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At least 163 records · Page 9

Ionic Liquid Facilitated Recovery of Metals and Oxygen from Regolith

Regolith, being largely composed of metal oxides, has the potential to be an excellent in situ source of metals, such as iron, nickel and aluminum, as well as oxygen. There is, however, no current technology that is suited for the in space separation of metal oxides into their constituent elements. Terrestrial methods require large volumes/masses of hazardous reagents. Alternative methods, such as molten oxide electrolysis, have been investigated, but these processes generally require high temperatures to operate. Such a requirement imposes significant material compatibility restraints, necessitates high energy inputs, and may pose a threat to the health and safety of the crew. This paper discusses a novel process that uses ionic liquids (ILs) to recover high purity metals and oxygen from regolith and meteorite materials. ILs are organic salts that are molten at or near room temperature, and can have a number of attractive properties including wide liquidus ranges and high thermal and electrochemical stability. The structure of an IL can be readily modified to tune these properties, allowing the synthesis of task specific ILs. Together, these attributes give ILs great utility in a number of space related areas, such environmental control and life support, in space repair and manufacture, and in situ resource utilization.

Karr, Laurel J.↗

Computational and Experimental Study of Li-doped Ionic Liquids at Electrified Interfaces

We evaluate the influence of Li-salt doping on the dynamics, capacitance, and structure of three ionic liquid electrolytes, [pyr14][TFSI], [pyr13][FSI], and [EMIM][BF4], using molecular dynamics and polarizable force fields. In this respect, our focus is on the properties of the electric double layer (EDL) formed by the electrolytes at the electrode surface as a function of surface potential (Psi). The rates of EDL formation are found to be on the order of hundreds of picoseconds and only slightly influenced by the addition of Li-salt. The EDLs of three electrolytes are shown to have different energy storage capacities, which we relate to the EDL formation free energy. The differential capacitance obtained from our computations exhibits asymmetry about the potential of zero charge and is consistent with the camel-like profiles noted from mean field theories and experiments on metallic electrodes. The introduction of Li-salt reduces the noted asymmetry in the differential capacitance profile. Complementary experimental capacitance measurements have been made on our three electrolytes in their neat forms and with Li-salt. The measurements, performed on glassy carbon electrodes, produce U-like profiles, and Li-salt doping is shown to strongly affect capacitance at high magnitudes of Psi. Differences in the theoretical and experimental shapes and magnitudes of capacitance are rationalized in terms of the electrode surface and pseudocapacitive effects. In both neat and Li-doped liquids, the details of the computational capacitance profile are well described by Psi-induced changes in the density and molecular orientation of ions in the molecular layer closest to the electrode. Our results suggest that the addition of Li+ induces disorder in the EDL, which originates from the strong binding of anions to Li+. An in-depth analysis of the distribution of Li+ in the EDL reveals that it does not readily enter the molecular layer at the electrode surface, preferring instead to be localized farther away from the surface in the second molecular layer. This behavior is validated through an analysis of the free energy of Li+ solvation as a function of distance from the electrode. Free energy wells are found to coincide with localized concentrations of Li+, the depths of which increase with Psi and suggest a source of impedance for Li+ to reach the electrode.

Haskins, Justin B.↗

Synthesis and Performance of 6FDA-Based Polyimide-Ionenes and Composites with Ionic Liquids as Gas Separation Membranes

Three new isomeric 6FDA-based polyimide-ionenes, with imidazolium moieties and varying regiochemistry (para-, meta-, and ortho- connectivity), and composites with three different ionic liquids (ILs) have been developed as gas separation membranes. The structural-property relationships and gas separation behaviors of the newly developed 6FDA polyimide-ionene + IL composites have been extensively studied. All the 6FDA-based polyimide-ionenes exhibited good compatibility with the ILs and produced homogeneous hybrid membranes with the high thermal stability of ~380 °C. Particularly, [6FDA I4A pXy][Tf2N] ionene + IL hybrids having [C4mim][Tf2N] and [Bnmim][Tf2N] ILs offered mechanically stable matrixes with high CO2 affinity. The permeability of CO2 was increased by factors of 2 and 3 for C4mim and Bnmim hybrids (2.15 to 6.32 barrers), respectively, compared to the neat [6FDA I4A pXy][Tf2N] without sacrificing their permselectivity for CO2/CH4 and CO2/N2 gas pairs.

Ionenes↗

Novel Aprotic Heterocyclic Anion-based Ionic Liquids for Carbon Dioxide Capture

Ionic liquids (ILs), or organic salts with melting points at or below room temperature are an incredibly versatile class of materials with many possible applications for NASA’s exploration needs. In particular, appropriately designed ILs can have a high affinity for absorbing carbon dioxide, making them excellent candidates for use as liquid sorbents in cabin air revitalization systems. Unfortunately, many of these ILs have high viscosity, which is only exacerbated by carbon dioxide uptake. High viscosity limits the rate of carbon dioxide uptake. A new class of IL sorbent containing aprotic heterocyclic anions (AHA) has been shown to offer excellent carbon dioxide uptake without a corresponding increase in viscosity. However, there is a paucity of sorption data for these AHA ILs at low partial pressures of carbon dioxide. This paper reports on the characterization of sorption behavior for AHA ILs previously reported in the literature at low concentrations of carbon dioxide and the synthesis and characterization of new, water miscible AHA ILs. Characterization of the new ILs includes measurement of density, viscosity, thermal stability, carbon dioxide capacity, carbon dioxide absorption kinetics, and water-IL vapor liquid equilibrium. Overall, these news ILs are promising alternatives to many of the commonly used IL sorbents.

