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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
NASA NTRS2022

Overcoming Universal Restrictions on Metal Selectivity by Protein Design

Selective metal coordination is central to the functions of metalloproteins:1,2 each metalloprotein must pair with its cognate metallocofactor to fulfl its biological role3 . However, achieving metal selectivity solely through a three-dimensional protein structure is a great challenge, because there is a limited set of metal-coordinating amino acid functionalities and proteins are inherently fexible, which impedes steric selection of metals3,4 . Metal-binding afnities of natural proteins are primarily dictated by the electronic properties of metal ions and follow the Irving–Williams series5 (Mn2+ < Fe2+ < Co2+ < Ni2+ Zn2+) with few exceptions6,7 . Accordingly, metalloproteins overwhelmingly bind Cu2+ and Zn2+ in isolation, regardless of the nature of their active sites and their cognate metal ions1,3,8 . This led organisms to evolve complex homeostatic machinery and non-equilibrium strategies to achieve correct metal speciation1,3,8–10. Here we report an artifcial dimeric protein, (AB)2, that thermodynamically overcomes the Irving–Williams restrictions in vitro and in cells, favouring the binding of lower-Irving–Williams transition metals over Cu2+, the most dominant ion in the Irving–Williams series. Counter to the convention in molecular design of achieving specifcity through structural preorganization, (AB)2 was deliberately designed to be fexible. This fexibility enabled (AB)2 to adopt mutually exclusive, metal-dependent conformational states, which led to the discovery of structurally coupled coordination sites that disfavour Cu2+ ions by enforcing an unfavourable coordination geometry. Aside from highlighting fexibility as a valuable element in protein design, our results illustrate design principles for constructing selective metal sequestration agents.

Tae Su Choi↗
NASA NTRS2014

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

humic acid↗
NASA NTRS1976

Shear strength of metal-sapphire contacts

The shear strength of polycrystalline Ag, Cu, Ni, and Fe contacts on clean (0001) sapphire has been studied in ultrahigh vacuum. Both clean metal surfaces and surfaces exposed to O2, Cl2, and C2H4 were used. The results indicate that there are two sources of strength of Al2O3-metal contacts: an intrinsic one that depends on the particular clean metal in contact with Al2O3 and an additional one due to intermediate films. The shear strength of the clean metal contacts correlated directly with the free energy of oxide formation for the lowest metal oxide, in accord with the hypothesis that a chemical bond is formed between metal cations and oxygen anions in the sapphire surface. Contacts formed by metals exposed to chlorine exhibited uniformly low shear strength indicative of van der Waals bonding between chlorinated metal surfaces and sapphire. Contacts formed by metals exposed to oxygen exhibited enhanced shear strength, in accord with the hypothesis that an intermediate oxide layer increases interfacial strength.

Pepper, S. V.↗
NASA NTRS1976

Friction and transfer behavior of pyrolytic boron nitride in contact with various metals

Sliding friction experiments were conducted with pyrolytic boron nitride in sliding contact with itself and various metals. Auger emission spectroscopy was used to monitor transfer of pyrolytic boron nitride to metals and metals to pyrolytic boron nitride. Results indicate that the friction coefficient for pyrolytic boron nitride in contact with metals can be related to the chemical activity of the metals and more particularly to the d valence bond character of the metal. Transfer was found to occur to all metals except silver and gold and the amount of transfer was less in the presence than in the absence of metal oxide. Friction was less for pyrolytic boron nitride in contact with a metal in air than in vacuum.

Buckley, D. H.↗
NASA NTRS1979

Magnetite-sulfide-metal complexes in the Allende meteorite

A model of liquid immiscibility is presented that seemingly accounts for the sulfide-oxide-metal complexes that are present in olivine-rich chondrules in the Allende meteorite. The four major assemblages that are identified are: (1) magnetite + Ni-Fe metal; (2) magnetite + troilite + Ni-Fe metal; (3) magnetite + troilite + pentlandite + Ni-Fe metal; and (4) troilite + or - pentlandite. Specific attention is focused on oxide-metal associations and experimental data confirm earlier suggestions that magnetite results from the oxidation of an initially high-Fe-content metal alloy. Oxidation decreases the modal abundance of the Fe metal and this is accompanied by substantial increases in Ni contents which reach a maximum of approximately 70 wt % Ni. The proposed oxidation mechanism is entirely consistent with condensation of Fe-metal + olivine (Fa5) that subsequently reequilibrated at lower temperatures. Although the sulfide constituents could also have formed by the reaction of Fe-Ni metal + gaseous H2S, sulfide immiscibility under increased conditions of partial O2 pressure is the preferred process.

