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NASA NTRS2010

Comparative Spectra of Oxygen-Rich Versus Carbon-Rich Circumstellar Shells: VY Canis Majoris and IRC(plus)10216 at 215-285 GHz

A sensitive (1sigma rms at 1 MHz resolution approx.3 mK) 1 mm spectral line survey (214.5-285.5 GHz) of VY Canis Majoris (VY CMa) and IRC +10216 has been conducted to compare the chemistries of oxygen- and carbon-rich circumstellar envelopes. This study was carried out using the Submillimeter Telescope of the Arizona Radio Observatory with a new Atacama Large Millimeter Array type receiver. This survey is the first to chemically characterize an O-rich circumstellar shell at millimeter wavelengths. In VY CMa, 128 emission features were detected arising from 18 different molecules; and in IRC +10216, 720 lines were observed, assigned to 32 different species. The 1 mm spectrum of VY CMa is dominated by SO, and SiS; in IRC +10216, C4H and SiC2 are the most recurrent species. Ten molecules were common to both sources: CO, SiS, SiO, CS, CN, HCN, HNC, NaCl, PN, and HCO(+). Sulfur plays an important role in VY CMa, but saturated/ unsaturated carbon dominates the molecular content of IRC +102.16, producing CH2NH, for example. Although the molecular complexity of IRC +10216 is greater, VY CMa supports a unique "inorganic" chemistry leading to the oxides PO, AlO, and AlOH. Only diatomic and triatomic compounds were observed in VY CMa, while species with four or more atoms are common in IRC +10216, reflecting carbon's ability to form multiple strong bonds, unlike oxygen. In VY CMa, a new water maser (v2 = 2) has been found, as well as vibrationally excited NaCl. Toward IRC +10216, vibrationally excited CCH was detected for the first time.

Tenebaum, E. D.↗

NASA NTRS2022

Structural and chemical complexity of minerals: An update

The complexities of chemical composition and crystal structure are fundamental characteristics of minerals that have high relevance to the understanding of their stability, occurrence and evolution. This review summarises recent developments in the field of mineral complexity and outlines possible directions for its future elaboration. The database of structural and chemical complexity parameters of minerals is updated by H-correction of structures with unknown H positions and the inclusion of new data. The revised average complexity values (arithmetic means) for all minerals are 3.54(2) bits/atom and 345(10) bits/cell (based upon 4443 structure reports). The distributions of atomic information amounts, chemIG and strIG, versus the number of mineral species fit the normal modes, whereas the distributions of total complexities, chemIG,total and strIG,total, along with numbers of atoms per formula and per unit cell are log normal. The three most complex mineral species known today are ewingite, morrisonite and ilmajokite, all either discovered or structurally characterised within the last five years. The most important complexity-generating mechanisms in minerals are: (1) the presence of isolated large clusters; (2) the presence of large clusters linked together to form three-dimensional frameworks; (3) formation of complex three-dimensional modular frameworks; (4) formation of complex modular layers; (5) high hydration state in salts with complex heteropolyhedral units; and (6) formation of ordered superstructures of relatively simple structure types. The relations between symmetry and complexity are considered. The analysis of temporal dynamics of mineralogical discoveries since 1875 with the step of 25 years show the increasing chemical and structural complexities of human knowledge of the mineral kingdom in the history of mineralogy. In the Earth’s history, both diversity and complexity of minerals experience dramatic increases associated with the formation of Earth’s continental crust, initiation of plate tectonics and the Great Oxidation event.

