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Anbukulandainathan, M. and Kulanjiappar, K. and Raju, T. and Muthukumaran, A. (2005) Cyclic voltammetry and RRDE studies on the electrochemical behaviour of azetidinone ester. Portugaliae Electrochimica Acta, 23 (3). pp. 355-365.
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Geetha, S. and Satheesh Kumar, K.K. and Trivedi, D.C. (2005) Conducting fabric reinforced polyaniline film using p-chlorophenol as secondary dopant for the control of electromagnetic radiations. Journal of Composite Materials, 39 (7). pp. 647-658.
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Microporous polymers with molecular sieving properties are promising for a wide range of applications in gas storage, molecular separations, catalysis, and energy storage. In this study, we report highly permeable and selective molecular sieves fabricated from crosslinked polymers of intrinsic microporosity (PIMs) incorporated with highly dispersed nanoscale fillers, including nonporous inorganic nanoparticles and microporous metal–organic framework (MOF) nanocrystals. We demonstrate that the combination of covalent crosslinking of microporous polymers via controlled thermal oxidation and tunable incorporation of nanofillers results in high-performance membranes with substantially enhanced permeability and molecular sieving selectivity, as demonstrated in separation of gas molecules, for example, air separation (O2/N2), CO2 separation from natural gas (CH4) or flue gas (CO2/N2), and H2 separation from N2 and CH4. After ageing over two years, these nanofiller-tuned molecular sieves became more selective and less permeable but maintained permeability levels that are still two orders of magnitude higher than conventional gas separation membranes.
PIMs polymers are a class of polymers with rigid and contorted backbone structure.8–16 The chemical structure of a representative PIM-1 is shown in Fig. 1a. In the solid state, rigid polymer chains (as visualized in Fig. 1b) cannot pack efficiently, forming interconnected cavities behaving like micropores. The pore structure in PIMs molecular sieves can be visualized as the hour-glass shaped interconnected cavities, as shown in Fig. 1c. The molecule-sized pores and intermolecular interactions allow high solubility of gas molecules, particularly condensable gases, while the bottlenecks or gates interconnecting pores behave as sieves for separating gas molecules with different sizes. Owing to the unique pore structure, these polymeric molecular sieves achieve both higher permeability and higher selectivity.1,17 Further structural modifications of PIMs include substituting side functional groups that may introduce stronger intermolecular forces (i.e. hydrogen bonding),13,18,19 or design of more rigid polymer backbone structure,14,15,20–23 producing more selective or permeable molecular sieves.
Fig. 1 Thermal-oxidative crosslinking of PIM-1 polymer nanocomposites incorporated with nanofillers. (a) Chemical structure of PIM-1 polymer. (b) 3D model of PIM-1 polymer chain segment. (c) Schematic diagram of molecular sieve membranes fabricated from PIMs polymer showing hour-glass-shaped interconnected cavities for rapid and selective transport of gas molecules (e.g. CO2 and CH4). (d) Molecular structure of ZIF-8. Yellow regions indicate Connolly surface probed by H2 molecules. (e) Schematic diagram showing rigid polymer chains incorporated with nanofillers are covalently crosslinked to three-dimensional networks upon thermal-oxidative processing at suitable temperature (350–450 °C) in the presence of trace amount of oxygen. (f) SEM image of ZIF-8 nanocrystals. Cross-sectional SEM images of (g) PIM-1/ZIF-8 after annealing at 120 °C under vacuum (1 mbar), (h) TOX-PIM-1/ZIF-8 crosslinked at 385 °C for 24 h under vacuum (1 mbar), (i) PIM-1/ZIF-8 after annealing at 300 °C for 48 h under vacuum (1 mbar). (j) PIM-1/SiO2 annealed at 120 °C, (k) TOX-PIM-1/SiO2 annealed at 385 °C for 24 h under vacuum (1 mbar). Samples were fractured in liquid nitrogen and coated with a thin layer of gold.
Mixed matrix membranes (MMMs), formed by incorporating molecular sieves or nanoscale fillers into polymer matrices, have also attracted significant interest.24–27 When the size of fillers in the polymer matrix is reduced to nanoscale, i.e. approximate to that of polymer chains, the properties of nanocomposite materials are strongly dependent on the interface between the polymer and fillers, where the local polymer chain mobility and conformation and their interactions vary significantly.26 Novel microporous materials, such as metal–organic frameworks (MOFs),28 with well-defined pores as shown in Fig. 1d, have been demonstrated as building blocks for molecular-sieving membranes,29–39 or as fillers in MMMs.40–47 Whilst often beneficial to membrane performance, the structure–property relationships of MMMs is complicated to predict, with diffusion and adsorption parameters varying from the bulk polymeric phase, to the interface with the fillers and potentially the internal surfaces of fillers.
PIM-1 polymer-based mixed matrix membranes have been prepared by solution mixing of PIM-1 polymer with various fillers including nonporous fillers and microporous materials, such as PIM-1/silica,48 PIM-1/ZIF-8,49 PIM-1/cages,50 PIM-1/POSS,51 PIM-1/MOFs,52 and PIM-1/porous aromatic frameworks (PAFs).53,54 In all of these studies, addition of fillers enhanced gas permeability of resulting composite membranes to certain extents, however the selectivity remained relatively unchanged (e.g. CO2/CH4 selectivity at 10–15) and far below the desirable level for practical gas separation technology, for example, CO2/CH4 selectivity at 30–40 for natural gas purification. PIM-1 polymer, the dominant phase in these composite membranes, limits the baseline of performance in gas separation. Novel approaches to production of molecular sieves and nanocomposites with both high permeability and high molecular selectivity are desirable for applications of the fast-growing class of microporous polymers including PIMs, for example, in membrane separations.
