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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Chemical constraints governing the origin of metabolism: the thermodynamic landscape of carbon group transformations under mild aqueous conditions

The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies (deltaG) were estimated for four types of reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed (1) that generally when carbon-carbon bond cleavage involves groups from different functional group classes (i.e., carboxylic acids, carbonyl groups, alcohols, and hydrocarbons), the transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) that the energy of carbon-carbon bond transformation is primarily determined by the functional group class of the group that changes oxidation state in the reaction (i.e., the functional group class of the group that donates the shared electron-pair during cleavage, or that accepts the incipient shared electron-pair during synthesis). In contrast, the energy of hydrogen transfer between carbon groups is determined by the functional group class of both the hydrogen-donor group and the hydrogen-acceptor group. From these and other observations we concluded that the chemistry involved in the origin of metabolism (and to a lesser degree modern metabolism) was strongly constrained by (1) the limited redox-based transformation energy of organic substrates that is readily dissipated in a few energetically favorable irreversible reactions; (2) the energy dominance of a few transformation half-reactions that determines whether carbon-carbon bond transformation (cleavage or synthesis) is energetically favorable (deltaG < -3.5 kcal/mol), reversible (deltaG between +/-3.5 kcal/mol), or unfavorable (deltaG > +3.5 kcal/mol); and (3) the dependence of carbon group transformation energy on the functional group class (i.e., oxidation state) of participating groups that in turn is contingent on prior reactions and precursors in the synthetic pathway.

Carbon/chemistry/metabolism↗
NASA NTRS2004

Experimental Study of Lunar and SNC Magmas

The research described in this progress report involved the study of petrological, geochemical, and volcanic processes that occur on the Moon and the SNC meteorite parent body, generally accepted to be Mars. The link between these studies is that they focus on two terrestrial-type parent bodies somewhat smaller than earth, and the fact that they focus on the types of magmas (magma compositions) present, the role of volatiles in magmatic processes, and on processes of magma evolution on these planets. We are also interested in how these processes and magma types varied over time.In earlier work on the A15 green and A17 orange lunar glasses, we discovered a variety of metal blebs. Some of these Fe-Ni metal blebs occur in the glass; others (in A17) were found in olivine phenocrysts that we find make up about 2 vol 96 of the orange glass magma. The importance of these metal spheres is that they fix the oxidation state of the parent magma during the eruption, and also indicate changes during the eruption . They also yield important information about the composition of the gas phase present, the gas that drove the lunar fire-fountaining. During the tenure of this grant, we have continued to work on the remaining questions regarding the origin and evolution of the gas phase in lunar basaltic magmas, what they indicate about the lunar interior, and how the gas affects volcanic eruptions. Work on Martian magmas petrogenesis questions during the tenure of this grant has resulted in advances in our methods of evaluating magmatic oxidation state variations in Mars and some new insights into the compositional variations that existed in the SNC magmas over time . Additionally, Minitti has continued to work on the problem of possible shock effects on the abundance and distribution of water in Mars minerals.

Rutherford, Malcolm J.↗
NASA NTRS2002

Electron energy loss spectroscopy techniques for the study of microbial chromium(VI) reduction

Electron energy loss spectroscopy (EELS) techniques were used to determine oxidation state, at high spatial resolution, of chromium associated with the metal-reducing bacteria, Shewanella oneidensis, in anaerobic cultures containing Cr(VI)O4(2-). These techniques were applied to fixed cells examined in thin section by conventional transmission electron microscopy (TEM) as well as unfixed, hydrated bacteria examined by environmental cell (EC)-TEM. Two distinct populations of bacteria were observed by TEM: bacteria exhibiting low image contrast and bacteria exhibiting high contrast in their cell membrane (or boundary) structure which was often encrusted with high-contrast precipitates. Measurements by EELS demonstrated that cell boundaries became saturated with low concentrations of Cr and the precipitates encrusting bacterial cells contained a reduced form of Cr in oxidation state + 3 or lower.

