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NASA NTRS2005

Solar Effects on Global Climate Due to Cosmic Rays and Solar Energetic Particles

Although the work reported here does not directly connect solar variability with global climate change, this research establishes a plausible quantitative causative link between observed solar activity and apparently correlated variations in terrestrial climate parameters. Specifically, we have demonstrated that ion-mediated nucleation of atmospheric particles is a likely, and likely widespread, phenomenon that relates solar variability to changes in the microphysical properties of clouds. To investigate this relationship, we have constructed and applied a new model describing the formation and evolution of ionic clusters under a range of atmospheric conditions throughout the lower atmosphere. The activation of large ionic clusters into cloud nuclei is predicted to be favorable in the upper troposphere and mesosphere, and possibly in the lower stratosphere. The model developed under this grant needs to be extended to include additional cluster families, and should be incorporated into microphysical models to further test the cause-and-effect linkages that may ultimately explain key aspects of the connections between solar variability and climate.

Turco, R. P.↗

NASA NTRS2006

Design and Certification of the Extravehicular Activity Mobility Unit (EMU) Water Processing Jumper

The Extravehicular Mobility Units (EMUs) onboard the International Space Station (ISS) experienced a failure due to cooling water contamination from biomass and corrosion byproducts forming solids around the EMU pump rotor. The coolant had no biocide and a low pH which induced biofilm growth and corrosion precipitates, respectively. NASA JSC was tasked with building hardware to clean the ionic, organic, and particulate load from the EMU coolant loop before and after Extravehicular Activity (EVAs). Based on a return sample of the EMU coolant loop, the chemical load was well understood, but there was not sufficient volume of the returned sample to analyze particulates. Through work with EMU specialists, chemists, (EVA) Mission Operations Directorate (MOD) representation, safety and mission assurance, astronaut crew, and team engineers, requirements were developed for the EMU Water Processing hardware (sometimes referred to as the Airlock Coolant Loop Recovery [A/L CLR] system). Those requirements ranged from the operable level of ionic, organic, and particulate load, interfaces to the EMU, maximum cycle time, operating pressure drop, flow rate, and temperature, leakage rates, and biocide levels for storage. Design work began in February 2005 and certification was completed in April 2005 to support a return to flight launch date of May 12, 2005. This paper will discuss the details of the design and certification of the EMU Water Processing hardware and its components

Peterson, Laurie J.↗

NASA NTRS2007

Microfluidic System Simulation Including the Electro-Viscous Effect

This paper describes a practical approach using a general purpose lumped-parameter computer program, GFSSP (Generalized Fluid System Simulation Program) for calculating flow distribution in a network of micro-channels including electro-viscous effects due to the existence of electrical double layer (EDL). In this study, an empirical formulation for calculating an effective viscosity of ionic solutions based on dimensional analysis is described to account for surface charge and bulk fluid conductivity, which give rise to electro-viscous effect in microfluidics network. Two dimensional slit micro flow data was used to determine the model coefficients. Geometry effect is then included through a Poiseuille number correlation in GFSSP. The bi-power model was used to calculate flow distribution of isotropically etched straight channel and T-junction microflows involving ionic solutions. Performance of the proposed model is assessed against experimental test data.

Rojas, Eileen↗

NASA NTRS2006

The Use of Liquid Isopropyl Alcohol and Hydrogen Peroxide Gas Plasma to Biologically Decontaminate Spacecraft Electronics

Legitimate concern exists regarding sending spacecraft and their associated hardware to solar system bodies where they could possibly contaminate the body's surface with terrestrial microorganisms. The NASA approved guidelines for sterilization as set forth in NPG 8020.12C, which is consistent with the biological contamination control objectives of the Committee on Space Research (COSPAR), recommends subjecting the spacecraft and its associated hardware to dry heat-a dry heat regimen that could potentially employ a temperature of 110(deg)C for up to 200 hours. Such a temperature exposure could prove detrimental to the spacecraft electronics. The stimulated growth of intermetallic compounds (IMCs) in metallic interconnects and/or thermal degradation of organic materials composing much of the hardware could take place over a prolonged temperature regimen. Such detrimental phenomena would almost certainly compromise the integrity and reliability of the electronics. Investigation of sterilization procedures in the medical field suggests that hydrogen peroxide (H202) gas plasma (HPGP) technology can effectively function as an alternative to heat sterilization, especially for heat-sensitive items. Treatment with isopropyl alcohol (IPA) in liquid form prior to exposure of the hardware to HPGP should also prove beneficial. Although IPA is not a sterilant, it is frequently used as a disinfectant because of its bactericidal properties. The use of IPA in electronics cleaning is widely recognized and has been utilized for many years with no adverse affects reported. In addition, IPA is the principal ingredient of the test fluid used in ionic contamination testers to assess the amount of ionic contamination found on the surfaces of printed wiring assemblies. This paper will set forth experimental data confirming the feasibility of the IPA/H202 approach to reach acceptable microbial reduction (MR) levels of spacecraft electronic hardware. In addition, a proposed process flow in which both IPA liquid and HPGP are utilized will be presented in Section 7.0.