Recently, we reported that linear PIM-1 polymer can be transformed to a new class of highly crosslinked, insoluble, infusible, and microporous polymer networks (TOX-PIMs) via thermo-oxidative crosslinking,55 demonstrating control of membrane molecular sieving properties through control of the reaction kinetics. Such processing leads to membrane materials with excellent selectivity (e.g. CO2/CH4 up to 70) but with an unsurprising loss in overall gas permeability (e.g. CO2 permeability at 1000 Barrer). Since many microporous polymeric materials are subject to ageing that further reduces permeability, in this work, we sought to improve the control of gas permeability in thermo-oxidatively crosslinked TOX-PIM materials by incorporating nanoscale fillers. The resulting nanofiller-tuned crosslinked polymer molecular sieves show an excellent selectivity and maintain the permeability at a significant level, despite the effects of ageing.
Our strategy of fabricating crosslinked nanocomposite membranes is visualized in Fig. 1e. Nanofillers are incorporated in rigid PIM polymer matrices and then exposed to controlled thermal oxidative crosslinking in the presence of trace amount of oxygen at suitable temperatures (350–450 °C). The thermal-oxidation and crosslinking reactions transform linear polymer chains to highly crosslinked, infusible, and insoluble networks where the size and shape selectivity (DA/DB) of gas molecules is enhanced in the polymer phase while maintaining high solubility (S) and solubility selectivity (SA/SB). On the other hand, nanofillers, regardless of their internal porosity, disrupt the packing of polymer chains and introduce extra free volume and defects at the interface owing to their high external surface area, consequently enhancing the absolute value of gas diffusivity (D) compared to pure polymer networks. Therefore, the combination of enhanced rigidity in polymer networks and nanofillers in composite membranes offers high permeability and sufficiently high selectivity for gas separation.
Polymer nanocomposite membranes were prepared using the solution mixing and casting method (ESI†). PIM-1 polymer was synthesized following the chemistry invented by Budd and McKeown (Fig. S1†).8 Nanoparticles were dispersed as colloids in chloroform and thoroughly mixed with PIM-1 polymer dissolved in chloroform giving a colloidal mixture, following our previously reported approach.56 In this study, two representative types of nanofillers were used: porous ZIF-8 nanocrystals (primary size of 70–100 nm, Fig. 1f) and nonporous inorganic nanoparticles (fumed silica, primary size of 12 nm). ZIF-8 was selected as a prototypical porous MOF owing to its easy synthesis in the form of nanoparticles, well-defined micropore structure, and high thermal stability. Silica was chosen as archetypal nonporous filler for polymer systems. After casting and slowly evaporating the solvent, we obtained self-standing, optically transparent and mechanically flexible polymer films (Fig. S2, ESI†). These PIM nanocomposite films were further exposed to thermal-oxidative crosslinking reactions, following the same protocol reported in our previous work.55 In this study, the thermal-oxidative crosslinking processing was performed by heating the polymer films at 385 °C under continuous vacuum (1 mbar) in a vacuum oven. Afterwards, crosslinked polymer and nanocomposite films became mainly insoluble both in traditional solvents for PIM-1, such as chloroform (see Fig. S2, ESI†), tetrahydrofuran or dichloromethane, and non-solvents (acetone, N-methyl-2-pyrrolidone, dimethylformamide, toluene, or alcohols). These crosslinked polymer films show certain degree of swelling in chloroform, confirming their polymeric nature. The optical transparency confirms the high degree of dispersion of small nanoparticles without formation of large particles or agglomeration, which would result in significant scattering of light and loss in transparency. Our high-magnification scanning electron microscopy (SEM) images of nanocomposite membranes, including PIM-1/ZIF-8 (Fig. 1g), PIM-1/SiO2 nanocomposites (Fig. 1j) clearly show that the nanofillers are well dispersed in the polymer, but we also observed the presence of mesopores in the polymer phase or around the nanoparticles. More SEM images are shown in Fig. S3–5 (ESI†). Furthermore, SEM-EDX analyses (Fig. S6 and S7, ESI†) confirmed the high dispersion of nanofillers in the crosslinked polymer matrices. Similar morphologies can be observed in other composites of PIM-1/nano-silica,48 PIM-1/ZIF-8,49 or PIM-1/cages crystals,50 where heterogeneous interfaces exist. The soluble fractions in most crosslinked samples are below 5 wt% and are of low molecular weight (Fig. S8, ESI†) indicating that a minimal degradation of the polymer occurs during the thermo-oxidative process. SEM images confirmed that the thermal treatment leads to densification of mesopores at the interfaces between polymer and nanofillers, as shown in Fig. 2h and k, though mesopores can still be observed. Thermal-oxidative degradations of PIM-1 polymer nanocomposites were confirmed in thermogravimetric analyzer (Fig. S9, ESI†), where the temperature and heating rate, concentration and flow rate of purging gas, and heat transfer could be well controlled. Therefore, the extent of thermal-oxidative crosslinking of polymer films could be carefully tailored by controlling the reaction kinetics.
