Search Results (5)

In this work, thin film composite (TFC) membranes were fabricated with the selective layer based on a blend of polyimide Matrimid^®5218 and polymer of intrinsic microporosity (PIM) composed of Tröger’s base, TB, and dimethylethanoanthracene units, PIM-EA(Me₂)-TB. The TFCs were prepared with different ratios of the two polymers and the effect of the PIM content in the blend of the gas transport properties was studied for pure He, H₂, O₂, N₂, CH₄, and CO₂ using the well-known time lag method. The prepared TFC membranes were further characterized by IR spectroscopy and scanning electron microscopy (SEM). The role of the support properties for the TFC membrane preparation was analysed for four different commercial porous supports (Nanostone Water PV 350, Vladipor Fluoroplast 50, Synder PAN 30 kDa, and Sulzer PAN UF). The Sulzer PAN UF support with a relatively small pore size favoured the formation of a defect-free dense layer. All the TFC membranes supported on Sulzer PAN UF presented a synergistic enhancement in CO₂ permeance, and CO₂/CH₄ and CO₂/N₂ ideal selectivity. The permeance increased about two orders of magnitude with respect to neat Matrimid, up to ca. 100 GPU, the ideal CO₂/CH₄ selectivity increased from approximately 10 to 14, and the CO₂/N₂ selectivity from approximately 20 to 26 compared to the thick dense reference membrane of PIM-EA(Me₂)-TB. The TFC membranes exhibited lower CO₂ permeances than expected on the basis of their thickness—most likely due to enhanced aging of thin films and to the low surface porosity of the support membrane, but a higher selectivity for the gas pairs CO₂/N₂, CO₂/CH₄, O₂/N₂, and H₂/N₂. Full article

The microscopic diffusion and the low frequency density of states (VDOS) of PIM-EA-TB(CH₃) are investigated by inelastic and quasi-elastic neutron scattering where also the demethylated counterpart of PIM-EA-TB(H₂) is considered. These intrinsic microporous polymers are characterized by large BET surface area values of several hundred m²/g and pore sizes between 0.5 and 2 nm. Detailed comparison is made to the archetype of polymers of intrinsic microporosity, PIM-1, and polynorbornenes also bearing a microporosity. Due to the wavelength of neutrons, the diffusion and vibrations can be addressed on microscopic length and time scales. From the inelastic neutron scattering experiments the low frequency density of states (VDOS) is estimated which shows excess contributions to the Debye-type VDOS known as Boson peak. It was found that the maximum frequency of the Boson peak decreases with increasing microporosity characterized by the BET surface area. However, besides the BET surface area, additional factors such as the backbone stiffness govern the maximum frequency of the Boson peak. Further the mean squared displacement related to microscopic motions was estimated from elastic fixed window scans. At temperatures above 175 K, the mean squared displacement PIM-EA-TB(CH₃) is higher than that for the demethylated counterpart PIM-EA-TB(H₂). The additional contribution found for PIM-EA-TB(CH₃) is ascribed to the rotation of the methyl group in this polymer because the only difference between the two structures is that PIM-EA-TB(CH₃) has methyl groups where PIM-EA-TB(H₂) has none. A detailed comparison of the molecular dynamics is also made to that of PIM-1 and the microporous polynorbornene PTCNSi1. The manuscript focuses on the importance of vibrations and the localized molecular mobility characterized by the microscopic diffusion on the gas transport in polymeric separation membranes. In the frame of the random gate model localized fluctuations can open or close bottlenecks between pores to enable the diffusion of gas molecules. Full article

A detailed comparison of the gas permeability of four Polymers of Intrinsic Microporosity containing Tröger’s base (TB-PIMs) is reported. In particular, we present the results of a systematic study of the differences between four related polymers, highlighting the importance of the role of methyl groups positioned at the bridgehead of ethanoanthracene (EA) and triptycene (Trip) components. The PIMs show BET surface areas between 845–1028 m² g⁻¹ and complete solubility in chloroform, which allowed for the casting of robust films that provided excellent permselectivities for O₂/N₂, CO₂/N₂, CO₂/CH₄ and H₂/CH₄ gas pairs so that some data surpass the 2008 Robeson upper bounds. Their interesting gas transport properties were mostly ascribed to a combination of high permeability and very strong size-selectivity of the polymers. Time lag measurements and determination of the gas diffusion coefficient of all polymers revealed that physical ageing strongly increased the size-selectivity, making them suitable for the preparation of thin film composite membranes. Full article

The effect on the gas transport properties of Matrimid^®5218 of blending with the polymer of intrinsic microporosity PIM-EA(H₂)-TB was studied by pure and mixed gas permeation measurements. Membranes of the two neat polymers and their 50/50 wt % blend were prepared by solution casting from a dilute solution in dichloromethane. The pure gas permeability and diffusion coefficients of H₂, He, O₂, N₂, CO₂ and CH₄ were determined by the time lag method in a traditional fixed volume gas permeation setup. Mixed gas permeability measurements with a 35/65 vol % CO₂/CH₄ mixture and a 15/85 vol % CO₂/N₂ mixture were performed on a novel variable volume setup with on-line mass spectrometric analysis of the permeate composition, with the unique feature that it is also able to determine the mixed gas diffusion coefficients. It was found that the permeability of Matrimid increased approximately 20-fold with the addition of 50 wt % PIM-EA(H₂)-TB. Mixed gas permeation measurements showed a slightly stronger pressure dependence for selectivity of separation of the CO₂/CH₄ mixture as compared to the CO₂/N₂ mixture, particularly for both the blended membrane and the pure PIM. The mixed gas selectivity was slightly higher than for pure gases, and although N₂ and CH₄ diffusion coefficients strongly increase in the presence of CO₂, their solubility is dramatically reduced as a result of competitive sorption. A full analysis is provided of the difference between the pure and mixed gas transport parameters of PIM-EA(H₂)-TB, Matrimid^®5218 and their 50:50 wt % blend, including unique mixed gas diffusion coefficients. Full article

Gas transport properties of PIM-EA(H₂)-TB, a microporous Tröger’s base polymer, were systematically studied over a range of pressure and temperature. Permeability coefficients of pure CO₂, N₂, CH₄ and H₂ were determined for upstream pressures up to 20 bar and temperatures up to 200 °C. PIM-EA(H₂)-TB exhibited high permeability coefficients in absence of plasticization phenomena. The permeability coefficient of N₂, CH₄ and H₂ increased with increasing temperature while CO₂ permeability decreased with increasing temperature as expected for a glassy polymer. The diffusion and solubility coefficients were also analysed individually and compared with other polymers of intrinsic microporosity. From these results, the activation energies of permeation, diffusion and sorption enthalpies were calculated using an Arrhenius equation. Full article