Evaluation Studies↗
NASA NTRS2003

Solid state potentiometric gaseous oxide sensor

A solid state electrochemical cell (10a) for measuring the concentration of a component of a gas mixture (12) includes first semiconductor electrode (14) and second semiconductor electrode (16) formed from first and second semiconductor materials, respectively. The materials are selected so as to undergo a change in resistivity upon contacting a gas component, such as CO or NO. An electrolyte (18) is provided in contact with the first and second semiconductor electrodes. A reference cell can be included in contact with the electrolyte. Preferably, a voltage response of the first semiconductor electrode is opposite in slope direction to that of the second semiconductor electrode to produce a voltage response equal to the sum of the absolute values of the control system uses measured pollutant concentrations to direct adjustment of engine combustion conditions.

Wachsman, Eric D.↗
NASA NTRS1980

The relation of mantle heterogeneity to the bulk composition and origin of the earth

The heterogeneity of the mantle can be viewed in the context of models for accretion of the terrestrial planets from the solar nebula. Oxygen isotope ratios and mineralogy indicate the existence of hot planetesimals of diverse compositions. Assuming that nebular condensates range from a reduced state near the sun to an oxidized state near Jupiter, a new model is proposed for heterogeneous accretion of the earth beginning with hot, reduced condensates and ending with cool, oxidized condensates. The Ganapathy-Anders cosmochemical model for the bulk composition of the earth was tested by summing measured compositions for the three outer zones and likely compositions for the inner zones. Revisions are suggested, including reduction of the content of the early condensate from that suggested by taking the U concentration as 30 ng/g, as suggested by the naive interpretation of the heat flow.

Smith, J. V.↗
NASA NTRS1993

Oxidation during metamorphism of the ordinary chondrites

It is suggested that some current concepts about the conditions of metamorphism in ordinary chondrites may be flawed. These meteorites display small systematic variations in the oxidation state of Fe. Evidence is presented that oxidation of Fe is linked to metamorphic grade in types 4-6 ordinary chondrites. This conclusion is at variance with a commonly accepted model for chondrite metamorphism that assumes Fe reduction by graphite.

Mcsween, Harry Y., Jr.↗
NASA NTRS1988

Photochemical and thermal modeling in the early atmosphere of the earth

The simplest carbon compounds, present in the terrestrial and planetary atmospheres, exhibit a wide range of oxidation states, carbon dioxide and methane being the most oxidized and the most reduced form of carbon, respectively. The question arises as to the origin and the interconversion among the carbon species. The chemical pathways for the conversion of CH4 to CO and CO2 are for the most part known. The reverse process, the reduction of CO to CH4 is however, poorly understood. A new reaction is proposed, H2CO + H + M yields CH3O + M, which might play a fundamental role in the reduction of CO or CH4. An update is presented of nitrile photochemistry on Titan.

Yung, Yuk L.↗
NASA NTRS2019

X-Ray Photoelectron Spectroscopy

The interaction of photon and the electron goes back to the early part of 19th century emanating from the photo-electric effect depicted by none other than Albert Einstein (Ref 1) described in 1905, and the redistribution of kinetic energy resulting from the interaction of x-ray and solids reported during early part of the century (Ref.2). The spectrum resolutions obtained at that time was not sufficient to observe distinct peaks in spectra for materials. Thus, these phenomena hardly attracted any attention for many years following these discoveries. The modern X-ray Photoelectron Spectroscopy (XPS) has been possible by the extensive and significant contribution from Kai Siegbahn and others (Ref.3, 4) of Uppsala University. Siegbahn developed and employed a high-resolution electron spectrometer that revealed electron peaks in a spectrum emerging from the interaction of x-rays and solids. Eventually, Kai Siegbahn received Nobel Prize in 1981 for his contributions to XPS. Around 1958, shifts in elemental peaks were realized in compounds when the same elements are bound to other but different elements. This discovery resulted in the chemical state identification in various chemicals as well as the oxidation states of atoms in compounds. Because of these useful physical effects, the Uppsala group named XPS with a synonymous name of ESCA (Electron Spectroscopy for Chemical Analysis) used widely today and will be used here alternatively. Therefore, XPS or ESCA not only identifies the element, but also the compound these elements form, from their chemical shifts. Compared to other micro-analytical techniques such as Energy Dispersive (EDS) or Wavelength Dispersive (WDS) techniques, XPS analyzes only few atomic layers present on the surface. This was discovered early in 1966 (Ref. 5). While this has awarded a merit to the analytical technique to analyze very thin layers such as films and coatings, it often analyzes the adsorbed superficial gases and contaminations on a sample introduced to its analytical chamber. This necessitates the surface is cleaned and the underlying material, material of interest, is exposed in a clean environment such that the material of interest is analyzed. The cleaning is accomplished by a scanning ion gun within the analytical chamber of the instrument. Ion gun uses an argon gas and is commonly attached in most modern machines. Reliable and efficient vacuum systems employed in modern machines does not allow adsorbed layers to rebuild after the surface is cleaned. Development of efficient and reliable vacuum pumps over these developmental years is yet another important step in the commercialization of XPS machines. Vacuum levels of better than 10-7 torr are essential to increase the mean free path of electrons released from the sample surface. Thus, modern machines are equipped with high capacity ion, turbo or cryogenic pumps in their analytical chambers. Today, XPS has advanced from an applied physics laboratory to industry for use in quality control as well as analysis of contaminants and has taken a dominant role in microanalysis. Its uniqueness arises from the fact that it is considered non-destructive compared to other common micro-analytical techniques using the electron and ion excitation sources. Polymers and plastics could be analyzed since the binding energies of saturated and unsaturated bonds in atoms could be separated. Extremely thin layers could be analyzed including materials with layered structures. The technique, though did not advance for many years, has now opened a new window for research as well as applications in industry due to its ability to separate and measure the chemical shifts in bound elements. Principles

