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The disclosure concerns a device suitable for removing air from water under both zero and one 'g' gravity conditions. The device is comprised of a pair of spaced membranes on being hydrophobic and the other being hydrophilic. The air-water mixture is introduced into the space therebetween, and the selective action of the membranes yields removal of the air from the water.
Efficient separation of lithium (Li + ) and magnesium (Mg 2+ ) is critical for enhancing sustainable lithium extraction from natural brines, which is vital for battery production and renewable energy technologies. Here we present a method for highly selective Li + /Mg 2+ separation driven by concentration gradients across negatively charged membranes with high charge densities. In contrast to typical electric field-driven transport in negatively charged membranes, where divalent cations generally permeate faster than monovalent cations, Li + ions in our system permeate the membrane at substantially higher rates than Mg 2+ ions. This unexpected selectivity stems from the selective ion partitioning properties of the membrane and the uphill transport of Mg 2+ ions against their external concentration gradient. We demonstrate the efficacy of this separation approach through bench-scale dialysis experiments using a model Atacama brine solution, achieving efficient separation of monovalent and divalent cations. As a result, the high separation efficiency observed in this study suggests a promising approach for monovalent/divalent ion separations, offering higher selectivity compared to current technologies.
Membranes, methods of making the membranes, and methods of using the membranes are described herein. The membranes can comprise a support layer, and a selective polymer layer disposed on the support layer. The selective polymer layer can comprise a selective polymer matrix and carbon nanotubes dispersed within the selective polymer matrix. The carbon nanotubes can comprise multi-walled carbon nanotubes wrapped in a hydrophilic polymer, such as polyvinylpyrrolidone or a copolymer thereof, such as poly(1-vinylpyrrolidone-co-vinyl acetate). The membranes can exhibit selective permeability to gases. As such, the membranes can be for the selective removal of carbon dioxide and/or hydrogen sulfide from hydrogen and/or nitrogen.
Membranes, methods of making the membranes, and methods of using the membranes are described herein. The membranes can comprise a gas permeable support and a continuous phase comprising a selective inorganic material disposed within the gas permeable support. In some embodiments, the membranes can exhibit a CO2:N2 selectivity of at least 10 at 24° C. The membranes can be bendable, such that when the membranes are wrapped around a 1.5-inch diameter cylinder and returned to a planar conformation, the CO2:N2 selectivity of the membranes is at least 25% of the CO2:N2 selectivity of the membranes prior to having been wrapped around the cylinder.
Membranes having a permselective active layer of a copolymerized perfluorinated monomer and an non-fluorinated alkylvinylester monomer demonstrate superior selective permeability performance for separating gas mixtures compared to membranes of exclusively perfluorinated polymers. Preferred active layer compositions are copolymers of perfluoro-2,2-dimethyl-1,3 dioxole (PDD) copolymerized with an alkylvinyl ester such as vinyl acetate, and vinyl pivalate, and with alkylvinyl esters that are substantially hydrolyzed to provide copolymerized vinyl alcohol functionality. The membranes can have a thin, high diffusion rate, “gutter layer” of a fluorinated polymer highly permeable to nitrogen positioned between the active layer and a porous support layer. A novel copolymer effective in selectively permeable membranes is a copolymer of PDD and an alkylvinyl ester compound having the formula H2C═CHOC(O)R1 in which R1 is a linear or branched alkyl group of from 2 to 5 carbon atoms.
Stimuli-responsive materials offer new opportunities to resolve long-standing material challenges and are rapidly gaining pivotal roles in diverse applications. For example, smart protective garments that rapidly transport water vapor and autonomously block chemical threats are expected to enable an effective new paradigm of adaptive personal protection. However, the incorporation of these seemingly incompatible properties into a single responsive system remains elusive. Herein, a bistable membrane that can rapidly, selectively, and reversibly transition from a highly breathable state in a safe environment to a chemically protective state when exposed to organophosphate threats such as sarin is demonstrated. Dynamic response to chemical stimuli is achieved through the physical collapse of an ultrathin copolymer layer on the membrane surface, which efficiently gates transport through membrane pores composed of single-walled carbon nanotubes (SWNTs). The adoption of nanometer-wide SWNTs for ultrafast moisture conduction enables a simultaneous boost in size-sieving selectivity and water-vapor permeability by decreasing nanotube diameter, thereby overcoming the breathability/protection trade-off that limits conventional membrane materials. Adaptive multifunctional membranes based on this platform greatly extend the active use of a protective garment and present exciting opportunities in many other areas including separation processes, sensing, and smart delivery.
