of defect-free polyimide hollow fiber membranes for gas separations. Hacarlioglu. Sci. Gas separation by polysulfone hollow fiber membranes. Lau. Membr. Macromolecules 34 (2001) 9039.D. 229 (2004) 1. Goh. [137] J. Membr.E. Kusuki. He.H. Pinnau. Feng. Kim.C. Res. R. Mahajan. [169] H. Nakajima.-J. Sato. Appl. 14 (2004) 699. Natural gas permeation in polyimide membranes. Z. A. Kalika.F. K. Membr. T. S. T. T. H. Sci.P.923. Sci. Kwok. Nelson. Characterization of permeability and sorption in matrimid/C60 mixed matrix membranes. Li. G. Matsuura. Sorensen. [167] H. Rezac.D. Kawakami.W. [145] D.C. Miller. Koh.E.C. Miller. He.D. Chan. [148] M.L. A. Chung.Q. 73 (1999) 1471. Sci. Pinnau. Y. Sci. Membr. Koros. [174] K. S. B. Vu. J. Koops. Preparation and characterization of polyetherimide asymmetric hollow fiber membranes for gas separation. Tremblay. Polyethersulfone hollow fiber gas separation membranes prepared from NMP/alcohol solvent systems. K.T. C. Powell. J. Chem.Y. J. Membr. S.J. Li. Paul. Chung.J. Suzuki. T.-I. Ind. Won. Laverty. R. Freeman.H. B. J. Adv. Kang.K.-S. 739 (2005) 57. Membr. Koros.A. [146] R. Polyimide gas separation membranes. M. Characterization of asymmetric polysulphone membranes for gas separation.L. Lu. J. [132] M. Kawakami. Lin. M. Sch¨ oberl. [159] A.J. Y.S.D. Preparation and characterization of highflux polysulfone hollow fibre gas separation membranes. [136] T. Polym. Sci. 79 (2001) 275.R. H. 129 (1997) 47. 211 (2003) 91. Sci. Hayes. Kurdi.-H. [142] C.932.-S. [138] J. Patel. Materials selection guidelines for membranes that remove CO2 from gas mixtures.-S. G. Sci. K. [156] C. J. Desalination 145 (2002) 353. Mixed matrix membranes using carbon molecular sieves.M.K. Preparation of composite hollow fiber membranes of poly(ethylene oxide)-containing polyimide and their CO2 /N2 separation properties. Gas separation using coated membranes. Fouda. Preparation of defect-free asymmetric membranes for gas separation. 146 (1998) 31. H.981. Feasibility of thermal crosslinking of polyarylate gas-separation membranes using benzocyclobutene-based monomers.-H. Chng. Gallivan. W.J. Cao. Sci. J. Kai. Hayes. Nagaoka. J. [131] C. 75 (2000) 1554. 5 (1991) 215. J. [147] T. Okamoto.E. Membr. [141] J. Chem. Sci. J.R. 211 (2003) 311.J.896.J. Mater.J. Membr. Zimmerman. J. J. Fundamental.C. Pramoda. W. A. practical aspects of mixed matrix gas separation membranes. Membr.-S. Park. Nagaoka.K. Clausi. Koops.T. Sci. Sci. 238 (2004) 153.682 B1 (2001). Incorporation of zeolites into hybrid polymer matrices. K. [157] J. S.J. J. 211 (2003) 291.-S. [133] S. Effects of orientation relaxation and bore fluid chemistry on morphology and performance of polyethersulfone hollow fibers for gas separation. S.K. [170] G. Membr. Sci. 204 (2002) 247. S. Wallace. Transport properties of cross-linked polyimide membranes induced by different generations of diaminobutane (DAB) dendrimers. [166] R. [135] L. Shilton. S. Dudley. Membr. Koros. The effect of cross-linking on gas permeability in cross-linked poly(ethylene glycol diacrylate). [134] R. Membr. ACS Symp. S.859 B2 (2005). Kalakkunnath. [175] J. Kanamori. 115 (1996) 85. Preparation and experimental results. J. R. Y. C. [154] J. Beckham. Berry. [129] H. US Patent 6. W. Lin. The physical aging phenomenon of 6FDA–durene polyimide hollow fiber membranes. [149] P. Appl. Chung. S. Relationship between substructure resistance and gas separation properties of defect-free integrally skinned asymmetric membranes. R. Kaito. 125 (1997) 143. M. J. G. [130] H. [162] D. Sci. Amine-modified polyimide membranes.J. Singh. Lin.W.P. X. J. Tanaka. Sci. 226 (2003) 63. [139] W. Miller. J. 138 (1998) 193. 126 (2004) 12336. Niwi. Wind. W. Chung. Polym.K. J.T. J. Appl. Eng. Gas Sep. Paul. Gas separation characteristics of isomeric polyimide membrane prepared under shear stress. A. Paul. [168] D. Sci. H. [164] G. Moaddeb. Method of preparing composite gas separation membranes from perfluoropolymers. B.J. Shilton. W. Modeling permeation behavior. I. Dunkin. M. Am. [143] R. R. Highly CO2 -permeable and selective membranes derived from crosslinked poly(ethylene glycol) and its nanocomposites. Polysulfone gas separation hollow fiber membraneswith enhanced selectivity. Production of super selective polysulfone hollow fiber membranes for gas separation. S. Sci. Membr. R. J.717 B2 (2005). Wang. Mater. Z. 228 (2004) 227. Mixed matrix membranes using carbon molecular sieves. A. S. Nakagawa. Freeman. Kapantaidakis.846. L. E. T. Eng. Fabrication of 6FDA–durene polyimide asymmetric hollow fibers for gas separation. Yoshinaga. Wang. Macromolecules 38 (2005) 8394. Miller. W.K. Macromolecules 38 (2005) 8381. Sci. Polym. 