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At least 199 records · Page 11

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

Thompson, David W.↗

Metal-Silicate Segregation in Deforming Dunitic Rocks: Applications to Core Formation in Europa and Ganymede

Core formation is an important event in the evolution of a planetary body, affecting both the geochemical and geophysical properties of the body. Metal-silicate segregation could have proceeded either by settling of liquid metal through a magma ocean or by percolation of liquid metal through a solid silicate mantle. Percolation of metallic melt had previously been excluded as a viable segregation mechanism because metallic melts do not form an interconnected network under hydrostatic conditions, except at high melt fraction (>5 vol%), due to the high dihedral angle between metals and silicates (>60 ). Without an interconnected network, porous flow of metallic melt is impossible, leaving the magma ocean scenario as the only mechanism to form the core. Moment-of-inertia measurements of Europa and Ganymede from the Galileo probe indicate that they are differentiated. This evidence suggests that a method for segregating metals and silicates at temperatures low enough to retain volatile compounds must exist. We have investigated the effect of deformation on the distribution of metallic melts in silicates. We have deformed samples of olivine + 5-9 vol% Fe-S to strains of 2.5 in simple shear and find that the metallic melt segregates into melt-rich planes oriented at 20 to the shear plane. These metallic melt-rich bands are similar in structure to the silicate melt-rich bands reported by Holtzman, indicating that deformation can interconnect isolated metallic melt pockets and allow porous flow of non-wetting melts. Such a core formation process could have occurred in the jovian satellites.

Hustoft, J. W.↗

Joining and Assembly of Bulk Metallic Glass Composites Through Capacitive Discharge

Bulk metallic glasses (BMGs), a class of amorphous metals defined as having a thickness greater than 1 mm, are being broadly investigated by NASA for use in spacecraft hardware. Their unique properties, attained from their non-crystalline structure, motivate several game-changing aerospace applications. BMGs have low melting temperatures so they can be cheaply and repeatedly cast into complex net shapes, such as mirrors or electronic casings. They are extremely strong and wear-resistant, which motivates their use in gears and bearings. Amorphous metal coatings are hard, corrosion-resistant, and have high reflectivity. BMG composites, reinforced with soft second phases, can be fabricated into energy-absorbing cellular panels for orbital debris shielding. One limitation of BMG materials is their inability to be welded, bonded, brazed, or fastened in a convenient method to form larger structures. Cellular structures (which can be classified as trusses, foams, honeycombs, egg boxes, etc.) are useful for many NASA, commercial, and military aerospace applications, including low-density paneling and shields. Although conventional cellular structures exhibit high specific strength, their porous structures make them challenging to fabricate. In particular, metal cellular structures are extremely difficult to fabricate due to their high processing temperatures. Aluminum honeycomb sandwich panels, for example, are used widely as spacecraft shields due to their low density and ease of fabrication, but suffer from low strength. A desirable metal cellular structure is one with high strength, combined with low density and simple fabrication. The thermoplastic joining process described here allows for the fabrication of monolithic BMG truss-like structures that are 90% porous and have no heat-affected zone, weld, bond, or braze. This is accomplished by welding the nodes of stacked BMG composite panels using a localized capacitor discharge, forming a single monolithic structure. This removes many complicated and costly fabrication steps. Moreover, the cellular structures detailed in this work are among the highest- strength and most energy-absorbent materials known. This implies that a fabricated structure made from these materials would have unequaled mechanical properties compared to other metal foams or trusses. The process works by taking advantage of the electrical properties of the matrix material in the metal-matrix composite, which in this case is a metallic glass. Due to the random nanoscale arrangement of atoms (without any grain boundaries), the matrix glass exhibits a near-constant electrical resistivity as a function of temperature. By placing the composite panels between two copper electrode plates and discharging a capacitor, the entire matrix of the panel can be heated to approximately 700 C in 10 milliseconds, which is above the alloy s solidus but below the liquidus. By designing the geometry of the panels into the shape of an egg box, the electrical discharge localizes only in the tips of each pyramidal cell. By applying a forging load during discharge, the nodes of the panels can be fused together into a single piece, which then dissipates heat through radiation back into a glassy state. This means that two panels can be metallurgically fused into one panel with no heat-affected zone, creating a seamless connection between panels. During the process, the soft metal particles (dendrites) that are uniformly distributed in the glassy matrix to increase the toughness are completely unaffected by the thermoplastic joining. The novelty is that a truss (or foam-like) structure can be formed with excellent energy- absorbing capabilities without the need for machining. The technique allows for large-scale fabrication of panels, well-suited for spacecraft shields or military vehicle door panels. Crystalline metal cellular structures cannot be fabricated using the thermoplastic joining technique described here. If metal panels were te assembled into a cellular structure, they would either have to be welded, brazed, bonded, or fastened together, creating a weak spot in the structure at each connection. Welded parts require a welding material to be added to the joint and exhibit a soft and weak heat-affected zone. Brazing and bonding do not form a metallurgical joint and thus exhibit low strengths, especially when the panels are pulled apart and fasteners require high-stress-concentration holes to be drilled. No equivalent rapid heating method exists for assembling metal panels together into cellular structures, and thus, those parts must be foamed, machined, or investment cast if they are to form a monolithic structure. If the crystalline panels were to be joined using capacitive discharge, as with a spot welder, their bond would be very weak, and the panels would have to be extremely thin. In contrast, the strength of joined BMG parts has been demonstrated to have strength comparable to the parent material. This technique opens up the possibility of using large-scale BMG hardware in spacecraft, military, or commercial applications.

