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At least 55 records · Page 3

Slip-Cast Superconductive Parts

Complex shapes fabricated without machining. Nonaqueous slip-casting technique used to form complexly shaped parts from high-temperature superconductive materials like YBa(2)Cu(3)O(7-delta). Such parts useful in motors, vibration dampers, and bearings. In process, organic solvent used as liquid medium. Ceramic molds made by lost-wax process used instead of plaster-of-paris molds, used in aqueous slip-casting but impervious to organic solvents and cannot drain away liquid medium. Organic-solvent-based castings do not stick to ceramic molds as they do to plaster molds.

Wise, Stephanie A.↗

Development of High Conductivity Lithium-Ion Electrolytes for Low Temperature Cell Applications

NASA has continued interest in developing power sources which are capable of operating at low temperatures (-20 C and below) to enable future missions, such as the Mars Rover and Lander. Thus, under a program sponsored by the Mars Exploration Program, we have been involved in developing Li-ion batteries with improved low temperature performance. To accomplish this task, the focus of the research has been upon the development of advanced electrolyte systems with improved low temperature properties. This had led to the identification of a carbonate-based electrolyte, consisting of 1.0 M LiPF6 in EC + DEC + DMC (33:33:34), which has been shown to have excellent performance at -20 C in Li-ion AA-size prototype cells. Other groups are also actively engaged in developing electrolytes which can result in improved low temperature performance of Li-ion cells, including Polystor, Yardney, and Covalent. In addition to developing cells capable of operation at -20 C, there is continued interest in systems which can successfully operate at even lower temperatures (less than -30 C) and at high discharge rates (greater than C/2). Thus, we are currently focusing upon developing advanced electrolytes which are highly conductive at low temperatures and will result in cells capable of operation at -40 C. One approach to improve the low temperature conductivity of ethylene carbonate-based electrolytes involves adding co-solvents which will decrease the viscosity and extend the liquid range. Candidate solvent additives include formates, acetates, cyclic and aliphatic ethers, lactones, as well as other carbonates. Using this approach, we have prepared a number of electrolytes which contain methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), ethyl proprionate (EP), and 1,2-dimethoxyethane (DME), some of which have been characterized and reported. Other groups have also reported electrolytes based on mixtures of carbonates and acetates. In the present study, electrolytes which have been identified to have good low temperature conductivity and stability were incorporated into lithium-graphite cells for evaluation. Using various electrochemical methods, including ac impedence and DC micropolarization techniques, the film formation characteristics of graphite electrodes in contact with various lectrolyte formulations was investigated.

Smart, M. C.↗

Theory of hydrophobicity: transient cavities in molecular liquids

Observation of the size distribution of transient cavities in computer simulations of water, n-hexane, and n-dodecane under benchtop conditions shows that the sizes of cavities are more sharply defined in liquid water but the most-probable-size cavities are about the same size in each of these liquids. The calculated solvent atomic density in contact with these cavities shows that water applies more force per unit area of cavity surface than do the hydrocarbon liquids. This contact density, or "squeezing" force, reaches a maximum near cavity diameters of 2.4 angstroms. The results for liquid water are compared to the predictions of simple theories and, in addition, to results for a reference simple liquid. The numerical data for water at a range of temperatures are analyzed to extract a surface free energy contribution to the work of formation of atomic-size cavities. Comparison with the liquid-vapor interfacial tensions of the model liquids studied here indicates that the surface free energies extracted for atomic-size cavities cannot be accurately identified with the macroscopic surface tensions of the systems.

NASA Center ARC↗

Microcapsules and Methods for Making

Methods of forming multi-lamellar microcapsules having alternating layers of hydrophilic and hydrophobic immiscible liquid phases have been developed using different polymer/solvent systems. The methods use liquid-liquid diffusion and simultaneous lateral phase separation, controlled by proper timed-sequence exposures of immiscible phases and low shear mixing, to form narrow size distributions of spherical, multilamellar microcapsules. The use of special formulations of solubilized drugs, surfactants, and polymeric co-surfactants in aqueous vehicles which are dispersed in hydrocarbon solvents containing small quantities of oil, low molecular weight co-surfactants and glycerides that are aqueous insoluble enables the formation of unique microcapsules which can carry large amounts of pharmaceuticals in both aqueous and non-aqueous solvent compartments. The liquid microcapsules are quickly formed in a single step and can include a polymeric outer 'skin' which protects the microcapsules during physical manipulation or exposure to high shear forces. Water-in-oil and oil-in-water microcapsules have been formed both in 1 x g and in microgravity, which contain several types of drugs co-encapsulated within different fluid compartments inside the same microcapsule. Large, spherical multi-lamellar microcapsules have been formed including a cytotoxic drug co-encapsulated with a radiocontrast medium which has advantages for chemoembolization of vascular tumors. In certain cases, crystals of the drug form inside the microcapsules providing zero-order and first order, sustained drug release kinetics.

