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Precision Cleaning of Oxygen Systems and Components

Currently, NASA uses Dichloropentafluoropropane (HCFC-225), a Class II ozone depleting substance (ODs), to clean contaminated oxygen systems. Starting in 20 15, the Montreal Protocols and Clean Air Act prohibit the production and importation of all hydrochlorofluorocarbons (HCFC), except for limited use in refrigeration applications. Thus, a new non-ozone depleting solvent needs to be developed for use in cleaning. Optimally, such a solvent should also be environmentally benign or green to avoid needing to replace the new solvent with yet another solvent in the future due to other environmental concerns. Work for the first year consisted of two parts. The first part was developing a method of testing the cleaning efficiency of potential solvents. Stainless steel coupons were contaminated with a known weight of various contaminants and contaminant combinations and then immersed in solvent for ten minutes. The coupons were then removed and dried in an oven until all solvent had evaporated. Once dry, the coupons were weighed and the mass of the non-volatile residue (NVR) left on the coupon was determined. The cleaning efficiency of the solvents is reported as percent cleaning, with 100% cleaning being zero NVR left on the test coupon. The second half of the first goal was to use the develop method to perform baseline testing on current solvents. The second part of the work was to begin exploring alternative cleaning solvents. A variety of hydrofluorocarbons (HFCs) were tested. Preliminary testing was also performed with ionic liquids and aqueous surfactant solutions. Once potential solvents were identified, an analysis of the performance and environmental characteristics of each was to be conducted. Four contaminants were specified for use in testing. These are Mil-Spec-H-5606 (5606), a hydraulic fluid, Mil-H-83282B (83282), another hydraulic fluid, diethylhexyl sebacate (Sebacate), and WD-40. The structures of these contaminants are all similar, with long aliphatic hydrocarbon chains of lengths between fifteen and fifty. Contaminants were tested both individually and in combination. All combinations were done with equal weights of the constituent contaminants.

McLaughlin, Russell

Ionic Liquids and New Proton Exchange Membranes for Fuel Cells

There is currently a great surge of activity in fuel cell research as laboratories across the world seek to take advantage of the high energy capacity provided by &el cells relative to those of other portable electrochemical power systems. Much of this activity is aimed at high temperature fie1 cells, and a vital component of such &el cells must be the availability of a high temperature stable proton-permeable membrane. NASA Glenn Research Center is greatly involved in developing this technology. Other approaches to the high temperature fuel cell involve the use of single- component or almost-single-component electrolytes that provide a path for protons through the cell. A heavily researched case is the phosphoric acid fuel cell, in which the electrolyte is almost pure phosphoric acid and the cathode reaction produces water directly. The phosphoric acid fie1 cell delivers an open circuit voltage of 0.9 V falling to about 0.7 V under operating conditions at 170 C. The proton transport mechanism is mainly vehicular in character according to the viscosity/conductance relation. Here we describe some Proton Transfer Ionic Liquids (PTILs) with low vapor pressure and high temperature stability that have conductivities of unprecedented magnitude for non-aqueous systems. The first requirement of an ionic liquid is that, contrary to experience with most liquids consisting of ions, it must have a melting point that is not much above room temperature. The limit commonly suggested is 100 C. PTILs constitute an interesting class of non-corrosive proton-exchange electrolyte, which can serve well in high temperature (T = 100 - 250 C) fuel cell applications. We will present cell performance data showing that the open circuit voltage output, and the performance of a simple H2(g)Pt/PTIL/Pt/O2(g) fuel cell may be superior to those of the equivalent phosphoric acid electrolyte fuel cell both at ambient temperature and temperatures up to and above 200 C. My work at NASA Glenn Research Center during this summer is to develop and characterize proton exchange membranes doped with ionic liquids. The main techniques used to characterize these materials are: Impedance Spectroscopy, NMR, DSC, TGA, DMA, IR, and SEM ...

Belieres, Jean-Philippe

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.

Interaction of a sodium ion with the water liquid-vapor interface

Molecular dynamics results are presented for the density profile of a sodium ion near the water liquid-vapor interface at 320 K. These results are compared with the predictions of a simple dielectric model for the interaction of a monovalent ion with this interface. The interfacial region described by the model profile is too narrow and the profile decreases too abruptly near the solution interface. Thus, the simple model does not provide a satisfactory description of the molecular dynamics results for ion positions within two molecular diameters from the solution interface where appreciable ion concentrations are observed. These results suggest that surfaces associated with dielectric models of ionic processes at aqueous solution interfaces should be located at least two molecular diameters inside the liquid phase. A free energy expense of about 2 kcal/mol is required to move the ion within two molecular layers of the free water liquid-vapor interface.

