A new series of thin film composite membranes with high CO₂ permeance (up to 8000 GPU) and CO₂/N₂ selectivity (up to 55.7) was designed and fabricated via coating PIM-1 solution in a mixture of chloroform and trichloroethylene on top of a cross-linked PTMSP gutter layer.

The first commercial hollow fiber and flat sheet gas separation membranes were produced in the late 1970s from the glassy polymers polysulfone and poly(vinyltrimethyl silane), respectively, and the first industrial application was hydrogen recovery from ammonia purge gas in the ammonia synthesis loop. Membranes based on glassy polymers (polysulfone, cellulose acetate, polyimides, substituted polycarbonate, and poly(phenylene oxide)) are currently used in various industrial processes, such as hydrogen purification, nitrogen production, and natural gas treatment. However, the glassy polymers are in a non-equilibrium state; therefore, these polymers undergo a process of physical aging, which is accompanied by the spontaneous reduction of free volume and gas permeability over time. The high free volume glassy polymers, such as poly(1-trimethylgermyl-1-propyne), polymers of intrinsic microporosity PIMs, and fluoropolymers Teflon^® AF and Hyflon^® AD, undergo significant physical aging. Herein, we outline the latest progress in the field of increasing durability and mitigating the physical aging of glassy polymer membrane materials and thin-film composite membranes for gas separation. Special attention is paid to such approaches as the addition of porous nanoparticles (via mixed matrix membranes), polymer crosslinking, and a combination of crosslinking and addition of nanoparticles.

The weak point of ionic liquids is their high viscosity, limiting the maximum polymer concentration in the forming solutions. A low-viscous co-solvent can reduce viscosity, but cellulose has none. This study demonstrates that dimethyl sulfoxide (DMSO), being non-solvent for cellulose, can act as a nominal co-solvent to improve its processing into a nanofiltration membrane by phase inversion. A study of the rheology of cellulose solutions in diluted ionic liquids ([EMIM]Ac, [EMIM]Cl, and [BMIM]Ac) containing up to 75% DMSO showed the possibility of decreasing the viscosity by up to 50 times while keeping the same cellulose concentration. Surprisingly, typical cellulose non-solvents (water, methanol, ethanol, and isopropanol) behave similarly, reducing the viscosity at low doses but causing structuring of the cellulose solution and its phase separation at high concentrations. According to laser interferometry, the nature of these non-solvents affects the mass transfer direction relative to the forming membrane and the substance interdiffusion rate, which increases by four-fold when passing from isopropanol to methanol or water. Examination of the nanofiltration characteristics of the obtained membranes showed that the dilution of ionic liquid enhances the rejection without changing the permeability, while the transition to alcohols increases the permeability while maintaining the rejection.

For the development of high efficiency porous supports for composite membrane preparation, polysulfone (PSf) hollow fiber membranes (outer diameter 1.57 mm, inner diameter 1.12 mm) were modified by air plasma using the low temperature plasma treatment pilot plant which is easily scalable to industrial level and the Piranha etch (H₂O₂ + H₂SO₄). Chemical and plasma modification affected only surface layers and did not cause PSf chemical structure change. The modifications led to surface roughness decrease, which is of great importance for further thin film composite (TFC) membranes fabrication by dense selective layer coating, and also reduced water and ethylene glycol contact angle values for modified hollow fibers surface. Furthermore, the membranes surface energy increased two-fold. The Piranha mixture chemical modification did not change the membranes average pore size and gas permeance values, while air plasma treatment increased pore size 1.5-fold and also 2 order enhanced membranes surface porosity. Since membranes surface porosity increased due to air plasma treatment the modified membranes were used as efficient supports for preparation of high permeance TFC membranes by using poly[1-(trimethylsilyl)-1-propyne] as an example for selective layer fabrication.

This work was focused on the mitigation of physical aging in thin-film composite (TFC) membranes (selective layer ~1 μm) based on polymer intrinsic microporosity (PTMSP) by the introduction of both soft, branched polyethyleneimine (PEI), and rigid, porous aromatic framework PAF-11, polymer additives. Self-standing mixed-matrix membranes of thicknesses in the range of 20–30 μm were also prepared with the same polymer and fillers. Based on 450 days of monitoring, it was observed that the neat PTMSP composite membrane underwent a severe decline of its gas transport properties, and the resultant CO₂ permeance was 14% (5.2 m³ (STP)/(m²·h·bar)) from the initial value measured for the freshly cast sample (75 m³ (STP)/(m²·h·bar)). The introduction of branched polyethyleneimine followed by its cross-linking allowed to us to improve the TFC performance maintaining CO₂ permeance at the level of 30% comparing with day zero. However, the best results were achieved by the combination of porous, rigid and soft, branched polymeric additives that enabled us to preserve the transport characteristics of TFC membrane as 43% (47 m³ (STP)/(m²·h·bar) after 450 days) from its initial values (110 m³ (STP)/(m²·h·bar)). Experimental data were fitted using the Kohlrausch–Williams–Watts function, and the limiting (equilibrium) values of the CO₂ and N₂ permeances of the TFC membranes were estimated. The limit value of CO₂ permeance for neat PTMSP TFC membrane was found to be 5.2 m³ (STP)/(m²·h·bar), while the value of 34 m³(STP)/(m²·h·bar) or 12,600 GPU was achieved for TFC membrane containing 4 wt% cross-linked PEI, and 30 wt% PAF-11. Based on the N₂ adsorption isotherms data, it was calculated that the reduction of the free volume was 1.5–3 times higher in neat PTMSP compared to the modified one. Bearing in mind the pronounced mitigation of physical aging by the introduction of both types of fillers, the developed high-performance membranes have great potential as support for the coating of an ultrathin, selective layer for gas separation.

The mitigation of the physical aging of thin-film composite (TFC) poly[1-trimethylsilyl-1-propyne] (PTMSP) membranes was studied via the simultaneous application of a polymer-selective layer crosslinking and mixed-matrix membrane approach. For the first time, a recently developed highly porous activated carbon material (infrared (IR) pyrolyzed poly[acrylonitrile] (PAN) or IR-PAN-a) was investigated as an additive to a PTMSP-selective layer for the reduction of aging in TFC membranes. The total electric energy spent on the IR irradiation treatment of IR-PAN-a particles was twice lower than conventional heating. The flat-sheet porous microfiltration membrane MFFK-1 was used as a support, and the crosslinked PTMSP/PEI loaded with a porous filler was applied as a selective layer (0.8–1.8 µm thick) to the TFC membranes. The initial IR-PAN-a sample was additionally milled to obtain a milled IR-PAN-aM sample with a monomodal particle size distribution of 500–800 nm. It was shown that IR-PAN-a, as a filler material with a high surface area and pore volume (2450 m²/g and 1.06 cm³/g, respectively) and a well-developed sponge-like structure, leads to the increase of the N₂, O₂, and CO₂ permeance of PTMSP-based hybrid membrane material and the decrease of the aging of PTMSP. The simultaneous effect of crosslinking and the addition of a highly porous filler essentially improved the aging behavior of PTMSP-based TFC membranes. The monomodal and narrow particle size distribution of highly porous activated IR-pyrolyzed PAN is a key factor for the production of TFC membranes with reduced aging. The highest stability was achieved by the addition of a milled IR-PAN-aM sample (10 wt%). TFC membrane permeance was 6300 GPU (30% of initial permeance) after 11,000 h of aging at ambient laboratory conditions.