Morrison, Dennis R.↗

Structure of the polymer-solvent interface

The first measurements of ellipticities from the liquid-liquid interface between polymer and solvent mixtures near their consolute points are reported. When scaled according to theory the ellipticities of high molecular weight polystyrene + solvent mixtures are consistent with those from simple, low molecular weight mixtures. The universal value of the scaled ellipticity is approximately 20 percent lower than that predicted by present theories.

Miles, Danny G., Jr.↗

Deposition and material response from Mach 0.3 burner rig combustion of SRC 2 fuels

Collectors at 1173K (900 C) were exposed to the combustion products of a Mach 0.3 burner rig fueled with various industrial turbine liquid fuels from solvent refined coals. Four fuels were employed: a naphtha, a light oil, a wash solvent and a mid-heavy distillate blend. The response of four superalloys (IN-100, U 700, IN 792 and M-509) to exposure to the combustion gases from the SRC-2 naphtha and resultant deposits was also determined. The SRC-2 fuel analysis and insights obtained during the combustion experience are discussed. Particular problems encountered were fuel instability and reactions of the fuel with hardware components. The major metallic elements which contributed to the deposits were copper, iron, chromium, calcium, aluminum, nickel, silicon, titanium, zinc, and sodium. The deposits were found to be mainly metal oxides. An equilibrium thermodynamic analysis was employed to predict the chemical composition of the deposits. The agreement between the predicted and observed compounds was excellent. No hot corrosion was observed. This was expected because the deposits contained very little sodium or potassium and consisted mainly of the unreactive oxides. However, the amounts of deposits formed indicated that fouling is a potential problem with the use of these fuels.

Santoro, G. J.↗

Room-Temperature-Cured Copolymers for Lithium Battery Gel Electrolytes

Polyimide-PEO copolymers (PEO signifies polyethylene oxide) that have branched rod-coil molecular structures and that can be cured into film form at room temperature have been invented for use as gel electrolytes for lithium-ion electric-power cells. These copolymers offer an alternative to previously patented branched rod-coil polyimides that have been considered for use as polymer electrolytes and that must be cured at a temperature of 200 C. In order to obtain sufficient conductivity for lithium ions in practical applications at and below room temperature, it is necessary to imbibe such a polymer with a suitable carbonate solvent or ionic liquid, but the high-temperature cure makes it impossible to incorporate and retain such a liquid within the polymer molecular framework. By eliminating the high-temperature cure, the present invention makes it possible to incorporate the required liquid.

Meador, Mary Ann B.↗

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

Tigelaar, Dean M.↗

Survey of application of radiation to preparative chemistry

The use of radiation for preparative chemistry in liquid solutions is investigated. General principles are presented and preparations involving reduction, oxidation, polymerization, and decomposition are given. The use of various solvents, water, other inorganic liquids and organic liquids for this purpose is discussed. Finally, a commentary is made on some specific applications where radiation chemistry as a preparative technique may be useful.

Philipp, W. H.↗

Branched Rod-Coil Polyimide-Poly(Alkylene Oxide) Copolymers and Electrolyte Compositions

Crosslinked polyimide-poly(alkylene oxide) copolymers capable of holding large volumes of liquid while maintaining good dimensional stability. Copolymers are derived at ambient temperatures from amine endcapped amic-acid oligomers subsequently imidized in solution at increased temperatures, followed by reaction with trifunctional compounds in the presence of various additives. Films of these copolymers hold over four times their weight at room temperature of liquids such as ionic liquids (RTIL) and/or carbonate solvents. These rod-coil polyimide copolymers are used to prepare polymeric electrolytes by adding to the copolymers various amounts of compounds such as ionic liquids (RTIL), lithium trifluoromethane-sulfonimide (LiTFSi) or other lithium salts, and alumina.

Meador, Maryann B.↗

Lithium Polymer Electrolytes and Solid State NMR

Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for participation on a variety of other projects, including aero-gels and carbon graphite mat en als. The goals of the polymer electrolyte research are to improve the physical properties of the polymers. This includes improving conductivity, durability, and expanding the temperature range over which it is effective. Currently, good conductivity is only present at high temperatures. My goals are to experiment with different arrangements of rods and coils to achieve these desirable properties. Some of my experiments include changing the number of repeat units in the polymer, the size of the diamines, and the types of coil. Analysis of these new polymers indicates improvement in some properties, such as lower glass transition temperature; however, they are not as flexible as desired. With further research we hope to produce polymers that encompass all of these properties to a high degree.

Berkeley, Emily R.↗

Resonance spectra of a paramagnetic probe dissolved in a viscous medium

A model is presented for calculating the paramagnetic resonance (EPR) spectrum of vanadyl acetylacetonate (VAAC) dissolved in either a liquid crystal or isotropic solvent. It employs density matrix formulation in the rotating reference frame. The molecules occupy several discrete angles with respect to the magnetic field and can relax to neighboring positions in a characteristic time tau(theta). The form of tau(theta) is found from a diffusion approach, and the magnitude of tau(theta) is a measure of how freely the VAAC probe tumbles in the solvent. Spectra are predicted for values of tau between 10 to the minus 11th power sec and 10 to the minus 7th power sec. The EPR spectrum, in the isotropic case, is obtained be summing the contributions from the allowed angles weighted by the polar volume element, sin theta. When applying the model to the nematic liquid crystal case it is also necessary to multiply by the Saupe distribution function. For this case tau(theta) is obtained from the diffusion approach in which two diffusion constants are employed to reflect the difference in the parallel and perpendicular components of the viscosity.

