Properties of nonaqueous electrolytes Quarterly report, 20 Dec. 1966 - 19 Mar. 1967
Properties of nonaqueous electrolytes - preparation of electrolytes, nuclear magnetic resonance structural studies, and physical property determinations
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Properties of nonaqueous electrolytes - preparation of electrolytes, nuclear magnetic resonance structural studies, and physical property determinations
Several model compounds which represent aspects of the chemical structure of the Langley Research Center thermoplastic (LARC-TPI) have been synthesized for comparison studies using wide angle X-ray scattering (WAXS) as the discriminatory tool. The model compounds included N-phenylphthalimide, 3,3',4,4'-benzophenonetetracarboxylic diphthalimide, and N,N'-diphenyl-3,3',4,4'-benzophenonetetracarboxylic diphthalimide. X-ray diffraction studies of appropriate model compounds can yield information to aid in the understanding of polymeric crystallographic structure. Crystallinity and physical property changes can thus be induced into materials having complicated structures by chemical and thermal processes.
A major research and technology program in Probabilistic Structural Analysis Methods (PSAM) is currently being sponsored by the NASA Lewis Research Center with Southwest Research Institute as the prime contractor. This program is motivated by the need to accurately predict structural response in an environment where the loadings, the material properties, and even the structure may be considered random. The heart of PSAM is a software package which combines advanced structural analysis codes with a fast probability integration (FPI) algorithm for the efficient calculation of stochastic structural response. The basic idea of PAAM is simple: make an approximate calculation of system response, including calculation of the associated probabilities, with minimal computation time and cost, based on a simplified representation of the geometry, loads, and material. The deterministic solution resulting should give a reasonable and realistic description of performance-limiting system responses, although some error will be inevitable. If the simple model has correctly captured the basic mechanics of the system, however, including the proper functional dependence of stress, frequency, etc. on design parameters, then the response sensitivities calculated may be of significantly higher accuracy.
Zinc telluride is of interest as a potential electronic device material, particularly as one component in an amorphous superlattice, which is a new class of interesting and potentially useful materials. Some structural and electronic properties of ZnTe films deposited by argon ion beam sputter depoairion are described. Films (up to 3000 angstroms thick) were deposited from a ZnTe target. A beam energy of 1000 eV and a current density of 4 mA/sq. cm. resulted in deposition rates of approximately 70 angstroms/min. The optical band gap was found to be approximately 1.1 eV, indicating an amorphous structure, as compared to a literature value of 2.26 eV for crystalline material. Intrinsic stress measurements showed a thickness dependence, varying from tensile for thicknesses below 850 angstroms to compressive for larger thicknesses. Room temperature conductivity measurement also showed a thickness dependence, with values ranging from 1.86 x to to the -6/ohm. cm. for 300 angstrom film to 2.56 x 10 to the -1/ohm. cm. for a 2600 angstrom film. Measurement of the temperature dependence of the conductivity for these films showed complicated behavior which was thickness dependent. Thinner films showed at least two distinct temperature dependent conductivity mechanisms, as described by a Mott-type model. Thicker films showed only one principal conductivity mechanism, similar to what might be expected for a material with more crystalline character.
Zinc telluride is of interest as a potential electronic device material, particularly as one component in an amorphous superlattice, which is a new class of interesting and potentially useful materials. Some structural and electronic properties of ZnTe films deposited by argon ion beam sputter deposition are described. Films (up to 3000 angstroms thick) were deposited from a ZnTe target. A beam energy of 1000 eV and a current density of 4 mA/sq cm resulted in deposition rates of approximately 70 angstroms/min. The optical band gap was found to be approximately 1.1 eV, indicating an amorphous structure, as compared to a literature value of 2.26 eV for crystalline material. Intrinsic stress measurements showed a thickness dependence, varying from tensile for thicknesses below 850 angstroms to compressive for larger thicknesses. Room temperature conductivity measurement also showed a thickness dependence, with values ranging from 1.86 x 10 to the -6th/ohm cm for 300 angstrom film to 2.56 x 10 to the -1/ohm cm for a 2600 angstrom film. Measurement of the temperature dependence of the conductivity for these films showed complicated behavior which was thickness dependent. Thinner films showed at least two distinct temperature dependent conductivity mechanisms, as described by a Mott-type model. Thicker films showed only one principal conductivity mechanism, similar to what might be expected for a material with more crystalline character.