Robust and cost-effective membrane-based separations are essential to solving many global crises, such as the lack of clean water. Even though the current polymer-based membranes are widely used for separations, their performance and precision can be enhanced by using a biomimetic membrane architecture that consists of highly permeable and selective channels embedded in a universal membrane matrix. Researchers have shown that artificial water and ion channels, such as carbon nanotube porins (CNTPs), embedded in lipid membranes can deliver strong separation performance. However, their applications are limited by the relative fragility and low stability of the lipid matrix. In this work, we demonstrate that CNTPs can co-assemble into two-dimension (2D) peptoid membrane nanosheets, opening up a way to produce highly programmable synthetic membranes with superior crystallinity and robustness. A combination of molecular dynamics (MD) simulations, Raman spectroscopy, X-ray diffraction (XRD), and atomic force microscopy (AFM) measurements to verify the co-assembly of CNTP and peptoids are used and show that it does not disrupt peptoid monomer packing within the membrane. In conclusion, these results provide a new option for designing affordable artificial membranes and highly robust nanoporous solids.
An effective cross-linking technique allows a viscous, highly gas permeable hydrophilic polyphosphazene to be cast as solid membrane films. By judicious blending with other polyphosphazenes to improve mechanical properties, a membrane exhibiting the highest CO2 permeability (610 barrer) combined with good CO2/N2 selectivity (35) among polyphosphazenes is described here. The material demonstrates performance stability after 500 hours of exposure to a coal-fired power plant flue gas, making it attractive for use in carbon capture applications. Its CO2/N2 selectivity under conditions up to full humidity is also stable, and although the gas permeability does decline, the performance is fully recovered upon drying. The high molecular weight of these heteropolymers also allows them to be cast as a thin selective layer on an asymmetric porous membrane, yielding CO2 permeance of 1200 GPU, CO2/N2 pure gas selectivity of 31, which does not decline over 2000 hours due to physical aging. In addition to gas separation membranes, this cross-linked polyphosphazene can potentially be extended to other applications such as drug delivery or proton exchange membranes which take advantage of the polyphosphazene’s versatile chemistry.
Nanofiltration membanes play a critical role in alleviating global water scarcity, affecting more than 4 billion people. Here, a new metal organic framework (MOF) sacrificicial strategy is designed to synthesize flux-enhancing nanofiltration membrane for efficient dye removal. With the aid of polyphenol chemistry, ZIF-67 MOF was first coated onto a porous support and in situ transformed into a selective layer by virtue of pyrrole polymerization. Trigerred by ammonium persulfate, polypyrrole selective layer functioalized nanofiltration membrane was fabricated when accompanying pore regulation by MOF self-sacrifice. The membrane demonstrated a flux enhancement of 745% than pristine polypyrrole (PPy) one with maintained rejection. Furthermore, the synergistic interactions among polypyrrole, polyphenol, and porous support endowed membrane with excellent stability during long term test. The designed MOF sacrificed route may open a new avenue for fabricating advanced energetic-efficient membranes with the reconstructed architecture towards diverse separation applications.
Ultrafiltration is examined for use as the first stage of a primary treatment process for spacecraft wastewater. It is hypothesized that ultrafiltration can effectively serve as pretreatment for a reverse osmosis system, removing the majority of organic material in a spacecraft wastewater. However, it is believed that the interaction between the membrane material and the surfactant found in the wastewater will have a significant impact on the fouling of the ultrafiltration membrane. In this study, five different ultrafiltration membrane materials are examined for the filtration of wastewater typical of that expected to be produced onboard the International Space Station. Membranes are used in an unstirred batch cell. Flux, organic carbon rejection, and recovery from fouling are measured. The results of this evaluation will be used to select the most promising membranes for further study.