NASA Center ARC

Modeling and Simulation of the Direct Methanol Fuel Cell

From intro.: The direct methanol liquid feed fuel cell uses aqueous solutions of methanol as fuel and oxygen or air as the oxidant and uses an ionically conducting polymer membrane such as Nafion(sup r)117 and the electrolyte. This type of direct oxidation cell is fuel versatile and offers significant advantages in terms of simplicity of design and operation...The present study focuses on the results of a phenomenological model based on current understanding of the various processed operating in these cells.

fuel cell methanol fuel cell methanol

Chemical and physical microenvironments at the Viking landing sites

Physical and chemical considerations permit the division of the near-surface regolith on Mars into at least six zones of distinct microenvironments. The zones are euphotic, duricrust/peds, tempofrost, permafrost, endolithic, and interfacial/transitional. Microenvironments vary significantly in temperature extremes, mean temperature, salt content, relative pressure of water vapor, UV and visible light irradiance, and exposure to ionizing radiation events (100 Mrad) and oxidative molecular species. From what is known of the chemistry of the atmosphere and regolith fines (soil), limits upon the aqueous chemistry of soil pastes may be estimated. Heat of wetting could reach 45 cal/g dry soil; initial pH is indeterminate between 1 and 10; ionic strength and salinity are predicted to be extremely high; freezing point depression is inadequate to provide quantities of liquid water except in special cases. The prospects for biotic survival are grim by terrestrial standards, but the extremes of biological resiliency are inaccessible to evaluation. Second-generation in situ experiments which will better define Martian microenvironments are clearly possible. Antarctic dry valleys are approximations to Martian conditions, but deviate significantly by at least half-a-dozen criteria.

Clark, B. C.

Working Fluids for Increasing Capacities of Heat Pipes

A theoretical and experimental investigation has shown that the capacities of heat pipes can be increased through suitable reformulation of their working fluids. The surface tensions of all of the working fluids heretofore used in heat pipes decrease with temperature. As explained in more detail below, the limits on the performance of a heat pipe are associated with the decrease in the surface tension of the working fluid with temperature, and so one can enhance performance by reformulating the working fluid so that its surface tension increases with temperature. This improvement is applicable to almost any kind of heat pipe in almost any environment. The heat-transfer capacity of a heat pipe in its normal operating-temperature range is subject to a capillary limit and a boiling limit. Both of these limits are associated with the temperature dependence of surface tension of the working fluid. In the case of a traditional working fluid, the decrease in surface tension with temperature causes a body of the liquid phase of the working fluid to move toward a region of lower temperature, thus preventing the desired spreading of the liquid in the heated portion of the heat pipe. As a result, the available capillary-pressure pumping head decreases as the temperature of the evaporator end of the heat pipe increases, and operation becomes unstable. Water has widely been used as a working fluid in heat pipes. Because the surface tension of water decreases with increasing temperature, the heat loads and other aspects of performance of heat pipes that contain water are limited. Dilute aqueous solutions of long-chain alcohols have shown promise as substitutes for water that can offer improved performance, because these solutions exhibit unusual surface-tension characteristics: Experiments have shown that in the cases of an aqueous solution of an alcohol, the molecules of which contain chains of more than four carbon atoms, the surface tension increases with temperature when the temperature exceeds a certain value. There are also other liquids that have surface tensions that increase with temperature and could be used as working fluids in heat pipes. For example, as a substitute for ammonia, which is the working fluid in some heat pipes, one could use a solution of ammonia and an ionic surfactant.

Chao, David F.

Hydrocarbon-Seeded Ignition System for Small Spacecraft Thrusters Using Ionic Liquid Propellants

"Green" propellants based on Ionic-liquids (ILs) like Ammonium DiNitramide and Hydroxyl Ammonium Nitrate have recently been developed as reduced-hazard replacements for hydrazine. Compared to hydrazine, ILs offer up to a 50% improvement in available density-specific impulse. These materials present minimal vapor hazard at room temperature, and this property makes IL's potentially advantageous for "ride-share" launch opportunities where hazards introduced by hydrazine servicing are cost-prohibitive. Even though ILs present a reduced hazard compared to hydrazine, in crystalline form they are potentially explosive and are mixed in aqueous solutions to buffer against explosion. Unfortunately, the high water content makes IL-propellants difficult to ignite and currently a reliable "coldstart" capability does not exist. For reliable ignition, IL-propellants catalyst beds must be pre-heated to greater than 350 C before firing. The required preheat power source is substantial and presents a significant disadvantage for SmallSats where power budgets are extremely limited. Design and development of a "micro-hybrid" igniter designed to act as a "drop-in" replacement for existing IL catalyst beds is presented. The design requires significantly lower input energy and offers a smaller overall form factor. Unlike single-use "squib" pyrotechnic igniters, the system allows the gas generation cycle to be terminated and reinitiated on demand.