Fig. 2 Gas sorption properties. (a) N2 adsorption–desorption isotherms of PIM-1 thin film, ZIF-8 nanocrystals, and PIM-1/ZIF-8 composite films at 77 K. Adsorption/desorption curves are shown as solid/open symbols, respectively. (b) Pore size distribution derived from the N2 adsorption isotherms based on NLDFT model. (c) N2 adsorption–desorption of PIM-1/ZIF-8 and crosslinked TOX-PIM-1/ZIF-8 composite films at 77 K. (d) Gas sorption isotherms of PIM-1/ZIF-8 (open symbols) and TOX-PIM-1/ZIF-8 (solid symbols) composites at 273 K, and (b) derived pore size distribution. All samples were degassed at 120 °C under high vacuum prior to gas sorption measurements. PIM-1 thin film (300 nm) was dried at 120 °C under vacuum; ZIF-8 nanocrystals were dried at 120 °C under vacuum; thick dense PIM-1/ZIF-8 film (∼50 μm) was dried at 120 °C under vacuum, with ZIF-8 loading at 20 wt%. TOX-PIM-1/ZIF-8 film was crosslinked by heating at 385 °C for 24 h under vacuum (1 mbar).
We used X-ray photoemission spectroscopy (XPS) to probe the chemical bonding states in the surface of polymer films. The high-resolution XPS spectra of O1s, N1s, and C1s of PIM-1 and TOX-PIM-1 films are given in Fig. S10 (ESI†). The major difference is the observation of a higher shoulder peak at binding energies of 531.68 eV in O1s spectra, and a new broad weak peak at 288.78 eV in C1s spectra, both of which are associated with the O–C O bonds owing to presence of residual oxidized groups in the TOX-PIM-1 film. The FTIR spectra of our TOX-PIM-1 and nanocomposite films (Fig. S11 and S12, ESI†) confirmed the presence of residual oxidised groups such as C O and O–H groups, a clear evidence of oxidation. The nitrile (C N) groups are relatively stable and peaks associated with imine groups (C N) are not observable. These changes of chemical bonding correspond to the thermal oxidation of PIM-1 polymer, with several possible initiation sites for chain reactions and crosslinking (Fig. S13, ESI†).
It is well known that nanoparticles dispersed in the polymer matrix serve as spacers for polymer chains, so that the polymer phases in polymer–nanoparticle composites are equivalent to thin films.57 Here, the loose packing in composite membranes is also reflected by lower thermal conductivity (Fig. S14, ESI†). We also studied the mechanical properties of nanocomposite films with stress–strain measurements (Table S1, ESI†) and nanoindentation tests (Table S2, ESI†). These crosslinked polymer nanocomposites show a certain degree of decay in mechanical properties, compared to TOX-PIM-1 film. Nevertheless, these nanocomposite films are still mechanically resilient and can be bended or handled for subsequent high-pressure gas permeation tests.
For nanocomposites incorporated with MOF nanofillers, XRD analysis (Fig. S15, ESI†) confirmed the high crystallinity of ZIF-8 nanoparticles in the polymer matrix after annealing at moderate temperatures (<200 °C). However, thermal processing at relatively higher temperature over an extended period induced partial degradation of ZIF-8, as reflected by the broadening and lower peaks in XRD patterns of nanocomposite membranes or ZIF-8 nanocrystals alone (Fig. S16, ESI†). The partial oxidative degradation of ZIF-8 may be related to the removal of methyl groups.58 Since those partially degraded ZIF-8 nanoparticles still retain their size (Fig. S17, ESI†) and serve as spacers in nanocomposites, the physical effects of such degradation on the polymer network are not significant.
The solubility of various gases in polymer membranes were probed with a series of gas sorption measurements. In our previous work,55 we found that thermal-oxidatively crosslinked PIM-1 polymer films show an interesting gate-opening phenomena in nitrogen adsorption at low temperature of 77 K. Therefore, N2 adsorption at 77 K is not effective to probe the pore structure of microporous polymers, due to the kinetically-limited diffusion of large N2 molecules. In contrast, for PIM-1 thin films or open ZIF-8 framework (Fig. 2a), the sorption of nitrogen was not diffusion-limited. Polymer nanocomposite films annealed at moderate temperatures (120 °C) showed enhanced N2 sorption at a low pressure stage, similar to that of PIM-1 thin films (300 nm).
Fig. 2b confirms the microporosity of crystalline ZIF-8, and the broad size distribution of micropores in PIM-1 and composites. These N2 adsorption isotherms confirm that nanofiller-spaced polymer chains are loosely-packed and behave equivalently to thin films (surface area ∼ 800 m2 g−1). In contrast, crosslinked composite membranes show restricted sorption at low pressure (Fig. 2c), while the total quantity of adsorption at 1 bar does not significantly change. From a thermodynamic perspective, the polymer at low temperature of 77 K behaves as a ‘frozen’ state with lower segment mobility. Gas sorption isotherms of CO2, CH4 and N2 at 273 K (Fig. 2d) confirm that the gas solubility in thermal-oxidatively crosslinked nanocomposites is maintained at the same level as those unmodified samples. Pore size distributions derived from CO2 sorption isotherms at 273 K based on non-local density functional theory (NLDFT) method (Fig. S19, ESI†) indicates subtle modifications of ultramicropores (<7 Å). These adsorption isotherms confirm our hypothesis that thermal-oxidative crosslinking does not seriously diminish the fractional free volume (FFV); instead, the crosslinking primarily changes the size of gates and channels connecting free volume elements in the polymer phase, which result in significant changes in kinetics of gas diffusion.