microbial reduction↗

NASA NTRS2008

Cr.sup.4+-doped mixed alloy laser materials and lasers and methods using the materials

A laser medium includes a single crystal of Cr.sup.4+:Mg.sub.2-xM.sub.xSi.sub.1-yA.sub.yO.sub.4, where, where M is a bivalent ion having an ionic radius larger than Mg.sup.2+, and A is a tetravalent ion having an ionic radius larger than Si.sup.4+. In addition, either a) 0.ltoreq.x<2 and 0<y<1 or b) 0<x<2 and y is 0 or 1 with the proviso that if M is Ca.sup.2+ and x=1 then y is not 0. The laser medium can be used in a laser device, such as a tunable near infrared (NIR) laser.

Alfano, Robert R.↗

NASA NTRS2008

LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic voltammetry measurements, LiGa(OTf)4 and the other salts exhibited acceptably high electrochemical stability over the relatively wide potential window of 0 to 5 V versus Li+/Li. 13C nuclear-magneticresonance measurements yielded results that suggested that in comparison with the other candidate salts, LiGa(OTf)4 exhibits less ion pairing. Planned further development will include optimization of the salt and solvent contents of such electrolyte solutions and incorporation of LiGa(OTf)4 into gel and solid-state polymer electrolytes. Of the salts, LiGa(OTf)4 is expected to be especially desirable for incorporation into lithium polymer electrolytes, wherein decreased ion pairing is advantageous and the large delocalized anions can exert a plasticizing effect.

Reddy, V. Prakash↗

NASA NTRS2007

Ion-Conducting Organic/Inorganic Polymers

Ion-conducting polymers that are hybrids of organic and inorganic moieties and that are suitable for forming into solid-electrolyte membranes have been invented in an effort to improve upon the polymeric materials that have been used previously for such membranes. Examples of the prior materials include perfluorosulfonic acid-based formulations, polybenzimidazoles, sulfonated polyetherketone, sulfonated naphthalenic polyimides, and polyethylene oxide (PEO)-based formulations. Relative to the prior materials, the polymers of the present invention offer greater dimensional stability, greater ease of formation into mechanically resilient films, and acceptably high ionic conductivities over wider temperature ranges. Devices in which films made of these ion-conducting organic/inorganic polymers could be used include fuel cells, lithium batteries, chemical sensors, electrochemical capacitors, electrochromic windows and display devices, and analog memory devices. The synthesis of a polymer of this type (see Figure 1) starts with a reaction between an epoxide-functionalized alkoxysilane and a diamine. The product of this reaction is polymerized by hydrolysis and condensation of the alkoxysilane group, producing a molecular network that contains both organic and inorganic (silica) links. The silica in the network contributes to the ionic conductivity and to the desired thermal and mechanical properties. Examples of other diamines that have been used in the reaction sequence of Figure 1 are shown in Figure 2. One can use any of these diamines or any combination of them in proportions chosen to impart desired properties to the finished product. Alternatively or in addition, one could similarly vary the functionality of the alkoxysilane to obtain desired properties. The variety of available alkoxysilanes and diamines thus affords flexibility to optimize the organic/inorganic polymer for a given application.

Kinder, James D.↗

NASA NTRS2010

Confirmation of Soluble Sulfate at the Phoenix Landing Site: Implications for Martian Geochemistry and Habitability

Over the past several decades, elemental sulfur in martian soils and rocks has been detected by a number of missions using X-ray spectroscopy [1-3]. Optical spectroscopy has also provided evidence for widespread sulfates on Mars [4,5]. The ubiquitous presence of sulfur in soils has been interpreted as a widely distributed sulfate mineralogy [6]. However, direct confirmation as to the identity and solubility of the sulfur species in martian soil has never been obtained. One goal of the Wet Chemistry Laboratory (WCL) [7] on board the 2007 Phoenix Mars Lander [8] was to determine soluble sulfate in the martian soil. The WCL received three primary samples. Each sample was added to 25 mL of leaching solution and analysed for solvated ionic species, pH, and conductivity [9,10]. The analysis also showed a discrepancy between charge balance, ionic strength, and conductivity, suggesting unidentified anionic species.