Hofmann, Douglas C.↗

Systems and Methods for Fabricating Objects Including Amorphous Metal Using Techniques Akin to Additive Manufacturing

Systems and methods in accordance with embodiments of the invention fabricate objects including amorphous metals using techniques akin to additive manufacturing. In one embodiment, a method of fabricating an object that includes an amorphous metal includes: applying a first layer of molten metallic alloy to a surface; cooling the first layer of molten metallic alloy such that it solidifies and thereby forms a first layer including amorphous metal; subsequently applying at least one layer of molten metallic alloy onto a layer including amorphous metal; cooling each subsequently applied layer of molten metallic alloy such that it solidifies and thereby forms a layer including amorphous metal prior to the application of any adjacent layer of molten metallic alloy; where the aggregate of the solidified layers including amorphous metal forms a desired shape in the object to be fabricated; and removing at least the first layer including amorphous metal from the surface.

Hofmann, Douglas↗

Tribological properties of silicon carbide in metal removal process

Material properties are considered as they relate to adhesion, friction, and wear of single crystal silicon carbide in contact with metals and alloys that are likely to be involved in a metal removal process such as grinding. Metal removal from adhesion between sliding surfaces in contact and metal removal as a result of the silicon carbide sliding against a metal, indenting into it, and plowing a series of grooves or furrows are discussed. Fracture and deformation characteristics of the silicon carbide surface are also covered. The adhesion, friction, and metal transfer to silicon carbide is related to the relative chemical activity of the metals. The more active the metal, the higher the adhesion and friction, and the greater the metal transfer to silicon carbide. Atomic size and content of alloying elements play a dominant role in controlling adhesion, friction, and abrasive wear properties of alloys. The friction and abrasive wear (metal removal) decrease linearly as the shear strength of the bulk metal increases. They decrease as the solute to solvent atomic radius ratio increases or decreases linearly from unity, and with an increase of solute content. The surface fracture of silicon carbide is due to cleavages of 0001, 10(-1)0, and/or 11(-2)0 planes.

Miyoshi, K.↗

A study of ignition phenomena of bulk metals by radiant heating

Early research on combustion of metals was motivated by the knowledge of the large heat release and corresponding high temperatures associated with metal-oxygen reactions. The advent of space flight brought about an increased interest in the ignition and combustion of metallic particles as additives in solid rocket propellants. More recently, attention has been given to the flammability properties of bulk, structural metals due to the number of accidental explosions of metal components in high-pressure oxygen systems. The following work represents a preliminary study that is part of a broader research effort aimed at providing further insight into the phenomena of bulk metal combustion by looking at the effects of gravity on the ignition behavior of metals. The scope of this preliminary experimental study includes the use of a non-coherent, continuous radiation ignition source, the measurement of temperature profiles of a variety of metals and a qualitative observation of the ignition phenomena at normal gravity. The specific objectives of the investigation include: (1) a feasibility study of the use of a continuous radiation source for metal ignition; (2) testing and characterization of the ignition behavior of a variety of metals; and (3) building a preliminary experimental database on ignition of metals under normal gravity conditions.

