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3.5 3.0 2.5 2.0 1.5 1.0 0.5 550 nm 145 nm 50 nm 25 nm 18 nm 1 10 100 1000 Aging time (hr) 10000 Figure 10. Effect of membrane thickness and time on gas permeability properties of Matrimid®, a glassy polymer. For reasons that are not well understood, the physical aging process, and therefore the permeability, becomes dependent on membrane thickness once the thickness is less than about 1 micrometer. As the figure indicates, permeability differs by more than a factor of 6 when a relatively thick (550 nm) membrane at just a few hours past the start of the aging experiment is compared with an ultrathin (18 nm) membrane aged for about 1000 hours. These measurements were conducted at 35°C and at an oxygen pressure difference of 2 atm across the membrane.16 (which are based on converting the gas to oxygen anions), as the membrane becomes thinner to achieve high conductance, the separation efficiency drops as the reaction between the membrane material and the gas becomes limiting. Current membranes are typically gradient structures, comprising either multiple layers of different materials (e.g., multilayer composite membranes), variations in membrane material density through the structure of the membrane (e.g., asymmetric membranes), or both. The development of these structures has evolved in a largely Edisonian fashion. To achieve high performance and maintain integrity in operation—where membranes may be exposed (and respond) to gradients in pressure, temperature, and other parameters—the interfaces between different materials in a membrane or between regions of different density are critically important. As new membranes are developed, with ever thinner selective layers, the effect of the interface on the transport properties and robustness will become even more important. However, there is a large gap in the fundamental understanding of rational manipulation of interface properties to achieve desired structures (e.g., tailored 3D architectures) while maintaining the required robustness and outstanding transport properties. Currently, all synthetic polymer membranes are processed from solution in organic solvents, using processes such as those presented in Figure 11. This is the only known commercially feasible, large-scale method of making ultrathin gas separation membranes. However, because the membranes are soluble in organic solvents, the membranes are inherently sensitive to chemical attack by organic contaminants that are present in many emission streams. One potential route to resolving this conundrum involves solution processing of the materials as soluble precursors, followed by conversion into highly stable, robust, high- performance membranes using chemical processes initiated by heat, light, or microwave radiation, for example.17 The use of organic solvents in membrane processing has deleterious effects, however, because it contributes significantly to the cost of membrane manufacture and ultimately requires disposal of the solvents. The development of solventless strategies to prepare the multilayer structures required for high-performance gas separation membranes 32 O2 permeability (Barrer)PDF Image | 2020 Carbon Capture
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