More than 50 unequivocal peak-ring craters and multiringed impact basins have been identified on Venus from Earth-based Arecibo, Venera 15/16, and Magellan radar images. These ringed craters are relatively pristine, and so serve as an important new dataset that will further understanding of the structural and rheological properties of the venusian surface and of impact mechanics in general. They are also the most direct analogues for craters formed on the Earth in Phanerozoic time. Finite-element simulations of basin collapse and ring formation were undertaken in collaboration with V. J. Hillgren (University of Arizona). These calculations used an axisymmetric version of the viscoelastic finite element code TECTON, modeled structures on the scale of Klenova or Meitner, and demonstrated two major points. First, viscous flow and ring formation are possible on the timescale of crater collapse for the sizes of multiringed basins seen on Venus and heat flows appropriate to the plant. Second, an elastic lithosphere overlying a Newtonian viscous asthenosphere results mainly in uplift beneath the crater. Inward asthenospheric flow mainly occurs at deeper levels. Lithospheric response is dominantly vertical and flexural. Tensional stress maxima occur and ring formation by normal faulting is predicted in some cases, but these predicted rings occur too far out to explain observed ring spacings on Venus (or on the Moon). Overall, these estimates and models suggest that multiringed basin formation is indeed possible at the scales observed on Venus. Furthermore, due to the strong inverse dependence of solid-state viscosity on stress, the absence of Cordilleran-style ring faulting in craters smaller than Meitner or Klenova makes sense. The apparent increase in viscosity of shock-fluidized rock with crater diameter, greater interior temperatures accessed by larger, deeper craters, and decreased non-Newtonian viscosity associated with larger craters may conspire to make the transition with diameter from peak-ring crater to Orientale-type multiringed basin rather abrupt.
The goal was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of the degradation process. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. Modern advanced aerospace applications often require the use of structural materials in high pressure hydrogen environments at temperatures which range from low cryogenic temperatures to very high temperatures (1300 K and greater). Materials proposed for these applications, such as the titanium aluminides, beta-titanium alloys, nickel- and cobalt-based superalloys, molybdenum-rhenium alloys, beryllium, and various beryllides, need to possess a high degree of immunity from hydrogen induced degradation of mechanical properties. In the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak, in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in hydrogen while gamma titanium aluminide exhibits less degradation and beryllium essentially no degradation. The interaction of oxygen with the surface of these materials has been studied, also, in the present program.
A 16 parameter solar concentrator/heat receiver mass model is used in conjunction with Stirling and Brayton Power Conversion System (PCS) performance and mass computer codes to determine the effect of thermal energy storage (TES) material property changes on overall PCS mass as a function of steady state electrical power output. Included in the PCS mass model are component masses as a function of thermal power for: concentrator, heat receiver, heat exchangers (source unless integral with heat receiver, heat sink, regenerator), heat engine units with optional parallel redundancy, power conditioning and control (PC and C), PC and C radiator, main radiator, and structure. Critical TES properties are: melting temperature, heat of fusion, density of the liquid phase, and the ratio of solid-to-liquid density. Preliminary results indicate that even though overalll system efficiency increases with TES melting temperature up to 1400 K for concentrator surface accuracies of 1 mrad or better, reductions in the overall system mass beyond that achievable with lithium fluoride (LiF) can be accomplished only if the heat of fusion is at least 800 kJ/kg and the liquid density is comparable to that of LiF (1880 kg/cu m.
A 16 parameter solar concentrator/heat receiver mass model is used in conjunction with Stirling and Brayton Power Conversion System (PCS) performance and mass computer codes to determine the effect of thermal energy storage (TES) material property changes on overall PCS mass as a function of steady state electrical power output. Included in the PCS mass model are component masses as a function of thermal power for: concentrator, heat receiver, heat exchangers (source unless integral with heat receiver, heat sink, regenerator), heat engine units with optional parallel redundancy, power conditioning and control (PC and C), PC and C radiator, main radiator, and structure. Critical TES properties are: melting temperature, heat of fusion, density of the liquid phase, and the ratio of solid-to-liquid density. Preliminary results indicate that even though overall system efficiency increases with TES melting temperature up to 1400 K for concentrator surface accuracies of 1 mrad or better, reductions in the overall system mass beyond that achievable with lithium fluoride (LiF) can be accomplished only if the heat of fusion is at least 800 kJ/kg and the liquid density is comparable to that of LiF (1800 kg/cu m).