Whitmore, Stephen A.

Deposition, Accumulation, and Alteration of Cl(-), NO3(-), ClO4(-) and ClO3(-) Salts in a Hyper-Arid Polar Environment: Mass Balance and Isotopic Constraints

The salt fraction in permafrost soils/sediments of the McMurdo Dry Valleys (MDV) of Antarctica can be used as a proxy for cold desert geochemical processes and paleoclimate reconstruction. Previous analyses of the salt fraction in MDV permafrost soils have largely been conducted in coastal regions where permafrost soils are variably affected by aqueous processes and mixed inputs from marine and stratospheric sources. We expand upon this work by evaluating permafrost soil/sediments in University Valley, located in the ultraxerous zone where both liquid water transport and marine influences are minimal. We determined the abundances of Cl(-), NO3(-, ClO4(-)and ClO3(-)in dry and ice-cemented soil/sediments, snow and glacier ice, and also characterized Cl(-) and NO3(-) isotopically. The data are not consistent with salt deposition in a sublimation till, nor with nuclear weapon testing fall-out, and instead point to a dominantly stratospheric source and to varying degrees of post depositional transformation depending on the substrate, from minimal alteration in bare soils to significant alteration (photodegradation and/or volatilization) in snow and glacier ice. Ionic abundances in the dry permafrost layer indicate limited vertical transport under the current climate conditions, likely due to percolation of snowmelt. Subtle changes in ClO4(-)/NO3(-) ratios and NO3(-) isotopic composition with depth and location may reflect both transport related fractionation and depositional history. Low molar ratios of ClO3(-)/ClO4(-) in surface soils compared to deposition and other arid systems suggest significant post depositional loss of ClO3(-), possibly due to reduction by iron minerals, which may have important implications for oxy-chlorine species on Mars. Salt accumulation varies with distance along the valley and apparent accumulation times based on multiple methods range from approximately 10 to 30 kyr near the glacier to 70-200 kyr near the valley mouth. The relatively young age of the salts and relatively low and homogeneous anion concentrations in the ice-cemented sediments point to either a mechanism of recent salt removal, or to relatively modern permafrost soils (less than 1 million years). Together, our results show that near surface salts in University Valley serve as an end-member of stratospheric sources not subject to biological processes or extensive remobilization.

cold desert geochemical processes

Complex Organics from Laboratory Simulated Interstellar Ices

Many of the volatiles in interstellar dense clouds exist in ices surrounding dust grains. The low temperatures of these ices (T < 50 K) preclude most chemical reactions, but photolysis can drive reactions that produce a suite of new species, many of which are complex organics. We study the UV and proton radiation processing of interstellar ice analogs to explore links between interstellar chemistry, the organics in comets and meteorites, and the origin of life on Earth. The high D/H ratios in some interstellar species, and the knowledge that many of the organics in primitive meteorites are D-enriched, suggest that such links are plausible. Once identified, these species may serve as markers of interstellar heritage of cometary dust and meteorites. Of particular interest are our findings that UV photolysis of interstellar ice analogs produce molecules of importance in current living organisms, including quinones, amphiphiles, and amino acids. Quinones are essential in vital metabolic roles such as electron transport. Studies show that quinones should be made wherever polycyclic aromatic hydrocarbons are photolyzed in interstellar ices. In the case of anthracene-containing ices, we have observed the production of 9-anthrone and 9,10 anthraquinone, both of which have been observed in the Murchison meteorite. Amphiphiles are also made when mixed molecular ices are photolyzed. These amphiphiles self-assemble into fluorescent vesicles when placed in liquid water, as do Murchison extracts. Both have the ability to trap an ionic dye. Photolysis of plausible ices can also produce alanine, serine, and glycine as well as a number of small alcohols and amines. Flash heating of the room temperature residue generated by such experiments generates mass spectral distributions similar to those of IDPs. The detection of high D/H ratios in some interstellar molecular species, and the knowledge that many of the organics, such as hydroxy and amino acids, in primitive meteorites are D-enriched provides evidence for a connection between intact organic material in the interstellar medium and in meteorites. Thus, some of the oxidized aromatics, amphiphiles, amino acids, hydroxy acids, and other compounds found in meteorites may have had an interstellar ancestry and not solely a product of parent body aqueous alteration. Such compounds should also be targeted for searches of organics in cometary dust.

Dworkin, J. P.