Kaplan, J. I.↗

Improved ASTM G72 Test Method for Ensuring Adequate Fuel-to-Oxidizer Ratios

The ASTM G72/G72M-15 Standard Test Method for Autogenous Ignition Temperature of Liquids and Solids in a High-Pressure Oxygen-Enriched Environment is currently used to evaluate materials for the ignition susceptibility driven by exposure to external heat in an enriched oxygen environment. Testing performed on highly volatile liquids such as cleaning solvents has proven problematic due to inconsistent test results (non-ignitions). Non-ignition results can be misinterpreted as favorable oxygen compatibility, although they are more likely associated with inadequate fuel-to-oxidizer ratios. Forced evaporation during purging and inadequate sample size were identified as two potential causes for inadequate available sample material during testing. In an effort to maintain adequate fuel-to-oxidizer ratios within the reaction vessel during test, several parameters were considered, including sample size, pretest sample chilling, pretest purging, and test pressure. Tests on a variety of solvents exhibiting a range of volatilities are presented in this paper. A proposed improvement to the standard test protocol as a result of this evaluation is also presented. Execution of the final proposed improved test protocol outlines an incremental step method of determining optimal conditions using increased sample sizes while considering test system safety limits. The proposed improved test method increases confidence in results obtained by utilizing the ASTM G72 autogenous ignition temperature test method and can aid in the oxygen compatibility assessment of highly volatile liquids and other conditions that may lead to false non-ignition results.

Juarez, Alfredo↗

Improved ASTM G72 Test Method for Ensuring Adequate Fuel-to-Oxidizer Ratios

The ASTM G72/G72M-15 Standard Test Method for Autogenous Ignition Temperature of Liquids and Solids in a High-Pressure Oxygen-Enriched Environment is currently used to evaluate materials for the ignition susceptibility driven by exposure to external heat in an enriched oxygen environment. Testing performed on highly volatile liquids such as cleaning solvents has proven problematic due to inconsistent test results (non-ignitions). Non-ignition results can be misinterpreted as favorable oxygen compatibility, although they are more likely associated with inadequate fuel-to-oxidizer ratios. Forced evaporation during purging and inadequate sample size were identified as two potential causes for inadequate available sample material during testing. In an effort to maintain adequate fuel-to-oxidizer ratios within the reaction vessel during test, several parameters were considered, including sample size, pretest sample chilling, pretest purging, and test pressure. Tests on a variety of solvents exhibiting a range of volatilities are presented in this paper. A proposed improvement to the standard test protocol as a result of this evaluation is also presented. Execution of the final proposed improved test protocol outlines an incremental step method of determining optimal conditions using increased sample sizes while considering test system safety limits. The proposed improved test method increases confidence in results obtained by utilizing the ASTM G72 autogenous ignition temperature test method and can aid in the oxygen compatibility assessment of highly volatile liquids and other conditions that may lead to false non-ignition results.

Juarez, Alfredo↗

[Corrected Title: Solid-Phase Extraction of Polar Compounds from Water] Automated Electrostatics Environmental Chamber

A solid-phase extraction (SPE) process has been developed for removing alcohols, carboxylic acids, aldehydes, ketones, amines, and other polar organic compounds from water. This process can be either a subprocess of a water-reclamation process or a means of extracting organic compounds from water samples for gas-chromatographic analysis. This SPE process is an attractive alternative to an Environmental Protection Administration liquid-liquid extraction process that generates some pollution and does not work in a microgravitational environment. In this SPE process, one forces a water sample through a resin bed by use of positive pressure on the upstream side and/or suction on the downstream side, thereby causing organic compounds from the water to be adsorbed onto the resin. If gas-chromatographic analysis is to be done, the resin is dried by use of a suitable gas, then the adsorbed compounds are extracted from the resin by use of a solvent. Unlike the liquid-liquid process, the SPE process works in both microgravity and Earth gravity. In comparison with the liquid-liquid process, the SPE process is more efficient, extracts a wider range of organic compounds, generates less pollution, and costs less.

Sauer, Richard↗

Shear-induced surface alignment of polymer dispersed liquid crystal microdroplets on the boundary layer

Polymer dispersed liquid crystal thin films have been deposited on a glass substrate, utilizing the processes of polymerization and solvent evaporation induced phase separation. Liquid crystal microdroplets trapped on the upper surface of the thin film respond to the shear stress due to air or gas flow on the surface layer. Response to an applied step shear stress input on the surface layer has been measured by measuring the time response of the transmitted light intensity. Initial results on the measurements of the light transmission as a function of the air flow differential pressure indicate that these systems offer features suitable for boundary layer and gas flow sensors.

Parmar, D. S.↗