Branch, Melvin C.↗

Metallic copper in ordinary chondrites

Metallic Cu of moderately high purity (approximately 985 mg/g Cu, approximately 15 mg/g Ni) occurs in at least 66% of ordinary chondrites (OC) as heterogeneously distributed, small (typically less than or equal to 20 micrometers) rounded to irregular grains. The mean modal abundance of metallic Cu in H, L and LL chondrites is low: 1.0 to 1.4 x 10(exp -4) vol%, corresponding to only 4 - 5 % of the total Cu in OC whole rocks. In more than 75% of the metallic-Cu-bearing OC, at least some metallic Cu occurs at metallic-Fe-Ni-troilite grain boundaries. In some cases it also occurs within troilite, within metallic Fe-Ni, or at the boundaries these phases form with silicates or chromite. Ordinary chondrites that contain a relatively large number of occurrences of metallic Cu/sq mm have a tendency to have experienced moderately high degrees of shock. Shock processes can cause local melting and transportation of metallic Fe-Ni and troilte; because metallic Cu is mainly associated with these phases, it also gets redistributed during shock events. In the most common petrographic assemblage containing metallic Cu, the Cu is adjacent to small irregular troilite grains surrounded by taenite plus tetrataenite; this assemblage resembles fizzed troilite and may have formed by localized shock melting or remelting of a metal-troilite assemblage.

Rubin, Alan E.↗

Metal-silica sol-gel materials

The present invention relates to a single phase metal-silica sol-gel glass formed by the co-condensation of a transition metal with silicon atoms where the metal atoms are uniformly distributed within the sol-gel glass as individual metal centers. Any transition metal may be used in the sol-gel glasses. The present invention also relates to sensor materials where the sensor material is formed using the single phase metal-silica sol-gel glasses. The sensor materials may be in the form of a thin film or may be attached to an optical fiber. The present invention also relates to a method of sensing chemicals using the chemical sensors by monitoring the chromatic change of the metal-silica sol-gel glass when the chemical binds to the sensor. The present invention also relates to oxidation catalysts where a metal-silica sol-gel glass catalyzes the reaction. The present invention also relates to a method of performing oxidation reactions using the metal-silica sol-gel glasses. The present invention also relates to organopolymer metal-silica sol-gel composites where the pores of the metal-silica sol-gel glasses are filled with an organic polymer polymerized by the sol-gel glass.

Stiegman, Albert E.↗

Fabrication of Metallic Hollow Nanoparticles

Metal and semiconductor nanoshells, particularly transition metal nanoshells, are fabricated using dendrimer molecules. Metallic colloids, metallic ions or semiconductors are attached to amine groups on the dendrimer surface in stabilized solution for the surface seeding method and the surface seedless method, respectively. Subsequently, the process is repeated with additional metallic ions or semiconductor, a stabilizer, and NaBH.sub.4 to increase the wall thickness of the metallic or semiconductor lining on the dendrimer surface. Metallic or semiconductor ions are automatically reduced on the metallic or semiconductor nanoparticles causing the formation of hollow metallic or semiconductor nanoparticles. The void size of the formed hollow nanoparticles depends on the dendrimer generation. The thickness of the metallic or semiconductor thin film around the dendrimer depends on the repetition times and the size of initial metallic or semiconductor seeds.