Fig. 3 Gas transport properties. (a) Gas permeability (at 295 K) versus the kinetic diameter of gas molecules. (b) Solubility (at 295 K) versus the critical temperature of gas molecules. (c) Diffusivity (at 295 K) versus the square of effective diameter of gas molecules.59 In (a–c), the loading of SiO2 in TOX-PIM-1/SiO2 is 10 wt%, loading of ZIF-8 in TOX-PIM-1/ZIF-8 is 20 wt%. (d) Gas permeability, (e) ideal selectivity, (f) solubility (S), (g) solubility selectivity, (h) diffusion coefficient (D), and (i) diffusivity selectivity, as a function of the volume fraction of nanofiller in thermal-oxidatively crosslinked PIM-1 nanocomposite films. TOX-PIM-1 and nanocomposite films were oxidatively crosslinked at 385 °C for 24 h under vacuum (1 mbar). Data of nonporous nanosilica (solid symbols) and porous ZIF-8 (open symbols) at different loadings are plotted together in (d–i). TOX-PIM-1/ZIF-8 nanocomposites with loading of ZIF-8 nanocrystals at 5, 10, and 20 wt%, respectively. TOX-PIM-1/SiO2 nanocomposites with loading of silica nanoparticles at 1, 2, 5, 10, and 20 wt%, respectively. The volume fractions are derived based on weight loadings and densities of the polymer and nanofillers. Lines in (a–c), (d), and (e) are added to guide eyes.
Based on the solution-diffusion model and time-lag measurements, gas solubilities and diffusivities of these nanocomposites are derived. As shown in Fig. 3b and f, the gas solubilities at 295 K are close to those of pure PIM-1 polymers or crosslinked networks. This agrees well with the observation of constant gas solubilities measured from gas sorption isotherms at 273 K, for example, CO2 solubility is maintained at about 0.5 cm3 cm−3 cmHg. The diffusivity of various gas molecules are shown in Fig. 3c and h. Clearly, the incorporation of nanofillers enhances the diffusion of gas molecules, for example, the CO2 diffusivity increases from 2.2 × 10−7 cm2 s−1 to 8.3 × 10−7 cm2 s−1. Therefore, the increase of permeability is attributed to enhanced diffusivity (Fig. 2d). With the increasing loading of nanofillers regardless of their internal porosity, the solubility selectivity (SA/SB) remained relatively constant (i.e. CO2/CH4 about 4.0) while the diffusivity selectivity (DA/DB) decreased, for example, diffusivity selectivity of CO2/CH4 dropped from 19 to 7 (Fig. 3i). It is well known that gas diffusivity in molecular sieves could change over multiple magnitudes depending on the shape and geometry of pore apertures (Fig. S20, ESI†). Previous work has shown that nanofillers disrupt the packing of rigid polymer chains and physically change the microstructure and free volume elements of polymer phase.26 Here, the enhanced diffusion and compromised selectivity at high loading of nanofillers is due to a combination of molecular sieving in polymer phase and enhanced diffusion through interfacial defects.
The effects of nanofillers and thermal processing are more evident when we compare the gas transport properties with the Robeson's upper bound (Fig. 4). For composite membranes containing nonporous nanofillers such as fumed silica nanoparticles, the gas permeability is enhanced while the ideal selectivity is compromised as a function of silica loadings. Such observations agree well with previous study on PIM-1/silica composites.48 In the instances of PIM-1/ZIF-8 composites, the gas permeability was also enhanced while the changes in ideal selectivity varied for different gas pairs. The permeability of H2 increases significantly with the loading of ZIF-8, while the corresponding gas selectivity to large gas molecules show slight increase, e.g. H2/N2 from 14 to 18, H2/CH4 from 12 to 15. Similarly, O2 permeability shows a remarkable enhancement from ∼1000 to ∼1500 Barrer while the O2/N2 selectivity increases from 4 to 5. Compared to nanocomposites containing nonporous nanosilica filler, the samples with ZIF-8 show relatively higher selectivity. The gas transport properties of these nanocomposite membranes are similar to previous studies,48–50 and are determined by a number of factors: (i) the increase of free volume in loosely packed polymer due to disruption of nanoparticles and alcohol-swelling treatment, (ii) microcavities and defects at the interface between polymer and nanoparticle, and (iii) rapid diffusion through the porous fillers, all of which could enhance the gas diffusivity and consequently permeability of the composite films.
Fig. 4 Upper bound plots of selectivity versus permeability for important gas pairs of H2/N2, O2/N2, CO2/N2, and CO2/CH4. Robeson upper bound reported in 1991 and 2008 are plotted.2,3 Open squares: PIM-1 in literature; solid triangles: other PIMs in literature;13–15,20–22 solid squares (black): unmodified PIM-1; solid squares (red): TOX-PIM-1 membranes. Blue open circles: PIM-1/SiO2 composites; blue solid circles: TOX-PIM-1/SiO2; red open diamonds: PIM-1/ZIF-8; red solid diamonds: TOX-PIM-1/ZIF-8. The gas transport properties were measured from pure gas permeation at 4 bar and room temperature of 22 °C. PIM-1 and PIM-1 based nanocomposite films were annealed at 120 °C for 24 h. PIM-1/SiO2 nanocomposites with loading of SiO2 nanoparticles (primary particle size 12 nm) at 1, 2, 5, 10, 20, 30, 40 wt%, respectively. TOX-PIM-1/ZIF-8 and TOX-PIM-1/SiO2 nanocomposite films were oxidatively crosslinked at 385 °C for 24 h under vacuum (1 mbar). Note: individual data points for each nanocomposite loading may be cross-referenced from Fig. 3.
