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All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Oxidation Behavior of GRCop-84 Copper Alloy Assessed

NASA's goal of safe, affordable space transportation calls for increased reliability and lifetimes of launch vehicles, and significant reductions of launch costs. The areas targeted for enhanced performance in the next generation of reusable launch vehicles include combustion chambers and nozzle ramps; therefore, the search is on for suitable liner materials for these components. GRCop-84 (Cu-8Cr-4Nb), an advanced copper alloy developed at the NASA Glenn Research Center in conjunction with Case Western Reserve University, is a candidate. The current liner of the Space Shuttle Main Engine is another copper alloy, NARloy-Z (Cu-3Ag-0.1Zr). It provides a benchmark against which to compare the properties of candidate successors. The thermomechanical properties of GRCop-84 have been shown to be superior, and its physical properties comparable, to those of NARloy-Z. However, environmental durability issues control longevity in this application: because copper oxide scales are not highly protective, most copper alloys are quickly consumed in oxygen environments at elevated temperatures. In consequence, NARloy-Z and most other copper alloys are prone to blanching, a degradation process that occurs through cycles of oxidation-reduction as the oxide is repeatedly formed and removed because of microscale fluctuations in the oxygen-hydrogen fuel systems of rocket engines. The Space Shuttle Main Engine lining typically degraded by blanching-induced hot spots that lead to surface roughening, pore formation, and coolant leakage. Therefore, resistance to oxidation and blanching are key requirements for second-generation reusable launch vehicle liners. The rocket engine ambient includes H2 (fuel) and H2O (combustion product) and is, hence, under reduced oxygen partial pressures. Accordingly, our studies were expanded to include oxygen partial pressures as low as 322 parts per million (ppm) at the temperatures likely to be experienced in service. A comparison of 10-hr weight gains of GRCop-84, NARloy-Z, and pure copper in 0.032, 2.2, and 100 percent oxygen from 550 to 750 C is shown. In 2.2 vol% and higher oxygen content, GRCop-84 oxidation was slower than that of NARloy-Z or Cu, but that advantage was lost or diminished in 322-ppm O2. Over longer (50-hr) exposures in 1.0 atm O2, however, the advantage of GRCop-84 increased significantly, its oxidation rate becoming approximately 10 times slower than those of Cu and NARloy-Z from 500 to 700 C. Weight gains were moderate and the kinetics parabolic for all three materials in 2.2 vol% and higher oxygen content; however, in 322-ppm O2, the scales were nonprotective below about 650 C, as reflected in linear kinetics and large weight gains. The superior oxidation resistance of GRCop-84 is likely related to the kinetics of extra oxygen consumption to form the additional oxides of Cr and Nb detected beneath the GRCop-84 oxide layer. While we continue to evaluate the blanching resistance of GRCop-84 in other tests, these oxidation results indicate that GRCop-84 is suitable as a reusable launch vehicle liner, and in applications where it is desired to use a copper alloy but without the risk of oxidative failure. Three bar charts comparing overall specific weight gains by each of the three materials studied. The top chart is for oxidation in 1.0 atm of oxygen, the middle is for 2.2% oxygen (balance argon), and the bottom is for 0.0322% oxygen. GRCop-84 outperforms the other two materials, showing the least weight gain in nearly all cases.