Preflight predictions of the structural temperature distributions during entry are compared with data from the initial Shuttle flight. Finite element thermal analysis programming was used to model the heat flow on Shuttle structures and actual gas properties of air were employed in the analyses of aerodynamic heating. Laminar, separated, and turbulent heat fluxes were calculated for varying locations on the craft using velocity-attitude and angle-of-attack projections taken from the nominal STS-1 trajectory. Temperature time histories of the first flight are compared with laminar and turbulent flow assumptions and an unpredicted rapid cooling 1800 sec into entry is credited to inaccurate assumptions of structural heat dissipative properties or flow conditions in that time phase of the flight; additional discrepancies in descriptions of heating of the upper fuselage are attributed to a lack of knowledge of the complex flow patterns existing over that area of the Shuttle body.
This paper studies the properties of the transmission zeros of flexible structures with non-collocated sensors and actuators. These properties are shown to be considerably more complicated than for the case of collocated structures. In particular, a finite-dimensional non-collocated structure can have zeros which are general complex numbers, rather than purely real or imaginary quantities. Furthermore, the convergence of these zeros to the true values as the order of the model is increased is typically quite complicated.
The Hercules NASA ACT program was established to demonstrate and validate the low cost potential of the automated tow placement process for fabrication of aircraft primary structures. The program is currently being conducted as a cooperative program in collaboration with the Boeing ATCAS Program. The Hercules advanced tow placement process has been in development since 1982 and was developed specifically for composite aircraft structures. The second generation machine, now in operation at Hercules, is a production-ready machine that uses a low cost prepreg tow material form to produce structures with laminate properties equivalent to prepreg tape layup. Current program activities are focused on demonstration of the automated tow placement process for fabrication of subsonic transport aircraft fuselage crown quadrants. We are working with Boeing Commercial Aircraft and Douglas Aircraft during this phase of the program. The Douglas demonstration panels has co-cured skin/stringers, and the Boeing demonstration panel is an intricately bonded part with co-cured skin/stringers and co-bonded frames. Other aircraft structures that were evaluated for the automated tow placement process include engine nacelle components, fuselage pressure bulkheads, and fuselage tail cones. Because of the cylindrical shape of these structures, multiple parts can be fabricated on one two placement tool, thus reducing the cost per pound of the finished part.
Imaging radars with wavelengths in the range of 10 cm to 1 m can deeply penetrate the surface of an icy body, revealing details of the geomorphology, local structure, and electrical properties of the upper layers. Radar studies of icy surfaces on Earth have used the polarization state of backscatter echoes at multiple frequencies to characterize the surface and subsurface properties of glaciers, showing relatively smooth surfaces on the scale of radar wave-lengths, and subsurface scattering from volume scatterers consistent with ice pipes and lenses. These volume scattering effects are evident in enhanced polarization ratios over a limited range of backscatter incidence angles. The Galilean satellites exhibit similarly enhanced polarization ratios and volumetric scattering effects, but the observations are limited in angular resolution, leading to ambiguity in interpreting the scattering mechanisms and their structural implications.
Seventeen fluids of widely varying physical properties and molecular structure were chosen for study. Film thickness and traction were measured simultaneously in point contacts by interferometry, from which a new theory of traction was proposed. Film thickness was measured in line contacts by interferometry and electrical capacitance to establish correlation between these two methods. An interferometric method for the absolute determination of refractive index in the contact zone was developed and applied to point contact fluid entrapments. Electrical capacitance was used to study the thickness and properties of the soft surface film which sometimes forms near a metal-fluid interface.