For our TOX-PIM-1 composite films after crosslinking, the selectivities of all gas pairs are enhanced to a very promising level, at a slight trade-off of permeability. For composites exposed to the same processing history as TOX-PIM-1 polymer films, incorporating nanofillers into crosslinked PIM-1 network enhances the permeability while the ideal selectivity of gas pairs decreases as a function of the volume fractions of nanofillers. These nanocomposites are still far more selective than non-crosslinked nanocomposites.48,49 Such significant enhancement of gas selectivity along with the combination of high permeability allows the overall gas separation performance of these nanocomposites to surpass the Robeson upper bound for a range of gas pairs (such as CO2/CH4, O2/N2, H2/N2 and H2/CH4).
We also confirmed the enhanced gas permeability and excellent selectivity of thermal-oxidative crosslinked nanocomposite films in mixed gas permeation, with initially equimolar and CO2/CH4 mixture, as shown in Fig. 5a and b. For high free volume glassy polymers, CO2 and other condensable gases adsorbed in the polymer can increase the overall free volume and polymer chain segment mobility, termed as plasticization, which tends to result in lower selectivity at high CO2 partial pressure. At high pressure, the competing sorption of CO2 and CH4 further compromised the gas selectivity. Here, these thermo-oxidatively crosslinked networks show lower gas selectivity at high pressure, which are sufficiently selective for gas separation. The fractions of CH4 in the permeates through these selective films are below 5 vol% (CO2 purity above 95 vol%) (Fig. 5c), whereas it is as high 15 vol% for unmodified PIM-1 polymer membranes. The CO2/CH4 selectivity for commercial membranes (e.g. cellulose acetate) is about 20–30 below 10 bar and decreases to about 10–15 at higher pressure of 30 bar. Here, our membranes give higher selectivity at low pressure, therefore they produce similar gas purity, yet they are far more permeable than commercial membranes.
Fig. 5 Mixed gas transport properties and aging behaviour. (a) Gas permeability versus the fugacity of CO2 in feeding gas, (b) selectivity CO2/CH4versus fugacity of CO2 in feeding gas mixture, and (c) permeate concentrations for separation of CO2/CH4 (50/50 vol%) gas mixture. (d) Upper bound plot showing the gas transport properties of polymer films during ageing for two years. Commercial polymers are included for comparison: cellulose acetate (CA); polycarbonate (PC); Matrimid® 5218 polyimide (PI); polyetherimide (PEI); polyphenyleneoxide (PPO); polysulfone (PSF), polystyrene (PS), cited from ref. 60. PIM-1 and nanocomposite films were annealed at 120 °C for 24 h under vacuum. Crosslinked PIM-1 and nanocomposites, TOX-PIM-1/ZIF-8 (10 wt%) and TOX-PIM-1/silica (10 wt%), were prepared by heating at 385 °C for 24 h under vacuum (1 mbar). (d) Aging of crosslinked polymer films. Films aged for over two years, PIM-1 for about 750 days, TOX-PIM-1 aged for about 750 days, TOX-PIM-1/SiO2 (5 wt%) aged for about 740 days, TOX-PIM-1/ZIF-8 (5 wt%) aged for about 740 days. For comparison, the data of TOX-PIM-1 membrane reported in a previous work55 are included.
Physical ageing, resulting in gas permeability reduction over time, is a critical issue that limits the industrial applications of membranes fabricated from glassy polymers. Such physical ageing is especially severe for high-free-volume polymers.61 PIMs membranes also suffer from the physical ageing because entangled polymer chains still tend to conform and pack tightly over time. Various approaches have been investigated, such as chemical crosslinking,62,63 and incorporation of additives such as porous aromatic frameworks.53,54 Our recent work showed that TOX-PIM-1 networks still suffer from ageing to some extent, with gas permeability rapidly decreases in 30 days but then slowly stabilized over time.55 In this study, the aged crosslinked nanocomposites and TOX-PIM-1 still show loss in permeability, but the gas permeability and selectivity are maintained at a remarkably high level after ageing over two years (Fig. S21, ESI†), as compared with the upper bound in Fig. 5d. Interestingly, the selectivity of smaller gas molecules to large ones increased to remarkably high level. For example, the H2 permeability decreased to 1250 Barrer, while the H2/CH4 selectivity increased from ∼100 to 350 after ageing. These two-years-aged nanocomposites are still relatively more permeable and less selective compared to aged TOX-PIM-1 films. Furthermore, these aged polymer films maintain high permeability levels that are still two orders of magnitude higher than conventional polymer materials used for gas separation membranes, as presented in Fig. 5d. These data confirm that the thermal-oxidative crosslinking is an effective approach to enhance the rigidity and restrict the pore collapse in microporous polymeric networks.
Although this study is focused on the crosslinked microporous PIM polymer network incorporated with nanofillers, we also investigated thermo-oxidation at intermediate temperature (i.e. 300 °C), which induced oxidative degradation instead of crosslinking. Oxidative degradation also results in changes in physical and chemical properties, e.g. densification of polymer/filler interface (Fig. 1i), loss of ZIF-8 crystallinity (Fig. S15 and S16, ESI†), lower molecular weight (Fig. S18, ESI†), and diffusion-restricted gas sorption (Fig. S19, ESI†). These changes are related to the heterogeneous structure of nanocomposites where thermal oxidative degradation is prone to happen owing to disrupted polymer thin film and enhanced O2 diffusion. The restricted diffusion as observed in gas sorption may be related to local denser molecular packing, and intermolecular interactions in the oxidized polymer matrix, e.g. hydrogen bonding between oxidized polymer chains which would enhance the local rigidity of polymer chains.55,64 In addition, for those degraded PIM-1/ZIF-8 composites, the polymer–nanofiller interfaces are more complex, e.g. oxidation of polymer, degradation of ZIF-8, and interactions between them, for example, hydrogen bonding may form between oxidized groups in polymer segments (C O) with imidazole (N–H) groups at the boundary of ZIF-8. These complex interactions induced by thermal oxidation would lead to significant changes in the pore structure and gas transport properties. This also indicates that it is possible to combine MOF nanofillers with polymers with well defined surface chemistry and interactions at the interfaces.
