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At least 361 records · Page 20

Separation characteristics of cations and natural organic matter in electrodialysis

Natural organic matter (NOM) in water can cause the formation of disinfection byproducts (DBPs) when NOM reacts with a disinfectant such as chlorine. Nanofiltration (NF) and reverse osmosis (RO) are effective treatment methods to remove NOM. However, the simultaneous presence of both NOM and divalent cations such as Ca 2+ can enhance fouling in NF and RO. Therefore, an appropriate pretreatment to remove such cations before NF or RO would delay fouling and perhaps improve water recovery and NOM removal efficiency. Electrodialysis (ED) is potentially an excellent pretreatment method because it separates inorganic ions well using ion exchange membranes (IEMs) but does not separate NOM well because of its size and consequent low diffusivity. This research focused on ion and NOM separation with ED using three different types of commercially available IEM pairs, two different commercially available NOM sources, and six different influents at 500 mg/L total dissolved solids in the presence or absence of both hardness (Ca 2+ and Mg 2+ ) and NOM. The target waters of interest in this research were drinking water supplies that require little or no desalination but substantial removal of NOM; after NOM separation in NF or RO, some or all of the ED concentrate can be added to the NF/RO permeate to create the finished water prior to disinfection. The results indicate that ED can effectively separate alkaline earth metal ions without separation of NOM. Cation exchange membranes with high exchange capacity, high selectivity for divalent cations are desirable, and both anion and cation exchange membranes should have low affinity for organic adsorption. As a result, the process would work particularly well for NOM with relatively low hydrophobicity, since NOM adsorption to most surfaces increases with hydrophobicity.

36 MATERIALS SCIENCE↗

How to Get the Best Gas Separation Membranes from State-of-the-Art Glassy Polymers

Herein we focus on fundamental polymer science factors in membrane-based gas separation to open another chapter on this important topic. Realistically thinking about nano and angstrom scale matrix attributes that are translatable into higher performance thin glassy polymer asymmetric membrane layers in practical large-scale devices is crucial. Such thinking should be guided by expertise in both polymer and membrane communities to advance the state of the art. Polymer structures, membrane morphologies and effects of operating conditions are discussed here, using specific examples to illustrate key issues. Rubbery polymers are not the focus of this discussion, since they lack diffusive discrimination for size-similar penetrants, which glassy polymers provide and make them the focus here. Four scalable subtopics guide necessary thinking: (i) plasticization; (ii) anti-plasticization†2; (iii) dual-mode transport involving saturation of unrelaxed free volume, and (iv) non-uniform free volume and stress profiles in thin skin glassy polymer asymmetric or composite membranes. Furthermore, using these subtopics in the context of macromolecular science we discuss issues needed to expand the state-of-the-art in gas separation membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA Redox Storage System Development Project

The Redox Storage System Technology Project was jointly supported by the U.S. Department of Energy and NASA. The objectives of the project were to develop the Redox flow battery concept and to probe its technical and economic viability. The iron and chromium redox couples were selected as the reactants. Membranes and electrodes were developed for the original mode of operating at 25 C with the reactants separated by an ion-exchange membrane. Analytical capabilities and system-level operating concepts were developed and verified in a 1-kW, 13-kWh preprototype system. A subsequent change was made in operating mode, going to 65 C and using mixed reactants. New membranes and a new electrode catalyst were developed, resulting in single cell operation as high as 80 mA/sq cm with energy efficiencies greater than 80 percent. Studies indicate a likely system cost of about $75/kWh. Standard Oil of Ohio (Sohio) has undertaken further development of the Redox system. An exclusive patent license was obtained from NASA by Sohio. Transfer of Redox technology to Sohio is supported by the NASA Technology Utilization Office.

Hagedorn, N. H.↗

Cycling Performance of the Iron-Chromium Redox Energy Storage System

Extended charge-discharge cycling of this electrochemical storage system at 65 C was performed on 14.5 sq cm single cells and a four cell, 867 sq cm bipolar stack. Both the anolyte and catholyte reactant fluids contained 1 molar concentrations of iron and chromium chlorides in hydrochloric acid and were separated by a low-selectivity, cation-exchange membrane. The effect of cycling on the chromium electrode and the cation-exchange membrane was determined. Bismuth and bismuth-lead catalyzed chromium electrodes and a radiation-grafted polyethylene membrane were evaluated by cycling between 5 and 85 percent state-of-charge at 80 mA/sq cm and by periodic charge-discharge polarization measurements to 140 mA/sq cm. Gradual performance losses were observed during cycling but were recoverable by completely discharging the system. Good scale-up to the 867 sq cm stack was achieved. The only difference appeared to be an unexplained resistive-type loss which resulted in a 75 percent W-hr efficiency (at 80 mA/sq cm versus 81 percent for the 14.5 sq cm cell). A new rebalance cell was developed to maintain reactant ionic balance. The cell successfully reduced ferric ions in the iron reactant stream to ferrous ions while chloride ions were oxidized to chlorine gas.