Haggerty, S. E.↗
NASA NTRS1986

The spectral and physical properties of metal in meteorite assemblages - Implications of asteroid surface materials

One of the objectives of the present paper is related to a definition of the spectral contribution of the nickel-iron metal component in meteoritic assemblages. Another objective is the elucidation of the chemical, physical, and petrographic properties of the metal grains which affect the spectral signature in asteroid surface materials. It is pointed out that an improved understanding of the spectral and physical properties of metal in asteroid regoliths should permit an improved characterization of these objects, and, in particular, a better evaluation of the differentiated or undifferentiated nature of the S-type and M-type asteroids. Attention is given to the spectra of iron and nickel-iron metals, the spectral effects of metal in chondritic assemblages, the spectral reflectance of metal grains in ordinary chondrites, the nature of the surfaces of chondritic metal grains, the origin of coats on chondritic metal grains, and the fragmentation of metal on asteroid surfaces.

Gaffey, M. J.↗
NASA NTRS1993

Liquid metal drop ejection

The aim of this project was to demonstrate the possibility of ejecting liquid metals using drop on demand printing technology. The plan was to make transducers for operation in the 100 MHz frequency range and to use these transducers to demonstrate the ability to eject drops of liquid metals such as gallium. Two transducers were made by indium bonding piezoelectric lithium niobate to quartz buffer rods. The lithium niobate plates were thinned by mechanical polishing to a thickness of 37 microns for operation at 100 MHz. Hemispherical lenses were polished in the opposite ends of the buffer rods. The lenses, which focus the sound waves in the liquid metal, had an F-number equals 1. A mechanical housing was made to hold the transducers and to allow precise control over the liquid level above the lens. We started by demonstrating the ability to eject drops of water on demand. The drops of water had a diameter of 15 microns which corresponds to the wavelength of the sound wave in the water. A videotape of this ejection was made. We then used a mixture of Gallium and Indium (used to lower the melting temperature of the Gallium) to demonstrate the ejection of liquid metal drops. This proved to be difficult because of the oxide skin which forms on the surface of the liquid. In some instances, we were able to eject metal drops, however, this was not consistent and reproducible. An experiment was set up at NASA-Lewis to stabilize the process of drop on demand liquid metal ejection. The object was to place the transducer and liquid metal in a vacuum station so that no oxide would form on the surface. We were successful in demonstrating that liquid metals could be ejected on demand and that this technology could be used for making sheet metal in space.

Khuri-Yakub, B. T.↗
NASA NTRS1993

Thermophysical properties of simple liquid metals: A brief review of theory

In this paper, we review the current theory of the thermophysical properties of simple liquid metals. The emphasis is on thermodynamic properties, but we also briefly discuss the nonequilibrium properties of liquid metals. We begin by defining a 'simple liquid metal' as one in which the valence electrons interact only weakly with the ionic cores, so that the interaction can be treated by perturbation theory. We then write down the equilibrium Hamiltonian of a liquid metal as a sum of five terms: the bare ion-ion interaction, the electron-electron interaction, the bare electron-ion interaction, and the kinetic energies of electrons and ions. Since the electron-ion interaction can be treated by perturbation, the electronic part contributes in two ways to the Helmholtz free energy: it gives a density-dependent term which is independent of the arrangement of ions, and it acts to screen the ion-ion interaction, giving rise to effective ion-ion pair potentials which are density-dependent, in general. After sketching the form of a typical pair potential, we briefly enumerate some methods for calculating the ionic distribution function and hence the Helmholtz free energy of the liquid: monte Carlo simulations, molecular dynamics simulations, and thermodynamic perturbation theory. The final result is a general expression for the Helmholtz free energy of the liquid metal. It can be used to calculate a wide range of thermodynamic properties of simple metal liquids, which we enumerate. They include not only a range of thermodynamic coefficients of both metals and alloys, but also many aspects of the phase diagram, including freezing curves of pure elements and phase diagrams of liquid alloys (including liquidus and solidus curves). We briefly mention some key discoveries resulting from previous applications of this method, and point out that the same methods work for other materials not normally considered to be liquid metals (such as colloidal suspensions, in which the suspended microspheres behave like ions screened by the salt solution in which they are suspended). We conclude with a brief discussion of some non-equilibrium (i.e., transport) properties which can be treated by an extension of these methods. These include electrical resistivity, thermal conductivity, viscosity, atomic self-diffusion coefficients, concentration diffusion coefficients in alloys, surface tension and thermal emissivity. Finally, we briefly mention two methods by which the theory might be extended to non-simple liquid metals: these are empirical techniques (i.e., empirical two- and three-body potentials), and numerical many-body approaches. Both may be potentially applicable to extremely complex systems, such as nonstoichiometric liquid semiconductor alloys.