Thomas-Ogbuji, Linus U.↗
NASA NTRS1995

Effects of confinement on partially premixed flames

Partially premixed combustion is an intermediate regime between the limiting cases of premixed and nonpremixed combustion. Although combustion problems are generally approached from one of these two limiting cases, there are many practical situations where flames cannot be considered as purely premixed or nonpremixed, and thus the partially premixed approach must be used. In partially premixed combustion, mechanisms from the premixed and nonpremixed regimes can coexist, and as a result some interesting new phenomena can arise. One such phenomenon is the flame stabilization in laminar mixing layers by triple flames. One of the first observations of triple flames was made by Phillips (1965), who investigated a triple flame propagating in a methane mixing layer. Kioni et al. (1993) also examined triple flames both experimentally and numerically. There have also been numerous analytical studies on the shape and propagation of triple flames under various assumptions by Dold (1989), Dold et al. (1991), and Hartley and Dold (1991). In terms of modeling, Muller et al. (1994) have combined the flamelet formulations for premixed and nonpremixed combustion in order to treat lifted diffusion flames. One common feature in the analytical and numerical studies mentioned above is the assumption of zero heat release, which is necessary to make the problem tractable. The effect of heat release on triple flames was investigated by Ruetsch et al. (1995), where for the unconfined case, flame speeds larger than their premixed counterparts were found. One of the most important practical situations in which these conditions arise is in lifted turbulent jet diffusion flames. At a critical velocity the burning zone of a fuel jet lifts off from the nozzle, moves to increasing distances as the jet velocity increases, and finally blows off. The mechanisms that control these phenomena, i.e. that determine the stability of these flames, are still not understood. In addition to regions where diffusion flame stabilization takes place, partially premixed conditions also exist during the ignition process in nonpremixed systems. Numerical simulations by Reveillon et al. (1994) of the ignition process in a weakly stirred mixture of fuel and oxidizer show that triple flames propagate along lines of stoichiometric mixture fraction throughout the fluid. In addition, Peters (1994) notes that NO(x) emissions are likely to be large in such transient cases, and therefore an understanding of triple flames can provide information concerning pollutant formation. This study extends the work previously done and examines the effects of lateral confinement on partially premixed flames. Once again, we study both the flame structure and propagation.

Ruetsch, G. R.↗
NASA NTRS1979

Modelling turbulent flame ignition and blowout

A statistical mixing model incorporating an overall rate equation to describe the fuel oxidation process was developed for studies of ignition and blowout in a combustor primary zone. This zone is treated as a partially stirred reactor whose composition is described by a statistical ensemble of equal mass fluid elements. This ensemble experiences mixing interactions, which represent the turbulent mixing process, at time intervals governed by an empirically determined mixing frequency. Each mixing interaction is computed by ramdomly selecting two different elements which are then allowed to mix completely so that they reach a mean composition depending on their thermodynamic states prior to mixing. The two elements then separate, and the chemical kinetics proceed depending on their new composition and temperature.

Radhakrishnan, K.↗
NASA NTRS1985

Thermal barrier coating system

An oxide thermal barrier coating comprises ZrO3-Yb2O3 that is plasma sprayed onto a previously applied bond coating. The zirconia is partially stabilized with about 124 w/o ytterbia to insure cubic, monoclinic, and terragonal phases.

Stecura, S.↗
NASA NTRS1997

Premixed Atmosphere and Convection Influences on Flame Inhibition and Combustion (Pacific)

Flame spread over flat solid fuel beds is a useful paradigm for studying the behavior of more complex two-phase nonpremixed flames. For practical applications, two of the most important elements of flame spreading are the effects of (1) the ambient atmosphere (e.g. pressure and composition) and (2) the flow environment on the spread rate and extinction conditions. Concerning (1), studies of flame spread in vitiated air and non-standard atmospheres such as those found in undersea vessels and spacecraft are particularly important for the assessment of fire hazards in these environments as well as determination of the effectiveness of fire suppressants. Concerning (2), the flow environment may vary widely even when no forced flow is present because of buoyancy effects. Consequently, the goal of this work is to employ microgravity (micro g) experiments to extend previous studies of the effects of ambient atmosphere and the flow environment on flame spread through the use of microgravity (micro g) experiments. Because of the considerable differences between upward (concurrent-flow) and downward (opposed-flow) flame spread at 1g (Williams, 1976, Fernandez-Pello, 1984), in this work both upward and downward 1g spread are tested. Two types of changes to the oxidizing atmosphere are considered in this work. One is the addition of sub-flammability-limit concentrations of a gaseous fuel ('partially premixed' atmospheres). This is of interest because in fires in enclosures, combustion may occur under poorly ventilated conditions, so that oxygen is partially depleted from the air and is replaced by combustible gases such as fuel vapors, H2 or CO. Subsequent fire spread over the solid fuel could occur under conditions of varying oxygen and gaseous fuel content. The potential significance of flame spread under vitiated or partially premixed conditions has been noted previously (Beyler, 1984). The second change is the diluent type, which affects the radiative properties of the mixture as well as the Lewis number (Le) of the reactants in the atmosphere, which for oxygen is defined as the thermal diffusivity of the bulk mixture divided by the mass diffusivity of oxygen into the bulk mixture. Understanding the effect of diluent type is desirable because in some undersea and spaceborne habitations, it is desirable to use diluent gases other than nitrogen. Prior experiments have shown that both radiation (Bhattacharjee and Altenkirch, 1993) and Lewis number (Zhang et al, 1992) effects are important in flame spreading problems.