Gahn, R. F.↗

Cycling performance of the iron-chromium redox energy storage system

Extended charge-discharge cycling of this electrochemical storage system at 65 C was performed on 14.5 sq cm single cells and a four cell, 867 sq cm bipolar stack. Both the anolyte and catholyte reactant fluids contained 1 molar concentrations of iron and chromium chlorides in hydrochloric acid and were separated by a low-selectivity, cation-exchange membrane. The effect of cycling on the chromium electrode and the cation-exchange membrane was determined. Bismuth and bismuth-lead catalyzed chromium electrodes and a radiation-grafted polyethylene membrane were evaluated by cycling between 5 and 85 percent state-of-charge at 80 mA/sq cm and by periodic charge-discharge polarization measurements to 140 mA/sq cm. Gradual performance losses were observed during cycling but were recoverable by completely discharging the system. Good scale-up to the 867 sq cm stack was achieved. The only difference appeared to be an unexplained resistive-type loss which resulted in a 75 percent W-hr efficiency (at 80 mA/sq cm versus 81 percent for the 14.5 sq cm cell). A new rebalance cell was developed to maintain reactant ionic balance. The cell successfully reduced ferric ions in the iron reactant stream to ferrous ions while chloride ions were oxidized to chlorine gas.

Gahn, R. F.↗

Ammonia Monitor

Ammonia monitor and method of use are disclosed. A continuous, real-time determination of the concentration of ammonia in an aqueous process stream is possible over a wide dynamic range of concentrations. No reagents are required because pH is controlled by an in-line solid-phase base. Ammonia is selectively transported across a membrane from the process stream to an analytical stream to an analytical stream under pH control. The specific electrical conductance of the analytical stream is measured and used to determine the concentration of ammonia.

Sauer, Richard L.↗

Buffer Gas Acquisition and Storage

The acquisition and storage of buffer gases (primarily argon and nitrogen) from the Mars atmosphere provides a valuable resource for blanketing and pressurizing fuel tanks and as a buffer gas for breathing air for manned missions. During the acquisition of carbon dioxide (CO2), whether by sorption bed or cryo-freezer, the accompanying buffer gases build up in the carbon dioxide acquisition system, reduce the flow of CO2 to the bed, and lower system efficiency. It is this build up of buffer gases that provide a convenient source, which must be removed, for efficient capture Of CO2 Removal of this buffer gas barrier greatly improves the charging rate of the CO2 acquisition bed and, thereby, maintains the fuel production rates required for a successful mission. Consequently, the acquisition, purification, and storage of these buffer gases are important goals of ISRU plans. Purity of the buffer gases is a concern e.g., if the CO, freezer operates at 140 K, the composition of the inert gas would be approximately 21 percent CO2, 50 percent nitrogen, and 29 percent argon. Although there are several approaches that could be used, this effort focused on a hollow-fiber membrane (HFM) separation method. This study measured the permeation rates of CO2, nitrogen (ND, and argon (Ar) through a multiple-membrane system and the individual membranes from room temperature to 193K and 10 kpa to 300 kPa. Concentrations were measured with a gas chromatograph that used a thermoconductivity (TCD) detector with helium (He) as the carrier gas. The general trend as the temperature was lowered was for the membranes to become more selective, In addition, the relative permeation rates between the three gases changed with temperature. The end result was to provide design parameters that could be used to separate CO2 from N2 and Ar.

