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All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Carbon petrology in cometary dust

Chondritic porous (CP) interplanetary dust particles (IDP's) are collected in the Earth's stratosphere. There exists an extensive database on major and minor element chemistry, stable isotopes, noble gas abundances and mineralogy of many CP IDP's, as well as infrared and Raman spectroscopic properties. For details on the mineralogy, chemistry and physical properties of IDP's, I refer to the reviews by Mackinnon and Rietmeijer (1987), Bradley et al. (1988) and Sandford (1987). Texture, mineralogy (Mackinnon and Rietmeijer, 1987) and chemistry (Schramm et al., 1989; Flynn and Sutton, 1991) support the notion that CP IDP's are a unique group of ultrafine-grained extraterrestiral materials that are distinct from any known meteorite class. Their fluffy, or porous, morphology suggests that CP IDP's probably endured minimal alteration by protoplanetary processes since their formation. It is generally accepted that CP IDP's are solid debris from short-period comets. The evidence is mostly circumstantial but this notion gained significant support based on the comet Halley dust data (Brownlee, 1990). In this paper, I will accept that CP IDP's are indeed cometary dust. The C/Si ratio in CP IDP's is 3.3 times higher than in CI carbonaceous chondrites (Schramm et al. 1989). The intraparticle carbon distribution is heteorogeneous (Rietmeijer and McKay, 1986). Carbon occurs both in oxidized and reduced forms. Analytical electron microscope (AEM) and Raman spectroscopic analyses have shown the presence of several carbon forms in CP IDP's but the data are scattered in the literature. Carbons in cometary CP IDP's are among the most pristine Solar System carbons available for laboratory study. Similar to a recently developed petrological model for the diversity of layer silicates in CP IDP's (Zolensky, 1991) that is useful to constrain in situ aqueous alteration in comets (Rietmeijer and Mackinnon, 1987a), I here present the first effort to develop a petrological concept of carbons in CP IDP's. This concept is useful to constrain comet evolution. I also present the philosophical constraint facing Earth Scientists in studies of protoplanets that require a new approach to cometary dust studies.

Rietmeijer, Frans J. M.↗
NASA NTRS2007

Making Single-Source Precursors of Ternary Semiconductors

A synthesis route has been developed for the commercial manufacture of single- source precursors of chalcopyrite semiconductor absorber layers of thin-film solar photovoltaic cells. A closely related class of single-source precursors of these semiconductors, and their synthesis routes, were reported in "Improved Single-Source Precursors for Solar-Cell Absorbers" (LEW-17445-1), NASA Tech Briefs, Vol. 31, No. 6 (June 2007), page 56. The present synthesis route is better suited to commercialization because it is simpler and involves the use of commercially available agents, yet offers the flexibility needed for synthesis of a variety of precursors. A single-source precursor of the type of interest here is denoted by the general formula L2M'(mu-ER)2M(ER)2, where L signifies a Lewis base; M signifies Al, In, or Ga; M' signifies Ag or Cu; R signifies an alkyl, aryl, silyl, or perfluorocarbon group; E signifies O, S, Se, or Te; and mu signifies a bridging ligand. This compound can be synthesized in a "one-pot" procedure from ingredients that are readily available from almost any chemical supplier. In a demonstration, the following synthesis was performed: Under anaerobic conditions, InCl3 was reacted with sodium ethanethiolate in methanol in a 1:4 molar ratio to afford the ionic stable intermediate compound Na+[In(SEt)4]- (where Et signifies ethyl group). After approximately 15 minutes, a heterogeneous solution of CuCl and the Lewis base PPh3 (where Ph signifies phenyl) in a 1:2 ratio in a mixture of CH3CN and CH2Cl2 was added directly to the freshly prepared Na+[In(SEt)4]-. After 24 hours, the reaction was essentially complete. The methanolic solution was concentrated, then the product was extracted with CH2Cl2, then the product was washed with dry ether and pentane. The product in its final form was a creamy white solid. Spectroscopic and elemental analysis confirmed that the product was (PPh3)2Cu(mu-SEt)2In(mu-SEt)2, which is known to be a precursor of the ternary semiconductor CuInS2.