Kim, Jae-Woo↗

Emission-Line Metallicities from the Faint Infrared Grism Survey and VLT/MUSE

We derive direct-measurement gas-phase metallicities of 7.4 < 12 + log(O/H) < 8.4 for 14 low-mass emission- line galaxies at 0.3 < z < 0.8 identified in the Faint Infrared Grism Survey. We use deep slitless G102 grism spectroscopy of the Hubble Ultra Deep Field, dispersing light from all objects in the field at wavelengths between 0.85 and 1.15 μm. We run an automatic search routine on these spectra to robustly identify 71 emission-line sources, using archival data from Very Large Telescope (VLT)/Multi-Unit Spectroscopic Explorer (MUSE) to measure additional lines and confirm redshifts. We identify 14 objects with 0.3 < z < 0.8 with measurable [O III] λ4363 Å emission lines in matching VLT/MUSE spectra. For these galaxies, we derive direct electron-temperature gas-phase metallicities with a range of 7.4 < 12 + log(O/H) < 8.4. With matching stellar masses in the range of 10(exp 7.9) Solar Mass < M(sub *) < 10(exp 10.4) Solar Mass, we construct a mass–metallicity (MZ) relation and find that the relation is offset to lower metallicities compared to metallicities derived from alternative methods (e.g., R(sub 23), O3N2, N2O2) and continuum selected samples. Using star formation rates derived from the Hα emission line, we calculate our galaxies’ position on the Fundamental Metallicity Relation, where we also find an offset toward lower metallicities. This demonstrates that this emission-line-selected sample probes objects of low stellar masses but even lower metallicities than many comparable surveys. We detect a trend suggesting galaxies with higher Specific Star Formation (SSFR) are more likely to have lower metallicity. This could be due to cold accretion of metal-poor gas that drives star formation, or could be because outflows of metal-rich stellar winds and SNe ejecta are more common in galaxies with higher SSFR.

Pharo, John↗

International Conference on Rapidly Quenched Metals, 2nd, Massachusetts Institute of Technology, Cambridge, Mass., November 17-19, 1975, Proceedings

The range of topics covered by the papers includes: rapid quenching (and specifically splat quenching) of metals, spin quenching, levitation melting, rapid quenching from liquid state; amorphous metal phases and metastable phases, metallic glasses, ribbons, splats, films, metal ribbon reinforced resins; crystallization of metallic glasses, and ferromagnetic amorphous alloys. Structural models for amorphous metals, splat-quenching equipment, and measurements of the properties of amorphous and noncrystalline metals and metallic glasses are also discussed, in addition to: fatigue events (crack propagation) in amorphous metals, fracture behavior in rapidly quenched metals, ductile superconducting Cu-Nb-Sn alloys, and semiconducting amorphous V205 alloy. Individual items are announced in this issue.

Source record↗

Method and apparatus for holding two separate metal pieces together for welding

A method of holding two separate metal pieces together for welding is described including the steps of overlapping a portion of one of the metal pieces on a portion of the other metal piece, encasing the overlapping metal piece in a compressible device, drawing the compressible device into an enclosure, and compressing a portion of the compressible device around the overlapping portions of the metal pieces for holding the metal pieces under constant and equal pressure during welding. The preferred apparatus for performing the method utilizes a support mechanism to support the two separate metal pieces in an overlapping configuration; a compressible device surrounding the support mechanism and at least one of the metal pieces, and a compressing device surrounding the compressible device for compressing the compressible device around the overlapping portions of the metal pieces, thus providing constant and equal pressure at all points on the overlapping portions of the metal pieces.

Mcclure, S. R.↗

Alkali metal for ultraviolet band-pass filter

An alkali metal filter having a layer of metallic bismuth deposited onto the alkali metal is provided. The metallic bismuth acts to stabilize the surface of the alkali metal to prevent substantial surface migration from occurring on the alkali metal, which may degrade optical characteristics of the filter. To this end, a layer of metallic bismuth is deposited by vapor deposition over the alkali metal to a depth of approximately 5 to 10 A. A complete alkali metal filter is described along with a method for fabricating the alkali metal filter.

Mardesich, Nick↗

Elevated initial Sr-87/Sr-86 in ordinary chondrite metal

The metal phase of ordinary chondrites has been found to contain a complex assemblage of non-metal phases, evidently formed when elements such as Si, Cr and P, originally dissolved in the metal, were subsequently oxidized and exsolved. We have investigated the Rb-Sr isotopic system in samples of H-chondrite metal, finding small but nontrivial amounts of Sr, apparently concentrated toward the surface of metal grains, and characterized by pronounced excesses of Sr-87/Sr-86 in chondritic metal can plausibly account for the characteristically elevated initial Sr-87/Sr-86 found in ordinary chondrite phosphates, but it remains unclear when and where the metal experienced the high Rb/Sr environment needed to account for such high Sr-87/Sr-86. We have previously reported Rb-Sr data for separated metal from Dhajala (H3), Forest Vale (H4) and Estacado (H6). Here we report data for two size fractions (80-160 and 280-450 microns) of separated metal from the H4 chondrite Ste. Marguerite. These samples were etched twice (.5N HCl for one hour) before dissolution (6N HCl). Aliquots of the solutions were spiked for Fe, Ca and Rb + Sr. The results for Ste. Marguerite metal are presented; errors are two-sigma and elemental concentrations are stated in terms of total sample weight.