Honda, Linton K.↗
NASA NTRS2007

Process for High-Rate Fabrication of Alumina Nanotemplates

An anodizing process, at an early stage of development at the time of reporting the information for this article, has shown promise as a means of fabricating alumina nanotemplates integrated with silicon wafers. Alumina nanotemplates are basically layers of alumina, typically several microns thick, in which are formed approximately regular hexagonal arrays of holes having typical diameters of the order of 10 to 100 nm. Interest in alumina nanotemplates has grown in recent years because they have been found to be useful as templates in the fabrication of nanoscale magnetic, electronic, optoelectronic, and other devices. The present anodizing process is attractive for the fabrication of alumina nanotemplates integrated with silicon wafers in two respects: (1) the process involves self-ordering of the holes; that is, the holes as formed by the process are spontaneously arranged in approximately regular hexagonal arrays; and (2) the rates of growth (that is, elongation) of the holes are high enough to make the process compatible with other processes used in the mass production of integrated circuits. In preparation for fabrication of alumina nanotemplates in this process, one first uses electron-beam evaporation to deposit thin films of titanium, followed by thin films of aluminum, on silicon wafers. Then the alumina nanotemplates are formed by anodizing the aluminum layers, as described below. In experiments in which the process was partially developed, the titanium films were 200 A thick and the aluminum films were 5 m thick. The aluminum films were oxidized to alumina, and the arrays of holes were formed by anodizing the aluminum in aqueous solutions of sulfuric and/or oxalic acid at room temperature (see figure). The diameters, spacings, and rates of growth of the holes were found to depend, variously, on the composition of the anodizing solution, the applied current, or the applied potential, as follows: In galvanostatically controlled anodizing, regardless of the chemical composition of the solution, relatively high current densities (50 to 100 mA/cm2) resulted in arrays of holes that were more nearly regular than were those formed at lower current densities. . The rates of elongation of the holes were found to depend linearly on the applied current density: the observed factor of proportionality was 1.2 (m/h)/(mA/cm2). For a given fixed current density and room temperature, the hole diameters were found to depend mainly on the chemical compositions of the anodizing solutions. The holes produced in sulfuric acid solutions were smaller than those produced in oxalic acid solutions. The arrays of holes produced in sulfuric acid were more ordered than were those produced in oxalic acid. . The breakdown voltage was found to decrease logarithmically with increasing concentration of sulfuric acid. The breakdown voltage was also found to decrease with temperature and to be accompanied by a decrease in hole diameter. The hole diameter was found to vary linearly with applied potential, with a slope of 2.1 nm/V. This slope differs from slopes (2.2 and 2.77 nm/V) reported for similar prior measurements on nanotemplates made from bulk aluminum. The differences among these slopes may be attributable to differences among impurities and defects in bulk and electron-beam-evaporated aluminum specimens.

Myung, Nosang↗
NASA NTRS2001

YC-1 activation of human soluble guanylyl cyclase has both heme-dependent and heme-independent components

YC-1 [3-(5'-hydroxymethyl-2'furyl)-1-benzyl indazole] is an allosteric activator of soluble guanylyl cyclase (sGC). YC-1 increases the catalytic rate of the enzyme and sensitizes the enzyme toward its gaseous activators nitric oxide or carbon monoxide. In other studies the administration of YC-1 to experimental animals resulted in the inhibition of the platelet-rich thrombosis and a decrease of the mean arterial pressure, which correlated with increased cGMP levels. However, details of YC-1 interaction with sGC and enzyme activation are incomplete. Although evidence in the literature indicates that YC-1 activation of sGC is strictly heme-dependent, this report presents evidence for both heme-dependent and heme-independent activation of sGC by YC-1. The oxidation of the sGC heme by 1H-(1,2,4)oxadiazole(4,3-a)quinoxalin-1-one completely inhibited the response to NO, but only partially attenuated activation by YC-1. We also observed activation by YC-1 of a mutant sGC, which lacks heme. These findings indicate that YC-1 activation of sGC can occur independently of heme, but that activation is substantially increased when the heme moiety is present in the enzyme.