Parrish, Clyde F.↗

Steady-State Vacuum Ultraviolet Exposure Facility With Automated Lamp Calibration and Sample Positioning Fabricated

The Next Generation Space Telescope (NGST) will be placed in an orbit that will subject it to constant solar radiation during its planned 10-year mission. A sunshield will be necessary to passively cool the telescope, protecting it from the Sun s energy and assuring proper operating temperatures for the telescope s instruments. This sunshield will be composed of metalized polymer multilayer insulation with an outer polymer membrane (12 to 25 mm in thickness) that will be metalized on the back to assure maximum reflectance of sunlight. The sunshield must maintain mechanical integrity and optical properties for the full 10 years. This durability requirement is most challenging for the outermost, constantly solar-facing polymer membrane of the sunshield. One of the potential threats to the membrane material s durability is from vacuum ultraviolet (VUV) radiation in wavelengths below 200 nm. Such radiation can be absorbed in the bulk of these thin polymer membrane materials and degrade the polymer s optical and mechanical properties. So that a suitable membrane material can be selected that demonstrates durability to solar VUV radiation, ground-based testing of candidate materials must be conducted to simulate the total 10- year VUV exposure expected during the Next Generation Space Telescope mission. The Steady State Vacuum Ultraviolet exposure facility was designed and fabricated at the NASA Glenn Research Center at Lewis Field to provide unattended 24-hr exposure of candidate materials to VUV radiation of 3 to 5 times the Sun s intensity in the wavelength range of 115 to 200 nm. The facility s chamber, which maintains a pressure of approximately 5 10(exp -6) torr, is divided into three individual exposure cells, each with a separate VUV source and sample-positioning mechanism. The three test cells are separated by a water-cooled copper shield plate assembly to minimize thermal effects from adjacent test cells. Part of the interior sample positioning mechanism of one test cell is shown in the illustration. Of primary concern in VUV exposure is the maintenance of constant measured radiation intensity so that the sample s total exposure can be determined in equivalent Sun hours. This is complicated by the fact that a VUV lamp s intensity degrades over time, necessitating a decrease in the distance between the test samples and the lamp. The facility overcomes this challenge by periodically measuring the lamp s intensity with a cesium-iodide phototube and adjusting the sample distance as required to maintain constant exposure intensity. Sample positioning and periodic phototube location under the lamp are both achieved by a single lead-screw assembly. The lamps can be isolated from the main vacuum chamber for cleaning or replacement so that samples are not exposed to the atmosphere during a test.

Sechkar, Edward A.↗

Contaminant Removal from Oxygen Production Systems for In Situ Resource Utilization

The In Situ Resource Utilization (ISRU) project has been developing technologies to produce oxygen from lunar regolith to provide consumables to a lunar outpost. The processes developed reduce metal oxides in the regolith to produce water, which is then electrolyzed to produce oxygen. Hydrochloic and hydrofluoric acids are byproducts of the reduction processes, as halide minerals are also reduced at oxide reduction conditions. Because of the stringent water quality requirements for electrolysis, there is a need for a contaminant removal process. The Contaminant Removal from Oxygen Production Systems (CROPS) team has been developing a separation process to remove these contaminants in the gas and liquid phase that eliminates the need for consumables. CROPS has been using Nafion, a highly water selective polymeric proton exchange membrane, to recover pure water from the contaminated solution. Membrane thickness, product stream flow rate, and acid solution temperature and concentration were varied with the goal of maximizing water permeation and acid rejection. The results show that water permeation increases with increasing solution temperature and product stream flow rate, while acid rejection increases with decreasing solution temperature and concentration. Thinner membranes allowed for higher water flux and acid rejection than thicker ones. These results were used in the development of the hardware built for the most recent Mars ISRU demonstration project.

Anthony, Stephen M.↗

Tuning gas separation performance of polyimide membranes with macrocyclic crown ether units

Membrane-based gas separation is an energy-efficient alternative to conventional thermally-driven separation processes. However, polymer membranes face the permeability-selectivity trade-off challenge, which stems from the broad size distribution of free volume voids. Here, this study reports a molecular design strategy to address this challenge through incorporating macrocyclic crown ether (CE) moieties into the backbone of Matrimid® polyimide, a commercial gas separation membrane. A series of CE-containing Matrimid®-like copolyimides were synthesized with systematically varied CE molar contents ranging from 3 to 20%. These copolyimides formed ductile, defect-free thin films suitable for membrane fabrication. Gas permeation tests revealed a non-monotonic relationship between permeability/selectivity and CE content. Notably, the copolyimide with only 5% CE demonstrated a 61% increase in CO 2 /CH 4 selectivity and a 13% increase in CO 2 permeability relative to pristine Matrimid®. Higher CE contents did not yield further performance improvements, which is likely due to the competing effects of chain packing disruption and π–π interactions among CE moieties at high content. This hypothesis was supported by wide-angle X-ray scattering (WAXS) analysis, density measurements, and fractional free volume calculations. These findings highlight the potential of macrocyclic crown ether incorporation strategies in fine tuning the microstructure of commercial polyimide gas separation membranes to surpass the traditional permeability-selectivity trade-off.