Panda, Binayak↗
NASA NTRS2000

Mars Oxidant: Proof of Concept and Quantitative Analysis

Textbooks make us believe that in every silicate mineral, on Earth, Mars and elsewhere, the oxygen anions exist in just one oxidation state, namely 2(-) as in 0(-2). Yet, a surprisingly large fraction of the oxygen anions in rock-forming minerals may exist in a more oxidized form, namely the 1- state, as 0(-) in peroxy. This has far-reaching consequences for understanding the Mars soil oxidant and its biocompatibility.

Freund, Friedemann↗
NASA NTRS1977

Experimental observations of the chemistry of the SiO2/Si interface

Changes in silicon surface preparation prior to thermal oxidation are shown to leave a signature by altering the final SiO2/Si interface structure. Surface analytical techniques, including XPS, static SIMS, ion milling, and newly developed wet-chemical profiling procedures are used to obtain detailed information on the chemical structure of the interface. The oxides are shown to be essentially SiO2 down to a narrow transitional interface layer (3-7 A). A number of discrete chemical species are observed in this interface layer, including different silicon bonds (e.g., C-, OH-, H-) and a range of oxidation states of silicon (0 to +4). The effect of surface preparation and the observed chemical species are correlated with oxide growth rate, surface-state density, and flatband shifts after irradiation.

Grunthaner, F. J.↗
NASA NTRS1995

Life as a planetary phenomenon: the colonization of Mars

Life is a planet-wide phenomenon in which its components incessantly move and interact. Life imperatively recycles its parts at the surface of the Earth in a chemical transformation and physical transport that depends utterly on the energy from a recent star, the Sun. Humanity, entirely dependent on other beings, plays a recent and relatively small part in the great phenomenon of life that transports and transforms the surface of the Earth. Our species accelerates but does not dominate the metabolism of the Earth system. Ironically, during the Apollo days of the sixties, fears were rampant that Martian or other extraterrestrial "germs" might "contaminate" our planet. After Viking, such fears are seen as the manifestation of cultural paranoia. The Viking missions complemented ground-based astronomical observation and yielded definitive evidence for the lack of life on the red planet. The Gaia hypothesis states that the surface temperature, composition of the reactive gases, oxidation state, alkalinity-acidity on today's Earth are kept homeorrhetically at values set by the sum of the activities of the current biota. Life, in other words, not only produces and maintains its immediate environment, but appears on Earth only as a planetary phenomenon. Since the natural tendency of all life is to grow exponentially to fill proximal volume, the question now "can life ecopoietically expand to Mars?" is entirely equivalent to the query of "can Gaia reproduce?".