A further discussion is on the difference between porous MOFs fillers and inorganic nanoparticles. Owing to the high internal porosity of MOFs and low density, a very small amount of MOF filler (less than 20 wt%) could give sufficient high interfacial areas that drastically change the gas transport properties. Compared to inorganic nanoparticles, MOF fillers are relatively vulnerable to degradation owing to the organic nature, yet their porous structure and functionalities along with tuneable interfacial interactions with polymers would still make them favourable candidates for composites.
One of the important features of polymer nanocomposites is the large surface area of interfaces between nanofillers and polymers. For unmodified PIM-1 and the nanofillers used in this study, their interactions lacks strong forces such as hydrogen bonding or covalent interactions, therefore the interface is mainly dominated by physical dispersion and altered chain mobility and packing. Increasing the volume fraction of nanofillers could significantly increase the interfacial area which controls the properties of nanocomposites including gas diffusion. Still the synergistic combination of covalent crosslinking of polymer phases with enhanced molecular sieving selectivity and enhanced diffusivity at interfaces introduced by dispersed nanoparticles lead to the overall enhanced permeability and sufficiently high selectivity that do not exist for covalently crosslinked polymer alone.
In this study we probed the structure of thick polymer nanocomposite films by gas adsorption and diffusion, whereas thin films would be used practically for membrane separation applications. The gas transport properties in thin film membranes would be different, particularly the ageing behaviour. Previously we have successfully demonstrated that crosslinking is also effective for PIM-1 thin films (∼100 nm) coated on inorganic substrates, research on thermally crosslinked thin film membranes is in progress and will be reported in future.
In a broad context, our work improves the fundamental understanding on molecular transport in the new class of PIMs polymers and nanocomposites. Since PIMs and other microporous polymers have been demonstrated as of great potential for applications, such as gas storage, adsorbents, sensors, catalyst supports, separators for batteries, membranes for gas separation and organic solvent nanofiltration, and hydrocarbons separation for oil refinery processes, we expect that our approach of controlled thermal processing and nanocomposites could be extended to fabrication and processing of the rapid-growing large family of microporous polymers including PIMs and functional nanocomposites for a wide range of applications.
In summary, we demonstrate an approach to the design of polymer molecular sieves fabricated from thermo-oxidatively crosslinked PIM-1 polymer networks incorporated with nonporous inorganic nanoparticles or microporous MOF nanocrystals. Thermal oxidative crosslinking of the PIM-1 polymer phase substantially enhances the gas selectivity of nanocomposites while the gas permeability remains at a remarkably high level. Incorporations of nanoscale fillers, either porous or nonporous, in the crosslinked PIM-1 polymer networks introduce extra channels and heterogeneous interfaces for enhanced diffusion of gas molecules while the gas solubility remains constant, consequently enhancing the overall gas permeability while maintaining sufficiently high selectivity. These highly permeable and selective nanocomposites are promising for a wide range of industrially important molecular separations in energy and environmental processes, such as removal of CO2 from natural gas, shale gas purification, biogas purification, air separation, hydrogen separation and recovery, and other molecular-level separations. Our report, with two-year ageing studies, also indicates the importance of enhancing permeability in this high-free-volume glassy polymer through nanofiller additions. We expect that our approach and findings would have broad scientific implications on understanding the structure and molecular transport phenomena in novel microporous polymeric molecular sieves and polymer nanocomposites, for a broad range of applications beyond gas separations.
This work was financially supported by the Engineering and Physical Sciences Research Council (EPSRC, UK), European Research Council (ERC) and an NPRP grant from the QNRF (Qatar). Q. S. acknowledges the financial support of China Scholarship Council and an Imperial College Junior Research Fellowship.
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SUSAN ILLSTON, United States District Judge.
On June 8, 2001, this Court heard argument on defendants' motion to dismiss plaintiffs complaint or, alternatively, motion for transfer of venue. Having considered the arguments of the parties and the papers submitted, the Court hereby DENIES defendants' motion to dismiss the complaint and GRANTS defendants' motion for transfer of venue for the reasons set forth below.
Plaintiff Starlight Company, Inc., successor in interest to Johnny Gu dba Starlight Company, is engaged in the business of recycling plastic bags in Oakland, California. Complaint at ¶ 1, 6. Defendant Arlington Plastics Machinery Inc., ("Arlington") is an Illinois corporation with its primary place of business in Elk Grove Village, Illinois. Arlington employs defendant Louis Baccarini ("Baccarini") as a sales executive. Complaint at ¶ 2-3.
Plaintiffs business uses a machine known as a "pelletizing line" to transfonn plastic bags into small plastic pellets that can then be used to make new plastic bags. Complaint at ¶ 6. Arlington sells new and used industrial machinery, including pelletizing lines. Id. at ¶ 7. In or around August 2000, Arlington, through its authorized agent Baccarini, entered into negotiations with Gu for the sale ofa used pelletizing line. 14. at ¶¶ 8-9.