NASA Discipline Cardiopulmonary↗
NASA NTRS1986

Sliding Seal Materials for Adiabatic Engines, Phase 2

An essential task in the development of the heavy-duty adiabatic diesel engine is identification and improvements of reliable, low-friction piston seal materials. In the present study, the sliding friction coefficients and wear rates of promising carbide, oxide, and nitride materials were measured under temperature, environmental, velocity, and loading conditions that are representative of the adiabatic engine environment. In addition, silicon nitride and partially stabilized zirconia disks were ion implanted with TiNi, Ni, Co, and Cr, and subsequently run against carbide pins, with the objective of producing reduced friction via solid lubrication at elevated temperature. In order to provide guidance needed to improve materials for this application, the program stressed fundamental understanding of the mechanisms involved in friction and wear. Electron microscopy was used to elucidate the micromechanisms of wear following wear testing, and Auger electron spectroscopy was used to evaluate interface/environment interactions which seemed to be important in the friction and wear process. Unmodified ceramic sliding couples were characterized at all temperatures by friction coefficients of 0.24 and above. The coefficient at 800 C in an oxidizing environment was reduced to below 0.1, for certain material combinations, by the ion implanation of TiNi or Co. This beneficial effect was found to derive from lubricious Ti, Ni, and Co oxides.

Lankford, J.↗
NASA NTRS1985

Space Transportatioin System (STS) propellant scavenging system study. Volume 3: Cost and work breakdown structure-dictionary

Fundamentally, the volumes of the oxidizer and fuel propellant scavenged from the orbiter and external tank determine the size and weight of the scavenging system. The optimization of system dimensions and weights is stimulated by the requirement to minimize the use of partial length of the orbiter payload bay. Thus, the cost estimates begin with weights established for the optimum design. Both the design, development, test, and evaluation and theoretical first unit hardware production costs are estimated from parametric cost weight scaling relations for four subsystems. For cryogenic propellants, the widely differing characteristics of the oxidizer and the fuel lead to two separate tank subsystems, in addition to the electrical and instrumentation subsystems. Hardwares costs also involve quantity, as an independent variable, since the number of production scavenging systems is not firm. For storable propellants, since the tankage volume of the oxidizer and fuel are equal, the hardware production costs for developing these systems are lower than for cryogenic propellants.

Source record↗
NASA NTRS2005

The Rio Tinto Basin, Spain: Mineralogy, Sedimentary Geobiology, and Implications for Interpretation of Outcrop Rocks at Meridiani Planum, Mars

Exploration by the NASA rover Opportunity has revealed sulfate- and hematite-rich sedimentary rocks exposed in craters and other surface features of Meridiani Planum, Mars. Modern, Holocene, and Plio-Pleistocene deposits of the Rio Tinto, southwestern Spain, provide at least a partial environmental analog to Meridiani Planum rocks, facilitating our understanding of Meridiani mineral precipitation and diagenesis, while informing considerations of martian astrobiology. Oxidation, thought to be biologically mediated, of pyritic ore bodies by groundwaters in the source area of the Rio Tinto generates headwaters enriched in sulfuric acid and ferric iron. Seasonal evaporation of river water drives precipitation of hydronium jarosite and schwertmannite, while (Mg,Al,Fe(sup 3+))-copiapite, coquimbite, gypsum, and other sulfate minerals precipitate nearby as efflorescences where locally variable source waters are brought to the surface by capillary action. During the wet season, hydrolysis of sulfate salts results in the precipitation of nanophase goethite. Holocene and Plio-Pleistocene terraces show increasing goethite crystallinity and then replacement of goethite with hematite through time. Hematite in Meridiani spherules also formed during diagenesis, although whether these replaced precursor goethite or precipitated directly from groundwaters is not known. The retention of jarosite and other soluble sulfate salts suggests that water limited the diagenesis of Meridiani rocks. Diverse prokaryotic and eukaryotic microorganisms inhabit acidic and seasonally dry Rio Tinto environments. Organic matter does not persist in Rio Tinto sediments, but biosignatures imparted to sedimentary rocks as macroscopic textures of coated microbial streamers, surface blisters formed by biogenic gas, and microfossils preserved as casts and molds in iron oxides help to shape strategies for astrobiological investigation of Meridiani outcrops.