This report describes a summary of the findings of the project. The technical work was divided into three activities: 1) technoeconomic analysis; 2) membrane component development (support layer, selective layer development, and gutter layer formulation); and 3) hollow fiber formation. The technoeconomic analysis includes operating, capital, and materials costs of an oxygen enrichment system with 1-3 stages. The analysis concluded that the desired gas quality (90-95% O2) cannot be reached with a single stage. The triple stage system yielded the best overall product quality at lower membrane performance levels but with the highest cost. For the membrane development activities, functionalized nanodiamonds have been shown to slightly improve membrane formation behaviors and gas permeability performance. For example, support layers based on polysulfone-nanodiamond composites have been formed that increase the material’s O2 permeability by over a factor of 150, however, at the cost of selectivity that suggests a change in transport mechanism. Furthermore, nanodiamonds have been found to improve membrane durability. Improvements in selective and gutter layers also have been accomplished. An additional accomplishment is the demonstration of phase inversion of polysulfone-nanodiamond composites that ensures that hollow fiber formation can be performed. Finally, the interfaces between support, gutter, and selective layers were briefly examined and the resulting membrane material consisting of all three layers gave good performance in an O2 separation from N2. The three-layer prototype membrane gave permeability of 29.2-32.2 Barrers, which equates to permeance of approximately 290-320 GPU, which is lower than the TEA informed goal of 500 GPU. O2/N2 selectivity ranged from 5.2-6.2, which is consistent with the less costly two-stage implementation of the technology. In summary, new materials have been developed for O2 concentration from air and are well-suited to a hollow fiber format.
NASA has been developing a new spacesuit, called the Exploration Extravehicular Mobility Unit (xEMU) for over a decade. This spacesuit is underdevelopment to support missions to the International Space Station (ISS) and also to the Moon. The xEMU uses controlled evaporative cooling through a membrane to reject waste heat from the crewmember, avionics, and environmental in-leak during autonomous operation. Given the unique mass and volume constraints imposed by the spacesuit application and the opportunities presented by the selection of a given membrane, the xEMU does not possess a separate feedwater loop to feed the evaporation process, rather the feedwater for the evaporation process is fed directly from the transport loop which collects heat from the sources within the suit. This has many benefits including mass/volume reductions from a lower component count within the system but does pose some additional potential constraints on water quality within the system in order to provide a working fluid that can be pumped, filtered, and used in contact with the remainder of the system while both avoiding fouling of the membrane as well as other deleterious effects such as creating conditions for corrosion of wetted surfaces within the transport loop. The discussion will seek to address the main sources of contamination and the applied controls. Sources considered will include: self-generated via materials selection and processes applied, influent working fluid, contamination of the influent working fluid via Ground Support Equipment (GSE) or processing equipment, microbial activity, and environmental influences such as elevated ambient CO2.
Polymeric membranes have been widely considered as one of the next-generation technologies for CO 2 capture from fossil fuel-derived flue gases. This separation modality requires novel polymeric materials that possess efficient CO 2 /N 2 separation properties, as well as chemical and mechanical stability for a multiyear membrane lifetime. In this paper, recent developments in polymeric membranes tailored for post-combustion carbon capture are reviewed. The selected polymeric materials encompass ether oxygen-rich polymers, polynorbornenes, ionic liquid membranes, and facilitated transport membranes. In each of the selected materials, noteworthy research efforts for material design and membrane formation are highlighted. The performances of the selected materials are compared in the CO 2 /N 2 selectivity-CO 2 permeance plot. As the only class of materials reviewed herein that have demonstrated the fabrication of thin-film composite membranes in scale, facilitated transport membranes have shown both high selectivity and permeance at relevant conditions for post-combustion carbon capture. Finally, comprehensive field tests are needed to resolve the technical gap between the material development and the commercial application.
Styrene-maleic acid (SMA) copolymers have recently gained attention for their ability to facilitate the detergent-free solubilization of membrane protein complexes and their native boundary lipids into polymer-encapsulated, nanosized lipid particles, referred to as SMALPs. However, the interfacial interactions between SMA and lipids, which dictate the mechanism, efficiency, and selectivity of lipid and membrane protein extraction, are barely understood. Our recent finding has shown that SMA 1440, a chemical derivative of the SMA family with a functionalized butoxyethanol group, was most active in galactolipid-rich membranes, as opposed to phospholipid membranes. In the present work, we have performed X-ray reflectometry (XRR) and neutron reflectometry (NR) on the lipid monolayers at the liquid–air interface followed by the SMA copolymer adsorption. XRR and Langmuir Π–A isotherms captured the fluidifying effect of galactolipids, which allowed SMA copolymers to infiltrate easily into the lipid membranes. NR results revealed the detailed structural arrangement of SMA 1440 copolymers within the membranes and highlighted the partition of butoxyethanol group into the lipid tail region. In conclusion, this work allows us to propose a possible mechanism for the membrane solubilization by SMA.