"We offer to purchaser the following articles for the purchase price specified above and subject to the terms and conditions set forth on the reverse side of this Agreement and Offer. This Agreement shall become effective upon, but not until, execution by ARLINGTON PLASTICS MACHINERY, INC. AND PURCHASER. Terms and conditions on reverse side are part of this agreement as effectively as though they precede the signature of purchaser." Id.
"MISCELLANEOUS. This contract and all causes of action relating to the sale and the terms hereof, or arising by virtue hereof shall be construed solely according to the laws of the State of Illinois. The Buyer and Seller agree that the courts shall be the sole, exclusive and only forum in which disputes arising hereunder or as a consequence hereof shall be adjudicated. The Buyer and Seller also agree that venue for all claims arising hereunder or by virtue hereof shall, at all times, be solely and exclusively in Cook County, Illinois. Buyer and Seller shall not be amenable to suit or other action in any forum or jurisdiction other than in the courts of Illinois regardless of the circumstances or facts of any claim hereunder or as a result hereof" Id.
In the months following the Contract date, disputes arose between the parties regarding the performance of various provisions of their agreement, including the machine's delivery date, inspection of the machine, and parts included in the machine. Complaint at ¶¶ 14-22. The parties attempted to resolve the matter informally via telephone conversations. Id. at ¶¶ 21-22, Stanwyck Decl. ¶ 3, Clarke Decl. ¶¶ 3-4. Plaintiff alleges that during one conversation between Plaintiffs attorney, Peter Stanwyck, and Arlington President Jack Clarke, Clarke told Stanwyck "if you want the expense of coming to Chicago and proving your case here, then go ahead." Stanwyck Decl. ¶ 3. Clarke explains that he was merely expressing "confusion as to why Plaintiff would be pursuing litigation in Chicago when we had already reached an understanding to resolve this dispute." Clarke Decl., ¶ 4.
On March 19, 2001, plaintiff filed suit alleging breach of contract, fraud, negligent misrepresentation, recission and declaratory relief. Defendants now move to dismiss the complaint for improper venue pursuant to Federal Rule of Civil Procedure 12(b)(3), based on the parties' contractual forum-selection clause which requires adjudication of all disputes arising from the Contract in Illinois. In the alternative, defendants move for transfer to the Northern District of Illinois for improper venue pursuant to 28 U.S.C. § 1406 (a).
Federal law governs the enforceability of forum-selection clauses in diversity actions. Manetti| Farrow, Inc. v. Gucci America. Inc., 858 F.2d 509, 513 (9th Cir. 1988). Furthermore, motions to dismiss based on a forum-selection clause are treated as a Rule 12(b)(3) motion to dismiss for improper venue. Arguetta v. Banco Mexicano, S.A., 87 F.3d 320, 324 (9th Cir. 1996). Therefore, the pleadings are not accepted as true, as would be required under a Rule 12(b)(6) analysis. Id. A forum-selection clause is prima facie valid and should not be set aside unless the party challenging enforcement can show it is "`unreasonable' under the circumstances." M/S Bremen v. Zapata Off-Shore Co., 407 U.S. 1, 10, 92 S.Ct. 1907, 1913 (1972). The Supreme Court re-interpreted the Bremen standard of "unreasonable under the circumstances" as a standard of "fundamental fairness." Carnival Cruise Lines, Inc. v. Shute, 499 U.S. 585, 595, 111 S.Ct. 1522, 1528 (1991). Such unfairness has been given a narrow interpretation and a party seeking to avoid a forum-selection clause must satisfy a "heavy burden of proof." Id. Unfairness can be proven only in limited circumstances, such as showing bad faith in the choice of venue or that the party signing the contract had inadequate notice of the provision. Id.
If a forum-selection clause is found valid and enforceable, courts have discretion to dismiss an action commenced in a forum other than that specified in the forum-selection clause or transfer the action to the district court located in the specified forum. 28 U.S.C. § 1406 (a). Courts should consider the basic equities of the case in deciding whether to transfer or dismiss, including any statute of limitations bar and the harshness of dismissal in light of such a bar, and the relative injustice imposed on the parties. King v. Russell, 963 F.2d 1301, 1304-05 (9th Cir. 1992).
Defendants argue that the forum-selection clause is valid and enforceable and therefore the Complaint should be dismissed. Plaintiff argues that the forum-selection clause should be invalidated due to inadequate notice and defendants' bad faith. Bad faith can be demonstrated by showing that a choice of forum is designed to discourage plaintiffs from pursuing legitimate claims or by showing that defendant obtained plaintiffs accession to the forum clause by fraud or overreaching. Carnival. 499 U.S. at 595, 111 S.Ct. at 1528.
Defendants operate their business out of Elk Grove, Illinois and selected Illinois as the forum state in order to "consolidate litigation involving far-flung operations." Reply at 7:24-26. As in Carnival, the clause here operates to provide Arlington with a forum in its principal place of business, which suggests a motive other than bad faith. Carnival, 499 U.S. at 595, 111 S.Ct. at 1528. While plaintiff offers some evidence (i.e., Clarke's statement made during telephone conversation with Stanwyck) that defendants believed their choice of forum would discourage the pursuit of plaintiff's lawsuit, this is not sufficient to overcome the presumption of validity courts traditionally give to forumC selection clauses when there is a reasonable basis, such as principal place of business, for the forum selected. See Carnival, 499 U.S. at 595, 111 S.Ct. at 1528; Effron v. Sun Line Cruises, 67 F.3d 7, 10 (2nd Cir. 1995).