Kounaves, S. P.↗

NASA NTRS2004

Zeolite Formation and Weathering Processes in Dry Valleys of Antartica: Martian Analogs

Terrestrial weathering processes in cold-desert climates such as the Dry Valleys of Antarctica may provide an excellent analog to chemical weathering and diagenesis of soils on Mars. Detailed studies of soil development and the chemical and mineralogical alterations occurring within soil columns in Wright Valley, Antarctica show incredible complexity in the upper meter of soil. Previous workers noted the ice-free Dry Valleys are the best terrestrial approximations to contemporary Mars. Images returned from the Pathfinder and Spirit landers show similarities to surfaces observed within the Dry Valleys. Similarities to Mars that exist in these valleys are: mean temperatures always below freezing (-20 C), no rainfall, sparse snowfall-rapidly removed by sublimation, desiccating winds, diurnal freeze-thaw cycles (even during daylight hours), low humidity, oxidative environment, relatively high solar radiation and low magnetic fields . The Dry Valley soils contain irregular distributions and low abundances of soil microorganisms that are somewhat unusual on Earth. Physical processes-such as sand abrasion-are dominant mechanisms of rock weathering in Antarctica. However, chemical weathering is also an important process even in such extreme climates. For example, ionic migration occurs even in frozen soils along liquid films on individual soil particles. It has also been shown that water with liquid-like properties is present in soils at temperatures on the order of approx.-80 C and it has been observed that the percentage of oxidized iron increases with increasing soil age and enrichments in oxidized iron occurs toward the surface. The presence of evaporates is evident and appear similar to "evaporite sites" within the Pathfinder and Spirit sites. Evaporites indicate ionic migration and chemical activity even in the permanently frozen zone. The presence of evaporates indicates that chemical weathering of rocks and possibly soils has been active. Authogenic zeolites have been identified within the soil columns because they are fragile; i.e. they are euhedral, unabraded, and unfractured, strongly suggesting in situ formation. Their presence in Antarctic samples is another indication that diagenic processes are active in cold-desert environments. The presence of zeolites, and other clays along with halites, sulfates, carbonates, and hydrates are to be expected within the soil columns on Mars at the Gusev and Isidis Planitia regions. The presence of such water-bearing minerals beneath the surface supplies one of the requirements to support biological activity on Mars.

Gibson, E. K., Jr.↗

NASA NTRS2011

NASA Tech Briefs, March 2011

Topics covered include: Optimal Tuner Selection for Kalman-Filter-Based Aircraft Engine Performance Estimation; Airborne Radar Interferometric Repeat-Pass Processing; Plug-and-Play Environmental Monitoring Spacecraft Subsystem; Power-Combined GaN Amplifier with 2.28-W Output Power at 87 GHz; Wallops Ship Surveillance System; Source Lines Counter (SLiC) Version 4.0; Guidance, Navigation, and Control Program; Single-Frame Terrain Mapping Software for Robotic Vehicles; Auto Draw from Excel Input Files; Observation Scheduling System; CFDP for Interplanetary Overlay Network; X-Windows Widget for Image Display; Binary-Signal Recovery; Volumetric 3D Display System with Static Screen; MMIC Replacement for Gunn Diode Oscillators; Feature Acquisition with Imbalanced Training Data; Mount Protects Thin-Walled Glass or Ceramic Tubes from Large Thermal and Vibration Loads; Carbon Nanotube-Based Structural Health Monitoring Sensors; Wireless Inductive Power Device Suppresses Blade Vibrations; Safe, Advanced, Adaptable Isolation System Eliminates the Need for Critical Lifts; Anti-Rotation Device Releasable by Insertion of a Tool; A Magnetically Coupled Cryogenic Pump; Single Piezo-Actuator Rotary-Hammering Drill; Fire-Retardant Polymeric Additives; Catalytic Generation of Lift Gases for Balloons; Ionic Liquids to Replace Hydrazine; Variable Emittance Electrochromics Using Ionic Electrolytes and Low Solar Absorptance Coatings; Spacecraft Radiator Freeze Protection Using a Regenerative Heat Exchanger; Multi-Mission Power Analysis Tool; Correction for Self-Heating When Using Thermometers as Heaters in Precision Control Applications; Gravitational Wave Detection with Single-Laser Atom Interferometers; Titanium Alloy Strong Back for IXO Mirror Segments; Improved Ambient Pressure Pyroelectric Ion Source; Multi-Modal Image Registration and Matching for Localization of a Balloon on Titan; Entanglement in Quantum-Classical Hybrid; Algorithm for Autonomous Landing; Quantum-Classical Hybrid for Information Processing; Small-Scale Dissipation in Binary-Species Transitional Mixing Layers; Superpixel-Augmented Endmember Detection for Hyperspectral Images; Coding for Parallel Links to Maximize the Expected Value of Decodable Messages; and Microwave Tissue Soldering for Immediate Wound Closure.