CO2 separation↗

Dual Modification of MOFs Improves Dispersion and Ionic Conductivity of Mixed Matrix Membranes

Nonaqueous redox flow batteries (NARFBs) are a promising class of energy storage devices, but the lack of a chemically stable, conductive membrane that exhibits size-selectivity over redox-active species prevents their broader implementation. Recently, metal–organic frameworks (MOFs) have been implemented into mixed-matrix membranes (MMMs) for NARFBs, but the effects of the MOF linker functionality on membrane properties are not well-understood. In this work, we develop a series of MOF-based MMMs by blending postsynthetically modified variants of UiO-66-NH2 with poly(ethylene-co-vinyl acetate). The modification of UiO-66-NH2 with sulfate groups initially resulted in poor dispersion throughout the MMMs, but when dual-modified with poly(N-isopropylacrylamide), MOF dispersion throughout the MMM was improved, and ionic conductivity was significantly higher than the UiO-66-NH2 MMMs. Furthermore, the dual-modified MMMs demonstrated excellent size-selectivity by blocking redox active species transport. This work demonstrates a synergy between the MOF functional groups to improve MMM properties critical for the development of practical NARFBs.

Carey, Cassidy A.↗

Printed Potentiometric Nitrate Sensors for Use in Soil

Plant-available nitrogen, often in the form of nitrate, is an essential nutrient for plant growth. However, excessive nitrate in the environment and watershed has harmful impacts on natural ecosystems and consequently human health. A distributed network of nitrate sensors could help to quantify and monitor nitrogen in agriculture and the environment. Here, we have developed fully printed potentiometric nitrate sensors and characterized their sensitivity and selectivity to nitrate. Each sensor comprises an ion-selective electrode and a reference electrode that are functionalized with polymeric membranes. The sensitivity of the printed ion-selective electrodes was characterized by measuring their potential with respect to a commercial silver/silver chloride reference electrode in varying concentrations of nitrate solutions. The sensitivity of the printed reference electrodes to nitrate was minimized with a membrane containing polyvinyl butyral (PVB), sodium chloride, and sodium nitrate. Selectivity studies with sulphate, chloride, phosphate, nitrite, ammonium, calcium, potassium, and magnesium showed that high concentrations of calcium can influence sensor behavior. The printed ion-selective and reference electrodes were combined to form a fully printed sensor with sensitivity of −48.0 ± 3.3 mV/dec between 0.62 and 6200 ppm nitrate in solution and −47 ± 4.1 mV/dec in peat soil.

Baumbauer, Carol L. (ORCID:0000000246747551)↗

Sieving Hydrogen Isotopes via Machine Learning Assisted Chemical Vapor Deposition (CVD) of High‐Quality Monolayer Hexagonal Boron Nitride (h‐BN) on Iron Foils

Atomically thin two-dimensional (2D) ceramics, such as monolayer hexagonal boron nitride (h-BN), present potential for disruptive advances in separations. However, sub-atomic scale separation of hydrogen isotopes (H + /D + ) require near pristine 2D material membranes, and scalable synthesis of such high-quality h-BN comparable to mechanically exfoliated crystals remains a significant challenge. Here, we report a scalable Fe-catalyzed chemical vapor deposition (CVD) process for bottom-up synthesis of large-area, high-quality monolayer h-BN films, overcoming key limitations of conventional ammonia-based routes. By leveraging mechanistic insights and higher CVD temperatures, we suppress multilayer formation and achieve uniform monolayer h-BN coverage on commercially available Fe foils. Machine learning enables systematic exploration of the complex, multi-dimensional CVD parameter space (growth time, temperature, precursor temperature, multilayer faction, coverage), providing data-driven approaches to visualize and identify process regimes facilitating predominantly monolayer h-BN growth with minimal secondary nuclei/ad-layers. The optimized Fe-catalyzed CVD h-BN membranes show high-quality as observed by proton/deuteron (H + /D + ) selectivity ≈8.45, approaching the highest quality benchmark of mechanically exfoliated h-BN (H + /D + selectivity ≈10) as well as significantly outperforming Cu-catalyzed CVD h-BN membranes (H + /D + selectivity ≈3.62, control selectivity ≈1.7). Our work provides a scalable cost-effective route for high-quality monolayer h-BN synthesis for sub-atomic scale separations (H + /D + ) and demonstrates the broader potential of machine learning-guided optimization of CVD for advancing synthesis of 2D materials.