complexity↗

NASA NTRS2001

The Cool Flames Experiment

A space-based experiment is currently under development to study diffusion-controlled, gas-phase, low temperature oxidation reactions, cool flames and auto-ignition in an unstirred, static reactor. At Earth's gravity (1g), natural convection due to self-heating during the course of slow reaction dominates diffusive transport and produces spatio-temporal variations in the thermal and thus species concentration profiles via the Arrhenius temperature dependence of the reaction rates. Natural convection is important in all terrestrial cool flame and auto-ignition studies, except for select low pressure, highly dilute (small temperature excess) studies in small vessels (i.e., small Rayleigh number). On Earth, natural convection occurs when the Rayleigh number (Ra) exceeds a critical value of approximately 600. Typical values of the Ra, associated with cool flames and auto-ignitions, range from 104-105 (or larger), a regime where both natural convection and conduction heat transport are important. When natural convection occurs, it alters the temperature, hydrodynamic, and species concentration fields, thus generating a multi-dimensional field that is extremely difficult, if not impossible, to be modeled analytically. This point has been emphasized recently by Kagan and co-workers who have shown that explosion limits can shift depending on the characteristic length scale associated with the natural convection. Moreover, natural convection in unstirred reactors is never "sufficiently strong to generate a spatially uniform temperature distribution throughout the reacting gas." Thus, an unstirred, nonisothermal reaction on Earth does not reduce to that generated in a mechanically, well-stirred system. Interestingly, however, thermal ignition theories and thermokinetic models neglect natural convection and assume a heat transfer correlation of the form: q=h(S/V)(T(bar) - Tw) where q is the heat loss per unit volume, h is the heat transfer coefficient, S/V is the surface to volume ratio, and (T(bar) - Tw ) is the spatially averaged temperature excess. This Newtonian form has been validated in spatially-uniform, well-stirred reactors, provided the effective heat transfer coefficient associated with the unsteady process is properly evaluated. Unfortunately, it is not a valid assumption for spatially-nonuniform temperature distributions induced by natural convection in unstirred reactors. "This is why the analysis of such a system is so difficult." Historically, the complexities associated with natural convection were perhaps recognized as early as 1938 when thermal ignition theory was first developed. In the 1955 text "Diffusion and Heat Exchange in Chemical Kinetics", Frank-Kamenetskii recognized that "the purely conductive theory can be applied at sufficiently low pressure and small dimensions of the vessel when the influence of natural convection can be disregarded." This was reiterated by Tyler in 1966 and further emphasized by Barnard and Harwood in 1974. Specifically, they state: "It is generally assumed that heat losses are purely conductive. While this may be valid for certain low pressure slow combustion regimes, it is unlikely to be true for the cool flame and ignition regimes." While this statement is true for terrestrial experiments, the purely conductive heat transport assumption is valid at microgravity (mu-g). Specifically, buoyant complexities are suppressed at mu-g and the reaction-diffusion structure associated with low temperature oxidation reactions, cool flames and auto-ignitions can be studied. Without natural convection, the system is simpler, does not require determination of the effective heat transfer coefficient, and is a testbed for analytic and numerical models that assume pure diffusive transport. In addition, mu-g experiments will provide baseline data that will improve our understanding of the effects of natural convection on Earth.

Pearlman, Howard↗

NASA NTRS1985

Finite element analysis of thermal barrier coatings

The near-term objective is to develop an understanding of the states of stresses and strains in a Zirconia-yttria thermal barrier coating (TBC) experiencing a given temperature drop. Results so obtained are expected to facilitate experimental work. In order to gain realistic insights into the distribution of stresses and strains in a complex TBC, the finite element approach was selected to model a cylindrical TBC specimen. Experimental evidence reported in the literature indicated the presence of rough interface between the ceramic coat and bond coat. Oxidation of the bond coat at ceramic-bond interface was observed, as was a small amount of cracking in the ceramics near the ceramic-bond interface. To account for these complex features, a plane-strain finite element computer program known as TBCOC was developed, taking advantage of a generic computer code known as MARC. This generic code was made available through the use of a supercomputer (Cray 1). The TBCOC model contains 1316 nodal points and 2140 finite elements. It is capable of a uniform isothermal loading. Results of a sample computer run are presented.

Chang, G. C.↗

NASA NTRS2012

Combustion, Complex Fluids, and Fluid Physics Experiments on the ISS

From the very first days of human spaceflight, NASA has been conducting experiments in space to understand the effect of weightlessness on physical and chemically reacting systems. NASA Glenn Research Center (GRC) in Cleveland, Ohio has been at the forefront of this research looking at both fundamental studies in microgravity as well as experiments targeted at reducing the risks to long duration human missions to the moon, Mars, and beyond. In the current International Space Station (ISS) era, we now have an orbiting laboratory that provides the highly desired condition of long-duration microgravity. This allows continuous and interactive research similar to Earth-based laboratories. Because of these capabilities, the ISS is an indispensible laboratory for low gravity research. NASA GRC has been actively involved in developing and operating facilities and experiments on the ISS since the beginning of a permanent human presence on November 2, 2000. As the lead Center both Combustion, Fluid Physics, and Acceleration Measurement GRC has led the successful implementation of an Acceleration Measurement systems, the Combustion Integrated Rack (CIR), the Fluids Integrated Rack (FIR) as well as the continued use of other facilities on the ISS. These facilities have supported combustion experiments in fundamental droplet combustion fire detection fire extinguishment soot phenomena flame liftoff and stability and material flammability. The fluids experiments have studied capillary flow magneto-rheological fluids colloidal systems extensional rheology pool and nucleate boiling phenomena. In this paper, we provide an overview of the experiments conducted on the ISS over the past 12 years. We also provide a look to the future development. Experiments presented in combustion include areas such as droplet combustion, gaseous diffusion flames, solid fuels, premixed flame studies, fire safety, and super critical oxidation processes. In fluid physics, experiments are discussed in multiphase flows, capillary phenomena, and heat pipes. Finally in complex fluids, experiments in rheology and soft condensed materials will be presented.