Plaintiffs claims that the forum-selection clause was obtained through fraud or overreaching are unconvincing. A forum-selection clause is unenforceable for fraud only "if the inclusion of that clause in the contract was the product of fraud or coercion." Scherk v. Alberto-Culver Co., 417 U.S. 506, 519 n. 14, 94 S.Ct. 2449, 2457 n. 14 (1974). The party seeking to invalidate a forum-selection clause must show that the clause itself was fraudulently included in the agreement, not claim the entire agreement was a product of fraud. Batchelder v. Kawamato, 147 F.3d 915, 919 (9th Cir. 1998). Plaintiff claims that "including the forum-selection clause under the heading "Miscellaneous', in and of itself could be considered to be a fraud." Opp. at 7:1-2. However, this does not satisfy the high bar for proving fraud in a contract which requires a showing of intent to mislead. Restatement (Second) of Contracts § 162 (1978). Particularly given that the Contract contained a warning directly above the signature line to read the terms and conditions on the reverse side, it does not appear that defendants' use of the heading "Miscellaneous" was an attempt to intentionally mislead plaintiff.
Plaintiff also argues that it was not given reasonable notice of the forum-selection clause. In Deiro v. American Airlines, 816 F.2d 1360 (9th Cir. 1987), the Ninth Circuit employed a two-pronged analysis in determining whether airline passengers are bound by "boilerplate" conditions located on passenger tickets. "The "proper test of reasonable notice is an analysis of the overall circumstances on a case-by-case basis, with an examination not only of the ticket itself, but also of any extrinsic factors indicating the passenger's ability to become meaningfully informed of the contractual terms at stake."' Id. at 1364 (quoting Shankles v. Costa Armatori, S.P.A., 722 F.2d 861, 866 (1st Cir. 1983)). In this case, both the physical attributes of the contract and the extrinsic factors pertaining to plaintiff's ability to inform itself of the contractual terms indicate that plaintiff had adequate notice of the forum-selection provision. A statement directly above the signature line on the face of the Contract clearly explains that the terms on the backside are binding. Although the forum-selection provision was included under the relatively vague heading of "Miscellaneous," this is not sufficient to demonstrate that plaintiff was unaware of the clause's existence. The "Terms and Conditions" are only one-page in length and this was an arms-length transaction between two commercial parties. Parties dealing at arms length have no duty to explain to each other the terms written in a contract. Cohen v. Wedbush, Noble4 Cookc. LneZ, 841 F.2d 282, 287 (9th Cir. 1988). It is not unreasonable to expect that when negotiating for the purchase of $130,000 worth of machinery, a party should familiarize itself with the relatively short terms of the agreement despite the color of the print, the font size, or the vague heading.
The adhesive nature of the terms and conditions does not render a forum-selection provision invalid. The Carnival court upheld a forum-selection provision, even though the non-negotiated contract was purely routime and doubtless nearly identical to every other commercial passage contract issued by petitioner and most other cruise lines." Carnival, 499 U.S. at 593, 111 S.Ct. at 1527. Sec also Fireman's Fund Insurance Company v. M.V. DSR Atlantic, 131 F.3d 1336, 1338 (9th Cir. 1997) (finding that if a forum-selection clause is unambiguous it is irrelevant if the contract is one of adhesion), Silva Encyclopedia Britannica, 239 F.3d 385, 386 (1st Cir. 2001) (upholding "boilerplate" forum-selection clause in an encyclopedia sales contract that appeared in small print on the back of the contract), Lambert v. Kysar, 963 F.2d 1110, 1113 (1st Cir. 1993) (upholding "boilerplate" forum-selection clause appearing on backside of form contract).
Finally, plaintiff argues that due to defendants' fraudulent conduct the entire Contract should be rescinded and the forum-selection clause should be found unenforceable. Plaintiff alleges that defendants intentionally made false promises during the Contract's formation and fraudulently induced plaintiff's assent. However, plaintiff presents no cases where a court has rescinded an entire contract for the purpose of invalidating a forum-selection clause. Granting a rescission of the Contract to invalidate the forum-selection clause would essentially give plaintiff the relief it seeks without requiring it to prove its case. As noted above, courts require that a party must plead specifically that a forum| selection clause was fraudulently ogtained to invalidate the provision. This requirement ensures that the effect of a court's ruling on a forum-selection clause is limited to the clause itself and will not deprive parties of a full opportunity to litigate other issues. When a contract includes a valid forum| selection clause, a court in the selected forum must determine whether rescission of the entire contract is ultimately appropriate.
The Court concludes the forum-selection clause is valid and enforceable. Any causes of action arising out of or implicating the contract containing the forum-selection clause are subject to that clause. Mimetti-Farrow, Inc., Gucci America, Inc., 858 F.2d 509, 514 (9th Cir. 1988). All causes of action alleged in the Complaint arise out of the September 2000 contract containing the forum-selection clause, therefore all causes are subject to it.
During oral argument, plaintiffs counsel indicated that transfer would be preferred over dismissal in the event that the Court upheld the forum-selection clause. The Court accepts plaintiff's request and finds that transfer to the Northern District of Illinois is appropriate in this case.
For the foregoing reasons, the Court DENIES defendants' motion to dismiss for improper venue and GRANTS defendants' motion for transfer of venue. [Docket No. 9] This action is TRANSFERRED to the Northern District of Illinois pursuant to the forum-selection clause in the Contract at issue.


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