141 (1998) 31. Kapantaidakis. Membr. J. K. Influence of crosslinking techique on the physical and transport properties of ethynyl-terminated monomer/polyetherimide asymmetric membranes. Staudt-Bickel. Phys. A. Khulbe. T.D. Matsuura. R. J. Membr. Rose. Res.M.C. Sci.B. [140] R. J.J. Purif. Asymmetric membranes by a two-stage gelation technique for gas separation: formation and characterization. 38 (2000) 765. 161 (1999) 229. Koros. Vu. Wang. Part B: Polym. J. Chem. Rezac. Wang. D. The effects of crosslinking chemistry on CO2 plasticization of polyimide gas separation membranes. [163] D. W. Adv. D. H.F. W. US Patent 4.Q. G. Hoshino.M. K. Marchese. Spontak. B. S.48 C. Thompson. Crosslinked and crosslinkable hollow fiber membrane and method of making same.393 1988. Appl. Polymer 40 (1999) 6499. J. Y. Chung. Membr. Teo. J. J.N. G. M. Funct. W. J. PAMAM dendrimerinduced cross-linking modification of polyimide membranes. 30 (1991) 1837. W. Pagliero. Qiao / Journal of Membrane Science 279 (2006) 1–49 [153] I. C. K. Koros. J.A. US Patent 4. [155] H. Langmuir 20 (2004) 2966. J. Transport properties of crosslinkable polyimide blends. C. Tabe-Mohammadi. U.

A. 37 (1988) 45. C. Ahn. The ageing phenomenon of polyethersulphone hollow fibre membranes for gas separation and their characteristics. T. H. [181] I. mechanisms and effects. Sci. Sci. Shilton.-H. Sci. G. Sci. Cassidy.P. Nakane. Sci. Idemoto. V. Husk. Zeng. T. Chng. 75 (2000) 1026.J. CO2 separation performances of composite membranes of 6FDA-based polyimides with a polar group. Macintosh. Res. Polym. H. 211 (2003) 41. K. J. Sci. Part B: Polym. Sci.M. J. Teoh. J. D. D. J. G.-J. D.J. Tullos. [178] T. J. Dunkin. Chem. Wijmans. T. N. J. H. Sharpe.R. G. 71 (1999) 2385. Y.L.G. D.F.C. Ind. S. Gordeyev. Koura.A. Shilton. Paul. Membr. J. Ann. . I. Membr. 42 (2003) 1190. [182] K. Application of poly(phthalazinone ether sulfone ketone)s to gas membrane separation.X. Appl. Chung. O’Brien. S.L. S. Mohanty. Membr. Membr. 152 (1999) 175. N. T. R. Acad. 188 (2001) 165. Xu. 229 (2004) 225. T. Sci. Kim. T.D. 37 (1988) 81. Gas transport properties of a series of poly(ether ketone) polymers. Moon. Haraya. Sci. Direct measurement of rheologically induced molecular orientation in gas separation hollow fibre membranes and effects on selectivity.J. Matsuda.Y. Teramoto. I. Membr. K. Peinemann. Blume. Kozhurnikova. [180] V.G.R. X. Relationship between gas separation properties and chemical structure in a series of aromatic polyimides. Sci. J. I.R. Kuroda. N. Preparation of 6FDA-based polyimide composite membrane by CVDP process. Gallivan. Gas transport properties of poly(arylether bissulfone)s and poly(arylether bisketone)s. Koros. S. Eng. Shilton. A. R. Separation performance of polyimide composite membrane prepared by dip coating process. 126 (1997) 133. Kazama.L. Qiao / Journal of Membrane Science 279 (2006) 1–49 [176] A. Kudryavtsev. 984 (2003) 318. Mohr. M.-S. Sci. I. Chung.A.F.K. S. Gordeyev. Chemical cross-linking modification of polyimide/poly(ether sulfone) dual-layer hollow-fiber membranes for gas separation. So. Liu.V. Polymer 32 (1991) 2387. H. Okadu. S. Yanagishita.E.-W. D.H. Membr.R.J. Kitamoto. J. Carbon dioxide and nitrogen transport properties of bis(phenyl)fluorene-based cardo polymer membranes. Jian. Yanagishita. S.-J.E. K. T. Kim. S. K. Haraya. Polym. G.D. J. Nozoye. Pinnau. Polysulfone hollow fiber gas separation membranes filled with submicron particles. Paul. Powell. S. Wang. P. Aitken. Li. Formation and analysis of a polyimide 49 [184] [185] [186] [187] [188] [189] [190] layer in composite membranes. Forced convection spinning of gas separation hollow fibre membranes: some underlying factors. Gas permeation through composite membranes. Sci. [177] S. W. [179] Y.-S. Bhardwaj. Polym. Park. Desalination 90 (1993) 55. Ismail. Phys.-J. 31 (1993) 983.L. J. J. Membr. D. Elyashevich. Dai. W.V.K. Membr. [183] G. Appl. V. Sklizkova. Y.K.G. Polotskaya. 207 (2002) 91. J. Nakane.