A consortium of innovative experts in additive manufacturing (AM) comprising Northrup Grumman Technical Services, University of Texas at El Paso (UTEP), Configurable Space Microsystems Innovations & Applications Center (COSMIAC), NASA Glenn Research Center (GRC), and Youngstown State University, have made significant breakthroughs in the goal of creating the first complete 3D printed small satellite. Since AM machines are relatively inexpensive, this should lead to many entrepreneurial opportunities for the small satellite community. Our technology advancements are focused on the challenges of embedding key components within the structure of the article. We have demonstrated, using advanced fused deposition modeling techniques, complex geometric shapes which optimize the spacecraft design. The UTEP Keck Center has developed a method that interrupts the printing process to insert components into specific cavities, resulting in a spacecraft that has minimal internal space allocated for what traditionally were functional purposes. This allows us to increase experiment and instrument capability by provided added volume in a confined small satellite space. Leveraging initial progress made on a NASA contract, the team investigated the potential of new materials that exploit the AM process, producing candidate compositions that exceed the capabilities of traditional materials. These "new materials" being produced and tested include some that have improved radiation shielding, increased permeability, enhanced thermal properties, better conductive properties, and increased structural performance. The team also investigated materials that were previously not possible to be made. Our testing included standard mechanical tests such as vibration, tensile, thermal cycling, and impact resistance as well as radiation and electromagnetic tests. The initial results of these products and their performance will be presented and compared with standard properties. The new materials with the highest probability to disrupt the future of small satellite systems by driving down costs will be highlighted, in conjunction with the electronic embedding process.
Recent measurements conducted from the Pioneer Venus probes and orbiter have provided a significantly improved definition of the solar net flux profile, the gaseous composition, temperature structure, and cloud properties of Venus' lower atmosphere. Using these data, we have carried out a series of one-dimensional radiative-convective equilibrium calculations to determine the viability of the greenhouse model of Venus' high surface temperature and to assess the chief contributors to the greenhouse effect. New sources of infrared opacity include the permitted transitions of SO2, CO, and HCl as well as opacity due to several pressure-induced transitions of CO2. We find that the observed surface temperature and lapse rate structure of the lower atmosphere can be reproduced quite closely with a greenhouse model that contains the water vapor abundance reported by the Venera spectrophotometer experiment. Thus the greenhouse effect can account for essentially all of Venus' high surface temperature. The prime sources of infrared opacity are, in order of importance, CO2, H2O, cloud particles, and SO2, with CO and HCl playing very minor roles.
ZnO is a wide-band-gap oxide material that has many applications. A new potential application of ZnO material is for light emitting devices since its structure and electrical properties are similar to that of the GaN material (a blue laser candidate). It also is a good substrate for fabricating GaN-based devices. Off-axis sputtering technique has revealed great potential in synthesizing excellent oxide materials because the negative ion bombardment is greatly reduced when adatoms condense on substrates. The surface of films grown by off-axis sputtering will be much smoother than that produced in a regular sputtering configuration. A growth mechanism is studied by investigating the morphology and structure of ZnO films under different growth conditions and orientations. ZnO films are deposited on (0001) sapphire and quartz substrates by off- axis sputtering deposition at various oxygen/argon mixture ratios and pressures and at different temperatures. All films reveal highly textured structures on quartz substrates and epitaxial growth on sapphire substrates. Two off-axis configurations, vertical and horizontal orientations are conducted to study the process of film growth, surface morphology, and film structure. X-ray diffraction, scanning probe microscopy, and electrical measurements are used to characterize these films. Detailed results will be discussed in the presentation. Keywords: ZnO, Photonic material, Off-axis sputtering, Growth mechanism
Traditional SiGe thermoelectrics have potential for enhanced figure of merit (ZT) via nano-structuring with a silicide phase, such as WSi2. A second phase of nano-sized silicides can theoretically reduce the lattice component of thermal conductivity without significantly reducing the electrical conductivity. However, experimentally achieving such improvements in line with the theory is complicated by factors such as control of silicide size during sintering, dopant segregation, matrix homogeneity, and sintering kinetics. Samples were prepared using powder metallurgy techniques; including mechano-chemical alloying, via ball milling, and spark plasma sintering for densification. Processing, micro-structural development, and thermoelectric properties will be discussed. Additionally, couple and device level characterization will be introduced.