Motil, Brian↗

NASA NTRS2004

Dielectric Constant Measurements on Lunar Soils and Terrestrial Minerals

The return to the Moon has ignited the need to characterize the lunar regolith using in situ methods. An examination of the lunar regolith samples collected by the Apollo astronauts indicates that only a few minerals (silicates and oxides) need be considered for in situ resource utilization (ISRU). This simplifies the measurement requirements and allows a detailed analysis using simple methods. Characterizing the physical properties of the rocks and soils is difficult because of many complex parameters such as soil temperature, mineral type, grain size, porosity, and soil conductivity. In this presentation, we will show that the dielectric constant measurement can provide simple detection for oxides such as TiO2, FeO, and water. Their presence is manifest by an unusually large imaginary permittivity.

Anderson, R. C.↗

NASA NTRS1977

A strategy for analysis of thermal decomposition of polymeric materials

Some analytical methods developed in flammability research are reviewed. Computerized analytical systems are used to separate, identify, and quantify components of complex mixtures of low-boiling volatiles, high-boiling volatiles, and solid residues resulting from pyrolysis, oxidative degradation, and flaming combustion processes. To demonstrate the procedure for determining a material's response to a thermal flux administered under dynamic conditions, the treatment of data is reported for samples of an aromatic polyamide fabric which were degraded under isothermal conditions of 550 C following a dynamic heating rate of 100 C/min from ambient to final temperature.

Einhorn, I. N.↗

NASA NTRS1986

Alloy chemistry and microstructural control to meet the demands of the automotive Stirling engine

The automotive Stirling engine now under development by DOE/NASA as an alternative to the internal combustion engine, imposes severe materials requirements for the hot portion of the engine. Materials selected must be low cost and contain a minimum of strategic elements so that availability is not a problem. Heater head tubes contain high pressure hydrogen on the inside and are exposed to hot combustion gases on the outside surface. The cylinders and regenerator housings must be readily castable into complex shapes having varying wall thicknesses and be amenable to brazing and welding operations. Also, high strength, oxidation resistance, resistance to hydrogen permeation, cyclic operation, and long-life are required. A research program conducted by NASA Lewis focused on alloy chemistry and microstructural control to achieve the desired properties over the life of the engine. Results of alloy selection, characterization, evaluation, and actual engine testing of selected materials are presented.

Stephens, J. R.↗

NASA NTRS1988

Alloy chemistry and microstructural control to meet the demands of the automotive Stirling engine

Stephens, Joseph R.↗

NASA NTRS1994

Origins of interstellar and solar system: Carbonaceous materials

Carbon is a crucial atom in cosmochemistry. It is well-established that carbon is synthesized in stellar interiors after the main sequence, is ejected by red giants as small carbonaceous grains during their 'carbon star' phase, resides in the interstellar medium, and was later incorporated into the solar system. The mechanisms of carbon grain formation and later chemical processing are complex because, with only small thermodynamic differences, carbon can take on a bewildering variety of forms: diamond; oxides; carbides; graphite; aliphatic hydrocarbons; polycyclic aromatic hydrocarbons (PAH's); fullerenes; amorphous carbon; and other compounds. These are evidence for many of the forms of carbon found in astronomical observations. We seek to understand the possible astrophysical sites and conditions of the origins of different forms of carbon by combining state-of-the-art capabilities of carbon chemistry with astrophysical modeling. The work is a collaboration between Prof. Frenklach, a leading carbon materials scientist with both laboratory and computer modeling expertise and Prof. Feigelson, an astrophysicist with interests in star formation. The largest effort under this grant was devoted to developing this concept into a comprehensive quantitative model. In addition to explaining the astronomical properties of red giants producing carbonaceous grains, our model also can incorporate recent meteoritic findings. Finally, our induced nucleation grain formation model provides a natural explanation for the widespread presence of PAH emission bands in the Galactic interstellar medium. A brief synopsis of other activities sponsored under this grant and a list of publications from this grant is included.