36 MATERIALS SCIENCE↗

Electrochemical Probing of Steric, Electrostatic and Hydrophobic Interactions of Large Cations in Polymers of Intrinsic Microporosity

Porous membranes have been used for many applications, including separations in biotechnology, the food industry, water purification, and even energy storage devices. The benefit of polymers of intrinsic microporosity (PIMs) is their consistently sized nanopore channels. Inherent functionalities of the PIM structure not only create these channels but are also available for further modifications that can change the interactions of ions and molecules inside of the pore. Here we design solid state nanopores on which are drop-casted two different PIMs, functionalized with either a cyano group or a carboxylic acid. Ionic transport through the membranes is investigated based on pore size and charge-charge interactions, as well as steric and hydrophobic interactions. Achieving specific ion selectivity with easily processable porous membranes opens new avenues for water purification strategies and energy storage.

25 ENERGY STORAGE↗

Continued Advancement of Supported Liquid Membranes for Carbon Dioxide Control in Extravehicular Activity Applications

The development of a new, robust, portable life support system (PLSS) is a high priority for NASA in order to support longer and safer extravehicular activity (EVA) missions. One of the critical PLSS functions is maintaining the carbon dioxide (CO2) concentration in the suit at acceptable levels. Although the Metal Oxide (MetOx) canister has historically performed very well, it has a finite CO2 adsorption capacity. Therefore, the size and weight of the unit would have to be increased to extend EVA times. Consequently, new CO2 control technologies must be developed in order to meet mission objectives without increasing the size of the PLSS. Recent work has centered on sorbents that can be regenerated during the EVA; however, this strategy increases the system complexity and power consumption. A much simpler approach is to employ a membrane that vents CO2 to space and retains oxygen (O2). A membrane has many advantages over current technology: it is a continuous system with no limit on capacity, it requires no consumables, and it does not need any hardware to switch beds between absorption and regeneration. Unfortunately, conventional gas separation membranes do not have the needed selectivity for use in the PLSS. However, the required performance could be obtained with a supported liquid membrane (SLM), which consists of a microporous material filled with a liquid that selectively reacts with CO2 over O2. In a recently completed Phase II SBIR project, Reaction Systems, Inc. achieved the required CO2 permeance and selectivity with an SLM in a flat sheet configuration. This paper describes work to convert the SLM into a more compact form and to scale it up to handle more representative process flow rates.

Wickham, David T.↗

Wastewater Brine Purification and Recovery through Electrodialysis Ion Exchange

Reutilizing resources onboard the International Space Station (ISS) and for future deep space missions are critical for mission longevity and sustainability. Wastewater brine produced from water recovery systems contain chemical species that could be processed into a potential fertilizer for future plant systems. This can be achieved through a process called electrodialysis ion exchange. Wastewater containing inorganic salt components are fed through a series of ion exchange membranes to produce fertilizer (a phosphate rich stream), electrolysis-grade water, and other useful commodities. Electrodialysis cells consisting of anion and cation exchange membranes, monovalent anion exchange membranes, and bipolar membranes were utilized to achieve selective ion exchange. The use of the electrodialysis cells were effective for both water extraction and ion separation. Ions successfully diffused across their respective membranes into the concentrate, acid, and base streams. This resulted in pure water, a phosphate rich stream, and a separate anion/hydrogen and cation/hydroxide stream. However, sulfate and some phosphate ions were able to diffuse through the monovalent anion exchange membrane into the acid stream. This resulted in predominantly phosphate ions remaining in the concentrate. Optimization of the process was accomplished by altering flowrates of each stream and initial volumes, adjusting the power input and resulting current through each cell, and varying the starting parameters by splitting the inorganic waste input into the diluate and the concentrate. As expected, increasing the flowrate and the power input to each cell reduced the overall time of the process. However, mission constraints may require a longer duration process in order to reduce the power consumption. Further analysis will be required to determine the power input necessary to achieve ion diffusion effectively and in a timely manner.

Ion Exchange Membranes↗