Fernandez-Remolar, David C.↗
NASA NTRS1971

Improved reflective coating for integrating spheres

Inorganic salts or oxide material is transparent in single-crystal form, has high refractive index, smooth cleavage, and chemical stability, is stable to radiations of interest, partially soluble and easily dispersed in liquid for spraying, and readily dried /cured/ with reasonable cohesion and adhesion, and has good mechanical stability.

Stuart, J. W.↗
NASA NTRS1978

Simultaneous stack gas scrubbing wastewater purification

Variations of a process for removing sulfur dioxide from stack gases and using it to treat municipal waste water are described. The once-through system lowers the pH of the scrubbing water from minor depressions to a pH of about 2.5 under certain conditions. A recycle system uses iron for catalytic oxidation of sulfurous acid to sulfuric acid allowing very large amounts of sulfur dioxide to be absorbed in a small portion of water. The partial recycle system uses municipal wastewater and iron as a scrubbing medium, followed by neutralization of the wastewater with lime to produce an iron hydroxide precipitation which, when removed, produces tertiary quality treated wastewater. The SO2 scrubber is described, test results are analyzed, and a preliminary capital cost estimate for the three processes is included.

Source record↗
NASA NTRS1985

The role of microstructure and phase distribution in the failure mechanisms and life prediction model for PSZ coatings

Partially Stabilized Zirconia (PSZ) may become widely used for Thermal Barrier Coatings (TBC). Failure of these coatings can occur due to thermal fatigue in oxidizing atmospheres. The failure is due to the strains that develop due to thermal gradients, differences in thermal expansion coefficients, and oxidation of the bond coating. The role of microstructure and the cubic, tetragonal, and monoclinic phase distribution in the strain development and subsequent failure will be discussed. An X-ray diffraction technique for accurate determination of the fraction of each phase in PSZ will be applied to understanding the phase transformations and strain development. These results will be discussed in terms of developing a model for life prediction in PSZ coatings during thermal cycling.

Sisson, R. D., Jr.↗
NASA NTRS2006

Volume Ice Radiolysis in the Outer Solar System

The primary energy flux of charged particle components of the heliospheric and magnetospheric environments of the solar system is primarily carried by highly penetrating energetic particles. Although laboratory experiments on production of organics and oxidants typically only address effects on very thin surface layers, energy deposition occurs on surfaces of icy bodies of the outer solar system to meters in depth. Time scales for significant radiolytic deposition vary from thousands of years at millimeter depths on Europa to billions of years in the meters-deep regolith of Kuiper Belt Objects. Radioisotope decay (e.g., K-40) also contributes to volume radiolysis as the only energy source at much greater depths. Radiolytic oxygen is a potential resource for life within Europa and a partial source of oxygen for Saturn's magnetosphere and Titan's upper atmosphere. Interactions of very high energy cosmic rays with ices at Titan's surface may provide one of the few sources of oxidants in that highly reducing environment. The red colors of low-inclination classical Kuiper Belt Objects at 40-50 AU, and Centaur objects originating from this same population, may arise from volume radiolysis of deep ice layers below more refractory radiation crusts eroded away by surface sputtering and micrometeoroid impacts. A variety of techniques are potentially available to measure volume radiolysis products and have been proposed for study as part of the new Space Physics of Life initiative at NASA Goddard Space Flight Center. The technique of Electron Paramagnetic Resonance (EPR) has been used in medical studies to measure oxidant production in irradiated human tissue for cancer treatment. Other potential techniques include optical absorption spectroscopy and standard wet chemical analysis. These and other potential techniques are briefly reviewed for applicability to problems in solar system ice radiolysis and astrobiology.

Cooper, John F.↗
NASA NTRS1971

Influence of the chemical bond on the K emission spectrum of oxygen and fluorine.

The K emission spectrum of oxygen and fluorine from a number of simple oxides and fluorides is divided into three to six sub-peaks. The spectra of many of these oxides and fluorides resemble one another owing to their basically ionic bonding. Certain sub-peaks, however, are ascribed to cross-over transitions and partially covalent energy levels. The different fluorine spectrum of Teflon is due to the hybrid nature of its covalent bonds.