Stroud, David↗
NASA NTRS1997

Internal and Surface Phenomena in Heterogenous Metal Combustion

The phenomenon of gas dissolution in burning metals was observed in recent metal combustion studies, but it could not be adequately explained by the traditional metal combustion models. The research reported here addresses heterogeneous metal combustion with emphasis on the processes of oxygen penetration inside burning metal and its influence on the metal combustion rate, temperature history, and disruptive burning. The unique feature of this work is the combination of the microgravity environment with a novel micro-arc generator of monodispersed metal droplets, ensuring repeatable formation and ignition of uniform metal droplets with a controllable initial temperature and velocity. Burning droplet temperature is measured in real time with a three wavelength pyrometer. In addition, particles are rapidly quenched at different combustion times, cross-sectioned, and examined using SEM-based techniques to retrieve the internal composition history of burning metal particles. When the initial velocity of a spherical particle is nearly zero, the microgravity environment makes it possible to study the flame structure, the development of flame nonsymmetry, and correlation of the flame shape with the heterogeneous combustion processes.

Dreizin, Edward L.↗
NASA NTRS1999

Combustion of Metals in Reduced-Gravity and Extra Terrestrial Environments

The combustion of metals is a field with important practical applications in rocket propellants, high-temperature flames, and material synthesis. Also, the safe operation of metal containers in high-pressure oxygen systems and with cryogenic fuels and oxidizers remains an important concern in industry. The increasing use of metallic components in spacecraft and space structures has also raised concerns about their flammability properties and fire suppression mechanisms. In addition, recent efforts to embark on unmanned and manned planetary exploration, such as on Mars, have also renewed the interest in metal/carbon-dioxide combustion as an effective in situ resource utilization technology. In spite of these practical applications, the understanding of the combustion properties of metals remains far behind that of the most commonly used fuels such as hydrocarbons. The lack of understanding is due to the many problems unique to metal- oxidizer reactions such as: low-temperature surface oxidation prior to ignition, heterogeneous reactions, very high combustion temperatures, product condensation, high emissivity of products, and multi-phase interactions. Very few analytical models (all neglecting the influence of gravity) have been developed to predict the burning characteristics and the flame structure details. Several experimental studies attempting to validate these models have used small metal particles to recreate gravity-free conditions. The high emissivity of the flames, rapid reaction, and intermittent explosions experienced by these particles have made the gathering of any useful information on burning rates and flame structure very difficult. The use of a reduced gravity environment is needed to clarify some of the complex interactions among the phenomena described above. First, the elimination of the intrusive buoyant flows that plague all combustion phenomena is of paramount importance in metal reactions due to the much higher temperatures reached during combustion. Second, a low-gravity environment is absolutely essential to remove the destructive effect of gravity on the shape of a molten metal droplet in order to study a spherically symmetric condition with large bulk samples. The larger size of the spherical metal droplet and the longer burning times available in reduced gravity extend the spatial and temporal dimensions to permit careful probing of the flame structure and dynamics. Third, the influence of the radiative heat transfer from the solid oxides can be studied more carefully by generating a stagnant spherical shell of condensed products undisturbed by buoyancy.

Branch, M.C.↗
NASA NTRS2006

Metal-Silicate Segregation in Asteroidal Meteorites

A fundamental process of planetary differentiation is the segregation of metal-sulfide and silicate phases, leading eventually to the formation of a metallic core. Asteroidal meteorites provide a glimpse of this process frozen in time from the early solar system. While chondrites represent starting materials, iron meteorites provide an end product where metal has been completely concentrated in a region of the parent asteroid. A complimentary end product is seen in metal-poor achondrites that have undergone significant igneous processing, such as angrites, HED's and the majority of aubrites. Metal-rich achondrites such as acapulcoite/lodranites, winonaites, ureilites, and metal-rich aubrites may represent intermediate stages in the metal segregation process. Among these, acapulcoite-lodranites and ureilites are examples of primary metal-bearing mantle restites, and therefore provide an opportunity to observe the metal segregation process that was captured in progress. In this study we use bulk trace element compositions of acapulcoites-lodranites and ureilites for this purpose.

Herrin, Jason S.↗
NASA NTRS2010

Process for Making a Noble Metal on Tin Oxide Catalyst

To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

Davis, Patricia↗
NASA NTRS1971

Metallization failures

Metallization-related failure mechanisms were shown to be a major cause of integrated circuit failures under accelerated stress conditions, as well as in actual use under field operation. The integrated circuit industry is aware of the problem and is attempting to solve it in one of two ways: (1) better understanding of the aluminum system, which is the most widely used metallization material for silicon integrated circuits both as a single level and multilevel metallization, or (2) evaluating alternative metal systems. Aluminum metallization offers many advantages, but also has limitations particularly at elevated temperatures and high current densities. As an alternative, multilayer systems of the general form, silicon device-metal-inorganic insulator-metal, are being considered to produce large scale integrated arrays. The merits and restrictions of metallization systems in current usage and systems under development are defined.