Source record↗

NASA NTRS2003

Rod/Coil Block Copolyimides for Ion-Conducting Membranes

Rod/coil block copolyimides that exhibit high levels of ionic conduction can be made into diverse products, including dimensionally stable solid electrolyte membranes that function well over wide temperature ranges in fuel cells and in lithium-ion electrochemical cells. These rod/coil block copolyimides were invented to overcome the limitations of polymers now used to make such membranes. They could also be useful in other electrochemical and perhaps some optical applications, as described below. The membranes of amorphous polyethylene oxide (PEO) now used in lithium-ion cells have acceptably large ionic conductivities only at temperatures above 60 C, precluding use in what would otherwise be many potential applications at lower temperatures. PEO is difficult to process, and, except at the highest molecular weights it is not very dimensionally stable. It would be desirable to operate fuel cells at temperatures above 80 C to take advantage of better kinetics of redox reactions and to reduce contamination of catalysts. Unfortunately, proton-conduction performance of a typical perfluorosulfonic polymer membrane now used as a solid electrolyte in a fuel cell decreases with increasing temperature above 80 C because of loss of water from within the membrane. The loss of water has been attributed to the hydrophobic nature of the polymer backbone. In addition, perfluorosulfonic polymers are expensive and are not sufficiently stable for long-term use. Rod/coil block copolyimides are so named because each molecule of such a polymer comprises short polyimide rod segments alternating with flexible polyether coil segments (see figure). The rods and coils can be linear, branched, or mixtures of linear and branched. A unique feature of these polymers is that the rods and coils are highly incompatible, giving rise to a phase separation with a high degree of ordering that creates nanoscale channels in which ions can travel freely. The conduction of ions can occur in the coil phase, the rod phase, or both phases.

Meador, Mary Ann B.↗

NASA NTRS2011

Li-Ion Cells Employing Electrolytes With Methyl Propionate and Ethyl Butyrate Co-Solvents

Future NASA missions aimed at exploring Mars and the outer planets require rechargeable batteries that can operate at low temperatures to satisfy the requirements of such applications as landers, rovers, and penetrators. A number of terrestrial applications, such as hybrid electric vehicles (HEVs) and electric vehicles (EVs) also require energy storage devices that can operate over a wide temperature range (i.e., -40 to +70 C), while still providing high power capability and long life. Currently, the state-of-the-art lithium-ion system has been demonstrated to operate over a wide range of temperatures (-30 to +40 C); however, the rate capability at the lower temperatures is very poor. These limitations at very low temperatures are due to poor electrolyte conductivity, poor lithium intercalation kinetics over the electrode surface layers, and poor ionic diffusion in the electrode bulk. Two wide-operating-temperature-range electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed include further optimization of electrolytes containing methyl propionate (MP) and ethyl butyrate (EB), which are effective co-solvents, to widen the operating temperature range beyond the baseline systems. Attention was focused on further optimizing ester-based electrolyte formulations that have exhibited the best performance at temperatures ranging from -60 to +60 C, with an emphasis upon improving the rate capability at -20 to -40 C. This was accomplished by increasing electrolyte salt concentration to 1.20M and increasing the ester content to 60 percent by volume to increase the ionic conductivity at low temperatures. Two JPL-developed electrolytes 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %) operate effectively over a wide temperature range in MCMB-LiNiCoAlO2 and Li4Ti5O12-LiNi-CoAlO2 prototype cells. These electrolytes have enabled high rate performance at low temperature (i.e., up to 2.0C rates at -50 C and 5.0C rates at -40 C), and good cycling performance over a wide temperature range (i.e., from -40 to +70 C). Current efforts are focused upon improving the high temperature resilience of the methyl propionatebased system through the use of electrolyte additives, which are envisioned to improve the nature of the solid electrolyte interphase (SEI) layers.