Lithium has been deemed a critical mineral of national importance that finds uses in a wide range of applications, and its demand has been rising significantly in recent years. The urgency of meeting this demand requires lithium extraction from various aqueous sources such as continental brines, geothermal brines, seawater, produced water, and battery waste. While direct lithium extraction (DLE) technologies such as adsorption, ion exchange, and solvent extraction have emerged as possible solutions, membrane technologies are also being investigated for various sources and at different stages of the recovery process. Here, we analyze the application of membranes for pretreatment of lithium source waters, bring management, lithium/magnesium separation, lithium/sodium separation, and lithium hydroxide conversion, and evaluate performance metrics for critical lithium separations from the literature. We explore the potential of membranes at every stage of the recovery process and describe their current status and future prospects. We describe hypothetical process trains with integrated membrane technologies for each source type and address their feasibility and challenges. The potential energy and water impacts of membrane-integrated and conventional DLE processes are also critically considered alongside performance and selectivity metrics, and this is illustrated using examples and calculated from published technical reports. This paper thus provides a comprehensive overview of the application of membranes along every stage of the lithium recovery process, emphasizing the versatility and potential of membrane technologies for critical mineral recovery.
The Development of a new, robust, portable life support system (PLSS) is currently a high NASA priority in order to support longer and safer extravehicular activity (EVA) missions that will be necessary as space travel extends to near-Earth asteroids and eventually Mars. One of the critical PLSS functions is maintaining the carbon dioxide (CO2) concentration in the suit at acceptable levels. The Metal Oxide (MetOx) canister has a finite CO2 adsorption capacity and therefore in order to extend mission times, the unit would have to be larger and heavier, which is undesirable; therefore new CO2 control technologies must be developed. While recent work has centered on the use of alternating sorbent beds that can be regenerated during the EVA, this strategy increases the system complexity and power consumption. A simpler approach is to use a membrane that vents CO2 to space but retains oxygen(O2). A membrane has many advantages over current technology: it is a continuous system with no theoretical capacity limit, it requires no consumables, and it requires no hardware for switching beds between absorption and regeneration. Conventional gas separation membranes do not have adequate selectivity for use in the PLSS, but the required performance could be obtained with a supported liquid membrane (SLM), which consists of a microporous film filled with a liquid that selectively reacts with CO2 over oxygen (O2). In a recently completed Phase II Small Business Innovative Research project, Reaction Systems developed a new reactive liquid that has effectively zero vapor pressure, making it an ideal candidate for use in an SLM. Results obtained with the SLM in a flat sheet configuration with representative pressures of CO2, O2, and water (H2O) have shown that the CO2 permeation rate and CO2/O2 selectivity requirements have been met. In addition, the SLM vents moisture to space very effectively. The SLM has also been prepared and tested in a hollow fiber form, which will be necessary to meet size requirements in the PLSS. In initial tests, the required CO2 permeance values have been obtained, while the current CO2/O2 selectivity values are somewhat lower than needed. However, the performance of the SLM is a strong function of the method used to impregnate the sorbent in the hollow fiber walls and rapid progress is being made in that area.
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Nanochannel-based fluidic diodes display ion selectivity and ion-current rectification (ICR), which may prove important in energy harvesting and biosensors. This paper reports asymmetric functionalization of the outer surface of a flexible nanochannel polymer membrane to create fluidic diodes that give ICR. Layer-by-layer (LbL) adsorption with cross-linking of only the underlying part of the polyelectrolyte nanofilm leads to a porosity step across the film. The combination of a high effective surface-charge density and the porosity step in the film leads to a remarkable maximum ICR factor of ~200 with a pH gradient across the film. Incorporation of pH-sensitive polyelectrolyte components enables the ICR factor to increase an order of magnitude on going from pH 8 to pH 3. Furthermore, the coated membrane shows excellent anion-selectivity. Thus, LbL adsorption with partial cross-linking provides a simple method for creating coated nanochannel membranes that serve as pH-responsive ionic diodes for potential chemical/biosensors.