Podosek, F. A.↗

Ultraviolet to near-infrared spectral distributions of star-forming galaxies: Metallicity and age effects

Spectral distributions from the UV to the near-IR of a sample of 44 star-forming galaxies are used to calculate the metallicity (O/H), star-formation rate (SFR) and age of the starbursts. The oxygen abundance covers the range 8.3 less than O/H less than 9.4 and nitrogen (N) is found to be mostly a product of secondary nucleosynthesis for O/H greater than 8.4. Due to its secondary origin, N/O ratios up to approximately equals 4 times the solar value can be obtained for metal-rich starbursts. The SFR ranges 0.01 to 100 solar mass/year. The lower metallicity galaxies seem to be experiencing an instantaneous burst of star formation, with ages ranging from under 5 x 10(exp 6) to 10(exp 7) yr. The highest metallicity galaxies are most probably experiencing a continuous burst. Correlations between the calculated quantities and several spectral features are investigated. We found a highly significant correlation between the equivalent width W(C IV lambda 1550)-a stellar (absorption) feature- and the oxygen abundance of the emitting gas (O/H). Thus we show for the first time that the stellar metallicity is well correlated with the gas metallicity in star-bursting galaxies. The equivalent width W(Si IV lambda 1400) and the emission line ratio (N II) lambda lambda 6548.84/H(sub alpha) also correlate well with O/H, and all three features can be used as metallicity indicators for star-forming galaxies. The continuum color between lambda 1400 and lambda 3500 (C(14 - 35)) is shown to correlate with O/H, although it is better correlated with E(B - V). It was not possible to disentangle the metallicity from the reddening effect in C(14- 35). We estimate that the reddening affecting the UV continuum is about half the one derived from the Balmer decrement of the emitting gas. The SFR correlates well with the galaxy luminosity and there is no dependence of the continuum color on the SFR. The higher metallicities are only found in the more luminous galaxies, while low metallicities are found over the whole luminosity interval (-16 less than M(sub B) less than -23, H(sub 0) = 50 km/sec/Mpc) covered by the sample.

Storchi-Bergmann, Thaisa↗

The Formation of Carbonaceous Material in the Early Solar Nebula: The Role of Metal Dusting

For many years it has been suggested that the carbonaceous material found in association with Fe/Ni metal and metal carbides in primitive bodies is linked to the Fischer–Tropsch reaction. This is especially true with chondritic-porous interplanetary dust particles, which are considered to have a cometary origin and are among some of the most primitive and least processed materials available for study. Another phenomenon which occurs under the same carburizing conditions as the Fischer–Tropsch reaction is called metal dusting and could be a possible pathway to forming some of the carbonaceous material found in primitive bodies. Metal dusting is a catastrophic corrosion of metal under these carburizing conditions that results in a porous mixture of carbonaceous material, metal, and metal carbides. In the case of pure iron, type I metal dusting results in the formation of a metastable iron carbide, typically cementite, Fe3C. While metal dusting has been studied industrially for over 50 years, it does not appear to have been applied to the formation of carbonaceous material in astrophysical settings. In this work, the general mechanism of metal dusting on iron is described and a thermodynamic analysis of the dusting phenomena applied to solar nebula conditions. Rate measurements are made with pure iron samples over the temperature range from 400°C to 950°C. In addition, the products from experimental runs at 500°C and 600°C are studied by transmission electron microscopy. Results show that iron carbide particles are formed with carbonaceous material consisting of poorly graphitized carbon.

Interplanetary dust↗

A Transmission Electron Microscopy Study of a Refractory Metal Grain from a Calcium-Aluminum-Rich Inclusion in the Leoville CV3 Chondrite

Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100

T. Ramprasad↗

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↗