Smart, Marshall C.↗

NASA NTRS2012

High-Temperature Shape Memory Polymers

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing radiation ( radiation, neutrons), or by chemical crosslinking to form a covalent permanent network. With respect to other shape memory polymers, this invention is novel in that it describes the use of a thermoplastic composition that can be thermally molded or solution-cast into complex "permanent" shapes, and then reheated or redissolved and recast from solution to prepare another shape. It is also unique in that the shape memory behavior is provided by a non-polymer additive.

Yoonessi, Mitra↗

NASA NTRS2012

Electrodeposition of Metals in Microgravity Conditions

Metal electrodeposition may introduce various morphological variations depending on the electrolytic conditions including cell configurations. For liquid electrolytes, a precise study of these deposits may be complicated by convective motion due to buoyancy. Zero-gravity (0-G) condition provided by drop shaft or parabolic flight gives a straightforward mean to avoid this effect: we present here 0-G electrodeposition experiments, which we compare to ground experiments (1-G). Two electrochemical systems were studied by laser interferometry, allowing to measure the concentration variations in the electrolyte: copper deposition from copper sulfate aqueous solution and lithium deposition from an ionic liquid containing LiTFSI. For copper, concentration variations were in good agreement with theory. For lithium, an apparent induction time was observed for the concentration evolution at 1-G: due to this induction time and to the low diffusion coefficient in ionic liquid, the concentration variations were hardly measurable in the parabolic flight 0-G periods of 20 seconds.

Nishikawa, K.↗

NASA NTRS2013

New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.

Bugga, Ratnakumar V.↗

NASA NTRS2009

Refractory Materials for Flame Deflector Protection System Corrosion Control: Refractory Ceramics Literature Survey

Ceramics can be defmed as a material consisting of hard brittle properties produced from inorganic and nonmetallic minerals made by firing at high temperatures. These materials are compounds between metallic and nonmetallic elements and are either totally ionic, or predominately ionic but having some covalent character. This definition allows for a large range of materials, not all applicable to refractory applications. As this report is focused on potential ceramic materials for high temperature, aggressive exposure applications, the ceramics reviewed as part of this report will focus on refractory ceramics specifically designed and used for these applications. Ceramic materials consist of a wide variety of products. Callister (2000) 1 characterized ceramic materials into six classifications: glasses, clay products, refractories, cements, abrasives, and advanced ceramics. Figure 1 shows this classification system. This review will focus mainly on refractory ceramics and cements as in general, the other classifications are neither applicable nor economical for use in large structures such as the flame trench. Although much work has been done in advanced ceramics over the past decade or so, these materials are likely cost prohibitive and would have to be fabricated off-site, transported to the NASA facilities, and installed, which make these even less feasible. Although the authors reviewed the literature on advanced ceramic refractories 2 center dot 3 center dot 4 center dot 5 center dot 6 center dot 7 center dot 8 center dot 9 center dot 10 center dot 11 center dot 12 after the review it was concluded that these materials should not be ' the focus of this report. A review is in progress on materials and systems for prefabricated refractory ceramic panels, but this review is focusing more on typical refractory materials for prefabricated systems, which could make the system more economically feasible. Refractory ceramics are used for a wide variety of applications. Figure 2 shows many ofthese applications, their life expectancy or requirement, and the exposure temperature for the refractory ceramic. Note that the exposure temperatures for refractory ceramics are very similar to the exposure conditions for specialty ceramics (rocket nozzles, space vehicle re-entry fields, etc.) and yet the life expectancy or requirement is relatively low. Currently NASA is repairing the refractory lining in the flame trench after every launch - although this is not a direct indication of low life expectancy, it does indicate that the current system may not be sufficiently durable to maximize economy. Better performing refractory ceramics are needed to improve the performance, economy, and safety during and after launches at the flame trenches at Kennedy Space Center (KSC). To achieve this goal a current study is underway to assess different refractory systems for possible use in the flame trenches at KSC. This report will target the potential applicability of refractory ceramics for use in the flame trenches. An overview of the different refractory ceramics will be provided (see Figure I). This will be followed with a brief description of the structure of refractory products, the properties and characteristics of different systems, the methodology for selecting refractories, and then a general design methodology. Based on these sections, future challenges and opportunities will be identified with the objective of improving the durability, performance, economy, and safety of the launch complex. Refractory ceramics are used for a wide variety of applications. Figure 2 shows many ofthese applications, their life expectancy or requirement, and the exposure temperature for the refractory ceramic. Note that the exposure temperatures for refractory ceramics are very similar to the exposure conditions for specialty ceramics (rocket nozzles, space vehicle re-entry fields, etc.) and yet the life expectancy or requirement is relatively low. Currently NASA is repairing the refractory lining in the flame trench after every launch - although this is not a direct indication of low life expectancy, it does indicate that the current system may not be sufficiently durable to maximize economy. Better performing refractory ceramics are needed to improve the performance, economy, and safety during and after launches at the flame trenches at Kennedy Space Center (KSC). To achieve this goal a current study is underway to assess different refractory systems for possible use in the flame trenches at KSC. This report will target the potential applicability of refractory ceramics for use in the flame trenches. An overview of the different refractory ceramics will be provided (see Figure I). This will be followed with a brief description of the structure of refractory products, the properties and characteristics of different systems, the methodology for selecting refractories, and then a general design methodology. Based on these sections, future challenges and opportunities will be identified with the objective of improving the durability, performance, economy, and safety of the launch complex.