Beatty, R.↗
NASA NTRS1973

Gallium and germanium in the metal and silicates of L- and LL-chondrites.

Concentrations of Ga and Ge in the metal of 31 L-, 8 LL- and 2 H-chondrites, and in the silicates of 12 L- and LL-chondrites have been determined by spectrophotometric methods. The ranges of Ga contents in the metal of L- and LL-chondrites are 1.1 to 36.9 ppm and 1.0 to 34.1 ppm, respectively. The Ge content in the metal is positively correlated with Ga and ranges from 89.1 to 160 ppm and from 126 to 308 ppm for L- and LL-chondrites, respectively. The Ga content in the silicates of L-chondrites varies from 4.0 to 8.9 ppm. The Ga and Ge contents in the metal are clearly lower in unequilibrated than in equilibrated L- and LL-group chondrites. Unequilibrated and equilibrated chondrites are well separated in the plots of Ga vs Ge in the metal, and the L- and LL-groups are also well resolved. The Ga and Ge in the metal are well correlated with petrologic grade. This suggests that Ga and Ge variations in the metal are related to thermal metamorphism. There is evidence of an enrichment of Ga in the metal due to shock reheating.

Chou, C.-L.↗
NASA NTRS1973

Chemistry and thermal history of metal particles in Luna 20 soils.

Individual metal particles from Luna 20 thin sections 521, 513 and 514 as well as several small metallic inclusions in silicate particles from Luna 20 thin sections 501 and 502 were examined using optical microscopy and the electron microprobe. All the metallic particles and inclusions analyzed are of meteoritic Co-Ni content as are most of the metallic particles from the Fra Mauro and the Apollo 16 highlands sites. It is proposed that most of the metal at these 3 sites had its origin in the meteoritic projectiles that bombarded and accumulated in the early lunar crust. It is apparent that the metallic particles and some of the metallic inclusions in the Luna 20 soil have been subjected to reheating on the moon and this process has removed any evidence of the original meteoritic microstructure of the metal.

Goldstein, J. I.↗
NASA NTRS1979

Metal-dielectric interactions

Metal direlectric surface interactions and dielectric films on metal substrates were investigated. Since interfacial interaction depends so heavily on the nature of the surfaces, analytical surface tools such as Auger emission spectroscopy, X-ray photoelectron spectroscopy and field ion microscopy were used to assist in surface and interfacial characterization. The results indicate that with metals contacting certain glasses in the clean state interfacial, bonding produces fractures in the glasses while when a film such as water is present, fractures occur in the metal near the interface. Friction forces were used to measure the interfacial bond strengths. Studies with metals contacting polymers using field ion microscopy revealed that strong bonding forces could develop being between a metal and polymer surface with polymer transferring to the metal surface in various ways depending upon the forces applied to the surface in contact. With the deposition of refractory carbides, silicides and borides onto metal and alloy substrates the presence of oxides at the interface or active gases in the deposition plasma were shown to alter interfacial properties and chemistry. Auger ion depth profile analysis indicated the chemical composition at the interface and this could be related to the mechanical, friction, and wear behavior of the coating.

Buckley, D. H.↗
NASA NTRS1981

Metal and associated phases in Bishunpur, a highly unequilibrated ordinary chondrite

Bishunpur is one of the most unequilibrated ordinary chondrites, and preserves a relatively unaltered record of solar nebular processes. A survey of three polished thin sections of Bishunpur revealed that metal occurs in three textural domains: (1) in the matrix, (2) within chondrules and (3) in coatings on chondrules. A table provides a textural classification of the various metal types found in Bishunpur and their composition. Electron-microprobe analyses are discussed, and similarities between Bishunpur metal and opaques and those in carbonaceous chondrites are considered. Attention is given to low-Ni kamacite grains in chondrule olivine, Si-bearing chondrule metal, spheroidal metal in chondrules, metal and sulfide-bearing rims, coarse matrix metal, and fine matrix metal formation.

Rambaldi, E. R.↗
NASA NTRS1982

Correlation of tensile and shear strengths of metals with their friction properties

The relation between the theoretical tensile and the shear strengths and the friction properties of metals in contact with diamond, boron nitride, silicon carbide, manganese-zinc ferrite, and the metals themselves in vacuum was investigated. The relationship between the actual shear strength and the friction properties of the metal was also investigated. An estimate of the theoretical uniaxial tensile strength was obtained in terms of the equilibrium surface energy, interplanar spacing of the planes perpendicular to the tensile axis, and the Young's modulus of elasticity. An estimate of the theoretical shear strength for metals was obtained from the shear modulus, the repeat distance of atoms in the direction of shear of the metal and the interplanar spacing of the shear planes. The coefficient of friction for metals was found to be related to the theoretical tensile, theoretical shear, and actual shear strengths of metals. The higher the strength of the metal, the lower the coefficient of friction.

Miyoshi, K.↗