Eric Townsend Fox↗

Monitoring of Ionic Silver Biocide with Capacitively-Coupled Contactless Conductivity Detection (C4D)

Monitoring of biocide dosing in spacecraft potable water systems is desirable to ensure dosing system operation and resultant microbial control. Electrolytic conductivity is linearly related to the concentration ionic silver (Ag+, the baseline biocide for future NASA missions) chemically dosed into highly purified water, and could serve as a proxy measurement. Traditional conductivity cells rely on immersed metal or graphite electrodes, which may potentially be subject to significant current-induced or auto-galvanic deposition of Ag+. Furthermore, oxide fouling may potentially induce measurement errors. Capacitively-coupled contactless conductivity detection (C4D) is a promising alternative. C4D uses electrodes placed outside an inert, non-conductive flow path, potentially mitigating such problems. We identified and purchased a commercial C4D system with claimed performance (conductivity range: 20 nS/cm to 4 µS/cm) appropriate for this application. We characterized the instrument’s performance with conductivity standards and Ag+ solutions. We began investigations considering practical and long-term detector operation, including potential current-induced deposition of conductive deposits at the tubing wall. In addition, we designed a side-stream flow system to provide liquid flow through the narrow tubing (1/16” outer diameter) required by the detector and characterized the performance of the combined C4D detector/flow system. Finally, we completed theoretical modeling of expected conductivity change with multiple dosing techniques and water chemistries.

Lance Dean Delzeit↗

Considerations on Electrolytic Conductivity Measurement for Monitoring of Ionic Silver Biocide Dosing

NASA interest in ionic silver (Ag+) as a biocide for spacecraft potable water systems motivates the development of Ag+ concentration sensors to ensure nominal dosing. The electrolytic conductivity change of highly-purified potable water is linearly related to the concentration of chemically-dosed Ag+ and could serve as a useful proxy measurement, while the conductivity change during electrolytic dosing may be less so, depending on the influent water chemistry and electrolytic efficiency. Understanding and mitigating the potentially deleterious effects of Ag+ interaction with conductivity measurement systems requires investigation. Issues associated with traditional conductivity cells, which rely on wetted(typically metal or graphite) electrodes, and capacitively-coupled contactless conductivity detection (C4D) for this application are considered. Traditional conductivity cells may potentially be subject to significant excitation-induced or auto-galvanic reduction of Ag+. These may result in Ag+ depletion or electrode fouling and associated measurement error. Proper selection of electrode material, excitation parameters, and cell geometry may limit such effects. C4D uses electrodes placed outside an inert, insulating material, with dielectric polarization enabling the production of an electric field and resultant current across the analyte solution. This approach could potentially mitigate problems with Ag+ depletion and fouling by eliminating the possibility of auto-galvanic deposition and reducing the Faradaic current density. However, it is necessary to confirm C4D performance at very low conductivity levels and to determine if long-term operation produces conductive deposits, which could result in measurement error. A commercial C4D system with 1/16” (1.59 mm)outer diameter flow tubing and claimed performance in the conductivity range appropriate for this application was identified, and its sensitivity in the upper parts of this range was confirmed in a preliminary experiment. A concept for a C4D detector that could allow for full rate flow-through using planar electrodes and thin-film dielectric layers is discussed.

silver↗

Periodic Solar Wind Structures Observed in Measurements of Elemental and Ionic Composition in situ at L1

Mesoscale periodic structures observed in solar wind plasma serve as an important diagnostic tool for constraining the processes that govern the formation of the solar wind. These structures have been observed in situ and in remote data as fluctuations in proton and electron density. However, only two events of this type have been reported regarding the elemental and ionic composition. Composition measurements are especially important in gaining an understanding of the origin of the solar wind as the composition is frozen into the plasma at the Sun and does not evolve as it advects through the heliosphere. Here, we present the analysis of four events containing mesoscale periodic solar wind structure during which the Iron and Magnesium number density data, measured by the Solar Wind Ion Composition Spectrometer (SWICS)on board the Advanced Composition Explorer spacecraft, are validated at statistically significant count levels. We use a spectral analysis method specifically designed to extract periodic signals from astrophysical time series and apply it to the SWICS 12-minute native resolution dataset. We find variations in the relative abundance of elements with low first ionization potential, mass dependencies, and charge state during time intervals in which mesoscale periodic structures are observed. These variations are linked to temporal or spatial variations in solar source regions and put constraints on the solar wind formation mechanisms that produce them. Techniques presented here are relevant for future, higher-resolution studies of data from new instruments such as Solar Orbiter’s Heavy Ion Sensor.

Irena Gershkovich↗