Calle, Luz Marina↗

NASA NTRS2013

The Mineralogical and Chemical Case for Habitability at Yellowknife Bay, Gale Crater, Mars

Sediments of the Yellowknife Bay formation (Gale crater) include the Sheepbed member, a mudstone cut by light-toned veins. Two drill samples, John Klein and Cumberland, were collected and analyzed by the CheMin XRD/XRF instrument and the Sample Analysis at Mars (SAM) evolved gas and isotopic analysis suite of instruments. Drill cuttings were also analyzed by the Alpha Particle X-ray Spectrometer (APXS) for bulk composition. The CheMin XRD analysis shows that the mudstone contains basaltic minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe-oxide/hydroxides, Fe-sulfides, amorphous materials, and trioctahedral phyllosilicates. SAM evolved gas analysis of higher-temperature OH matches the CheMin XRD estimate of ~20% clay minerals in the mudstone. The light-toned veins contain Ca-sulfates; anhydrite and bassanite are detected by XRD but gypsum is also indicated from Mastcam spectral mapping. These sulfates appear to be almost entirely restricted to late-diagenetic veins. The sulfate content of the mudstone matrix itself is lower than other sediments analyzed on Mars. The presence of phyllosilicates indicates that the activity of water was high during their formation and/or transport and deposition (should they have been detrital). Lack of chlorite places limits on the maximum temperature of alteration (likely <100 C). The presence of Ca-sulfates rather than Mg- or Fe-sulfates suggests that the pore water pH was near-neutral and of relatively low ionic strength (although x-ray amorphous Mg-and Fe- sulfates could be present and undetectable by CheMin). The presence of Fe and S in both reduced and oxidized states represents chemical disequilibria that could have been utilized by chemolithoautotrophic biota, if present. When compared to the nearby Rocknest sand shadow mineralogy or the normative mineralogy of Martian soil, both John Klein and Cumberland exhibit a near-absence of olivine and a surplus of magnetite (7-9% of the crystalline component). The magnetite is interpreted as an authigenic product formed when olivine was altered to phyllosilicate. Saponitization of olivine (a process analogous to serpentinization) could have produced H2 in situ. Indeed, early diagenetic hollow nodules ("minibowls") present in the Cumberland mudstone are interpreted by some as forming when gas bubbles accumulated in the unconsolidated mudstone. Lastly, all of these early diagenetic features appear to have been preserved with minimal alteration since their formation, as indicated by the ease of drilling (weak lithification, lack of cementing phases), the presence of 20-30% amorphous material, and the late-stage fracturing with emplacement of calcium sulfate veins and minibowl infills, where they were intersected by veins. A rough estimate of the minimum duration of the lacustrine environment is provided by the minimum thickness of the Sheepbed member. Given 1.5 meters, and applying a mean sediment accumulation rate for lacustrine strata of 1 m/1000 yrs yields a duration of 1,500 years. If the aqueous environments represented by overlying strata are considered, such as Gillespie Lake and Shaler, then this duration increases. The Sheepbed mudstone meets all the requirements of a habitable environment: Aqueous deposition at clement conditions of P, T, pH, Eh and ionic strength, plus the availability of sources of chemical energy.

Blake, David Frederick↗

NASA NTRS2014

Lithium-Based High Energy Density Flow Batteries

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

Bugga, Ratnakumar V.↗