Feigelson, Eric D.↗

NASA NTRS1972

Scanning electron microscopy, non-dispersive X-ray analysis and electron microprobe studies of lunar soil, rocks and microbreccia

Silicate glass of composition similar to brown lunar glass was reduced with carbon and hydrogen. The typical complex iron sulfide and metallic iron mound formed by reduction with carbon is zoned. Its interior is metallic iron or a mixture of iron sulfide and metallic iron. The outer layer is pure metallic iron which is generally discontinuous, but the surface of the mound next to the silicate host is iron sulfide. This type of mound commonly has a waist of metallic iron and a void beneath it. The silicate surface of the void is covered with droplets or stringers of iron sulfide. The complex iron sulfide and metallic iron mounds formed by reduction with hydrogen generally are zoned. The outer layer is iron sulfide or a mixture of iron sulfide and metallic iron but the interior is metallic iron and iron sulfide, and the mound material next to the silicate host is iron sulfide. On the surface of some complex mounds, globules of silicate material are present. In one example, the globules consist of particles of aluminum oxide surrounded by silicate material. In turn, the margin of the globules is surrounded by iron sulfide. Dimples are present and surface of the dimples is covered by dendritic sheaths of iron sulfide and isolated metallic iron globules.

Carter, J. L.↗

NASA NTRS1976

Thermomagnetic analysis of meteorites. III - C3 and C4 chondrites

Results are presented for thermomagnetic analysis in a controlled oxygen atmosphere of samples from thirteen C3 chondrites and two C4 chondrites. The examined meteorites are found to have rather diverse thermomagnetic properties, so they are placed into three groups on the basis of their thermomagnetic behavior and magnetic mineralogy: (1) those possibly containing magnetite before heating, but which display a large increase in saturation moment upon cooling to room temperature; (2) those containing magnetite as their major magnetic phase, but which show little change in saturation moment following the heating-cooling cycle; and (3) those which contain iron metal in addition to other magnetic phases. Upper limits are placed on the magnetite content of the five meteorites in group 1 by assuming that the initial saturation moment is due entirely to magnetite, and quantitative estimates of the magnetite content of the four meteorites in group 2 are determined from ambient-temperature saturation magnetization measurements. The data for the six meteorites in group 3 are discussed in terms of nickel content and troilite oxidation. It is concluded that since the magnetic and bulk mineralogies of carbonaceous chondrites are more varied and complex than indicated by whole-rock elemental analyses, the origin of such meteorites cannot be described by a simple model.

Herndon, J. M.↗

NASA NTRS1978

Solar photolysis of water

A cyclic process is described for the solar photolysis of water, including a first stage in which water is reduced in the presence of a Eu(+2) photooxidizable reagent producing hydrogen and spent oxidized Eu(+3) reagent. The spent reagent Eu(+3) is reduced by means of a transition metal ligand complex reductant, RuL(+3) in a photoexcited state, such as a ruthenium pyridyl complex. Due to competing reactions between the photolysis and regeneration products, the photooxidation reaction must be separated from the regeneration in space and time by supporting the reagent and/or the reductant on solid supports and utilizing pH, wavelength and flow control to maximize hydrogen and oxygen production.

Ryason, P. R.↗

NASA NTRS1986

Tensile behavior of Fe-40Al alloys with B and Zr additions

Both Fe-40Al and Fe-40Al-0.1Zr with and without B were produced by the hot extrusion of powdered metal. Tensile properties were determined from room temperature to 1100 K in air. All of the materials possessed some ductility at room temperature, and addition of B caused an increase in ductility and a change in fracture mode from intergranular to transgranular cleavage. At high temperatures, failure was caused primarily by the formation of grain boundary cavities in all of the alloys. The effect of Zr addition was unclear because of the complexity of the various microstructures. Comparison of air and vacuum testing at high temperatures revealed that an apparent oxidation assisted mechanism reduced high temperature ductility in these alloys, especially at 900 K.