Non-NASA Center↗
NASA NTRS1984

The evolution of the prebiotic atmosphere

One-dimensional radiative-convective and photochemical models are used to estimate the vertical temperature structure and composition of the earth's prebiotic atmosphere. Greatly enhanced CO2 levels (100-1000 times present) are required to keep the mean surface temperature above freezing in the face of decreased solar luminosity during the earth's early history. Such high CO2 partial pressures would have affected the atmospheric oxidation state by facilitating the photochemical production of soluble species including H2O2 and H2CO. Oxidation of ferrous iron in the oceans by H2O2 dissolved in rainwater should have kept the atmospheric H2 mixing ratio above 0.0002, and the ground-level O2 mixing ratio below 10 to the -11th, regardless of the magnitude of the rate of volcanic release of reduced gases.

Kasting, J. F.↗
NASA NTRS2011

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Valdez, Thomas I.↗
NASA NTRS2019

Oxidation of the Mantle Wedge by H+ in Aqueous Fluids: A New Interdisciplinary Approach

The observation that arc magmas are the most oxidized on Earth have led petrologists to question whether the subduction process might cause oxidation of the sub-arc mantle source. A strong correlation between the input of slab-derived aqueous fluid and Fe3(+)/ΣFe in arc magmas has led to the hypothesis that slab fluids may facilitiate the transfer of redox potential from oxidized slab material to mantle wedge and subsequently to primary arc melts. Despite this intuitive link, identifying an efficient and ubiquitous chemical process to transfer oxidation state in slab fluids has been challenging. Pure H2O alone is an inefficient oxidizer in the mantle, necessitating another oxidant within the fluid. Commonly invoked components include S or C, which are likely heterogeneously distributed within subducting slabs, and direct transfer of Fe3(+), which is only possible in very solute-rich fluids. Here we present a new mechanism to explain the oxidation of the sub-arc mantle by slab-derived aqueous fluid, wherein dissolved H(+)(aq) is reduced to H2(aq). Redox equilibrium is satisfied by electron transfer from Fe2(+)(s), which is oxidized in the rock to Fe3(+)(s) in the reaction: 2Fe2(+)(s) + 2H(+)(aq) = 2Fe3(+)(s) + H2(aq). This simple reaction was previously overlooked due to the assumption that all H must be bound by H2O molecules (i.e., no dissolved H), applicable to a pure H2O fluid, but not one with a solute load as addressed here. The application of thermodynamic modeling tools from aqueous geochemistry (DEW, EQ3/6) to mantle petrology predicts this reaction between mantle rock and slab fluid with our own experimentally constrained chemistry and fO2 (QFM+2). Mass transfer model results show an increase in Fe3(+)/ΣFe in mantle rock from MORB- like (0.15) to arc-like (0.2–0.3) values at reasonable fluid fluxes, co-incident with increasing H2 activity in the fluid. This can explain the stark correlation between slab fluid input into the mantle wedge and the observed fO2 of arc magmas. Moreover, it does not require diffusion of hydrogen out of the system. Instead, H2 remains dissolved in fluid in equilibrium with oxidized mantle rock.

Iacovino, Kayla↗
NASA NTRS1991

Near-edge study of gold-substituted YBa2Cu3O(7-delta)

The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using x-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

Ruckman, Mark W.↗
NASA NTRS1991

Near-edge study of gold-substituted YBa2Cu3O(7-delta)

The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using X-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

Ruckman, Mark W.↗
NASA NTRS2006

Oxygen Fugacity of the Upper Mantle of Mars. Evidence from the Partitioning Behavior of Vanadium in Y980459 (Y98) and other Olivine-Phyric Shergottites

Using partitioning behavior of V between olivine and basaltic liquid precisely calibrated for martian basalts, we determined the redox state of primitive (olivine-rich, high Mg#) martian basalts near their liquidus. The combination of oxidation state and incompatible element characteristics determined from early olivine indicates that correlations between fO2 and other geochemical characteristics observed in many martian basalts is also a fundamental characteristic of these primitive magmas. However, our data does not exhibit the range of fO2 observed in these previous studies.. We conclude that the fO2 for the martian upper mantle is approximately IW+1 and is incompatible-element depleted. It seems most likely (although clearly open to interpretation) that these mantle-derived magmas assimilated a more oxidizing (>IW+3), incompatible-element enriched, lower crustal component as they ponded at the base of the martian crust.

Shearer, C. K.↗