Koster, A. S.↗
NASA NTRS2000

Microgravity Processing of Oxide Superconductors

The primary goal is to understand the microstructures which develop under the nonequilibrium solidification conditions achieved by melt processing in copper oxide superconductor systems. More specifically, to define the liquidus at the Y- 1:2:3 composition, the Nd-1:2:3 composition, and several intermediate partial substitution points between pure Y-1:2:3 and Nd-1:2:3. A secondary goal has been to understand resultant solidification morphologies and pathways under a variety of experimental conditions and to use this knowledge to better characterize solidification phenomena in these systems.

Hofmeister, William H.↗
NASA NTRS1990

Impact fracture experiments simulating interstellar grain-grain collisions

Oxide and silicate grains condensing during the early phases of the formation of the solar system or in the outflow of stars are exposed to high partial pressures of the low-z elements H, C, N and O and their simple gaseous compounds. Though refractory minerals are nominally anhydrous and non-carbonate, if they crystallize in the presence of H2O, N2 and CO or CO2 gases, they dissolve traces of the gaseous components. The question arises: How does the presence of dissolved gases or gas components manifest itself when grain-grain collisions occur. What are the gases emitted when grains are shattered during a collision event. Researchers report on fracture experiments in ultrahigh vacuum (UHV, approximately less than 10 to the -8th power mbar) designed to measure (by means of a quadrupole mass spectrometer, QMS, with microns to ms time resolution) the emission of gases and vapors during and after impact (up to 1.5 sec). Two terrestrial materials were chosen which represent structural and compositional extremes: olivine (San Carlos, AZ), a densely packed Mg-Fe(2+) silicate from the upper mantle, available as 6 to 12 mm single crystals, and obsidian (Oregon), a structurally open, alkaline-SiO2-rich volcanic glass. In the olivine crystals OH- groups have been identified spectroscopically, as well as H2 molecules. Obsidian is a water-rich glass containing OH- besides H2O molecules. Olivine from the mantle often contains CO2, either as CO2-rich fluid in fluid inclusions or structurally dissolved or both. By analogy to synthetic glasses CO2 in the obsidian may be present in form of CO2 molecules in voids of molecular dimensions, or as carbonate anions, CO3(2-). No organic molecules have been detected spectroscopically in either material. Results indicate that refractory oxide/silicates which contain dissolved traces of the H2O and CO/CO2 components but no spectroscopically detectable traces of organics may release complex H-C-O (possibly H-C-N-O) molecules upon fracture, plus metal vapor. This points: (1) at complex reaction mechanisms between dissolved H2O, CO/CO2 (and N2) components within the mineral structure or during fracture, and (2) at the possibility that similar emission processes occur following grain-grain collisions in interstellar dust clouds.

Freund, Friedemann↗
NASA NTRS2010

Carbon Dioxide Control System for a Mars Space Suit Life Support System

Carbon dioxide (CO2) control during Extravehicular Activities (EVAs) on Mars will be challenging. Lithium hydroxide (LiOH) canisters have impractical logistics penalties, and regenerable metal oxide (MetOx) canisters weigh too much. Cycling bed systems and permeable membranes that are regenerable in space vacuum cannot vent on Mars due to the high partial pressure of CO2 in the atmosphere. Although sweep gas regeneration is under investigation, the feasibility, logistics penalties, and failure modes associated with this technique have not been fully determined. TDA Research, Inc. is developing a durable, high-capacity regenerable adsorbent that can remove CO2 from the space suit ventilation loop. The system design allows sorbent regeneration at or above 6 torr, eliminating the potential for Martian atmosphere to leak into the regeneration bed and into the ventilation loop. Regeneration during EVA eliminates the consumable requirement related to the use of LiOH canisters and the mission duration limitations imposed by MetOx system. The concept minimizes the amount of consumable to be brought from Earth and makes the mission more affordable, while providing great operational flexibility during EVA. The feasibility of the concept has been demonstrated in a series of bench-scale experiments and a preliminary system analysis. Results indicate that sorbent regeneration can be accomplished by applying a 14 C temperature swing, while regenerating at 13 torr (well above the Martian atmospheric pressure), withstanding over 1,000 adsorption/regeneration cycles. This paper presents the latest results from these sorbent and system development efforts.

Alptekin, Gokhan↗