Gaydosh, D. J.↗

NASA NTRS1990

In-situ integrated processing and characterization of thin films of high temperature superconductors, dielectrics and semiconductors by MOCVD

In this strategy of depositing the basic building blocks of superconductors, semiconductors, and dielectric having common elements, researchers deposited superconducting films of Y-Ba-Cu-O, semiconductor films of Cu2O, and dielectric films of BaF2 and Y2O3 by metal oxide chemical vapor deposition (MOCVD). By switching source materials entering the chamber, and by using direct writting capability, complex device structures like three-terminal hybrid semiconductors/superconductors transistors can be fabricated. The Y-Ba-Cu-O superconducting thin films on BaF2/YSZ substrates show a T(sub c) of 80 K and are textured with most of the grains having their c-axis or a-axis perpendicular to the substrate. Electrical characteristics as well as structural characteristics of superconductors and related materials obtained by x-ray defraction, electron microscopy, and energy dispersive x-ray analysis are discussed.

Singh, R.↗

NASA NTRS1991

In-situ integrated processing and characterization of thin films of high temperature superconductors, dielectrics and semiconductors by MOCVD

In this strategy of depositing the basic building blocks of superconductors, semiconductors, and dielectrics having common elements, researchers deposited superconducting films of Y-Ba-Cu-O, semiconductor films of Cu2O, and dielectric films of BaF2 and Y2O3 by metal oxide chemical vapor deposition (MOCVD). By switching source materials entering the chamber, and by using direct writing capability, complex device structures like three terminal hybrid semiconductor/superconductor transistors can be fabricated. The Y-Ba-Cu-O superconducting thin films on BaF2/YSZ substrates show a T(sub c) of 80 K and are textured with most of the grains having their c-axis or a-axis perpendicular to the substrate. Electrical characteristics as well as structural characteristics of superconductors and related materials obtained by x-ray deffraction, electron microscopy, and energy dispersive x-ray analysis are discussed.

Singh, R.↗

NASA NTRS1994

Fundamental phenomena on fuel decomposition and boundary layer combustion processes with applications to hybrid rocket motors

An experimental study on the fundamental processes involved in fuel decomposition and boundary layer combustion in hybrid rocket motors is being conducted at the High Pressure Combustion Laboratory of the Pennsylvania State University. This research should provide an engineering technology base for development of large scale hybrid rocket motors as well as a fundamental understanding of the complex processes involved in hybrid propulsion. A high pressure slab motor has been designed for conducting experimental investigations. Oxidizer (LOX or GOX) is injected through the head-end over a solid fuel (HTPB) surface. Experiments using fuels supplied by NASA designated industrial companies will also be conducted. The study focuses on the following areas: measurement and observation of solid fuel burning with LOX or GOX, correlation of solid fuel regression rate with operating conditions, measurement of flame temperature and radical species concentrations, determination of the solid fuel subsurface temperature profile, and utilization of experimental data for validation of a companion theoretical study also being conducted at PSU.

Kuo, Kenneth K.↗

NASA NTRS2022

The Long-Term Evolution of the Atmosphere of Venus: Processes and Feedback Mechanisms

This work reviews the long-term evolution of the atmosphere of Venus, and modulation of its composition by interior/exterior cycling. The formation and evolution of Venus’s atmosphere, leading to contemporary surface conditions, remain hotly debated topics, and involve questions that tie into many disciplines. We explore these various inter-related mechanisms which shaped the evolution of the atmosphere, starting with the volatile sources and sinks. Going from the deep interior to the top of the atmosphere, we describe volcanic out-gassing, surface-atmosphere interactions, and atmosphere escape. Furthermore, we address more complex aspects of the history of Venus, including the role of Late Accretion impacts, how magnetic field generation is tied into long-term evolution, and the implications of geochemical and geodynamical feedback cycles for atmospheric evolution. We highlight plausible end-member evolutionary pathways that Venus could have followed, from accretion to its present-day state, based on modeling and observations. In a first scenario, the planet was desiccated by atmospheric escape during the magma ocean phase. In a second scenario, Venus could have harbored surface liquid water for long periods of time, until its temperate climate was destabilized and it entered a runaway greenhouse phase. In a third scenario, Venus’s inefficient outgassing could have kept water inside the planet, where hy- drogen was trapped in the core and the mantle was oxidized. We discuss existing evidence and future observations/missions required to refine our understanding of the planet’s history and of the complex feedback cycles between the interior, surface, and atmosphere that have been operating in the past, present or future of Venus.

Venus↗