Hepp, Aloysius↗
NASA NTRS2004

Vibration Characteristics Determined for Stainless Steel Sandwich Panels With a Metal Foam Core for Lightweight Fan Blade Design

The goal of this project at the NASA Glenn Research Center is to provide fan materials that are safer, weigh less, and cost less than the currently used titanium alloy or polymer matrix composite fans. The proposed material system is a sandwich fan construction made up of thin solid face sheets and a lightweight metal foam core. The stiffness of the sandwich structure is increased by separating the two face sheets by the foam layer. The resulting structure has a high stiffness and lighter weight in comparison to the solid facesheet material alone. The face sheets carry the applied in-plane and bending loads (ref. 1). The metal foam core must resist the transverse shear and transverse normal loads, as well as keep the facings supported and working as a single unit. Metal foams have ranges of mechanical properties, such as light weight, impact resistance, and vibration suppression (ref. 2), which makes them more suitable for use in lightweight fan structures. Metal foams have been available for decades (refs. 3 and 4), but the difficulties in the original processes and high costs have prevented their widespread use. However, advances in production techniques and cost reduction have created a new interest in this class of materials (ref. 5). The material chosen for the face sheet and the metal foam for this study was the aerospace-grade stainless steel 17-4PH. This steel was chosen because of its attractive mechanical properties and the ease with which it can be made through the powder metallurgy process (ref. 6). The advantages of a metal foam core, in comparison to a typical honeycomb core, are material isotropy and the ease of forming complex geometries, such as fan blades. A section of a 17-4PH sandwich structure is shown in the following photograph. Part of process of designing any blade is to determine the natural frequencies of the particular blade shape. A designer needs to predict the resonance frequencies of a new blade design to properly identify a useful operating range. Operating a blade at or near the resonance frequencies leads to high-cycle fatigue, which ultimately limits the blade's durability and life. So the aim of this study is to determine the variation of the resonance frequencies for an idealized sandwich blade as a function of its face-sheet thickness, core thickness, and foam density. The finite element method is used to determine the natural frequencies for an idealized rectangular sandwich blade. The proven Lanczos method (ref. 7) is used in the study to extract the natural frequency.

Ghosn, Louis J.↗
NASA NTRS2013

High-Pressure Lightweight Thrusters

Returning samples of Martian soil and rock to Earth is of great interest to scientists. There were numerous studies to evaluate Mars Sample Return (MSR) mission architectures, technology needs, development plans, and requirements. The largest propulsion risk element of the MSR mission is the Mars Ascent Vehicle (MAV). Along with the baseline solid-propellant vehicle, liquid propellants have been considered. Similar requirements apply to other lander ascent engines and reaction control systems. The performance of current state-ofthe- art liquid propellant engines can be significantly improved by increasing both combustion temperature and pressure. Pump-fed propulsion is suggested for a single-stage bipropellant MAV. Achieving a 90-percent stage propellant fraction is thought to be possible on a 100-kg scale, including sufficient thrust for lifting off Mars. To increase the performance of storable bipropellant rocket engines, a high-pressure, lightweight combustion chamber was designed. Iridium liner electrodeposition was investigated on complex-shaped thrust chamber mandrels. Dense, uniform iridium liners were produced on chamber and cylindrical mandrels. Carbon/carbon composite (C/C) structures were braided over iridium-lined mandrels and densified by chemical vapor infiltration. Niobium deposition was evaluated for forming a metallic attachment flange on the carbon/ carbon structure. The new thrust chamber was designed to exceed state-of-the-art performance, and was manufactured with an 83-percent weight savings. High-performance C/Cs possess a unique set of properties that make them desirable materials for high-temperature structures used in rocket propulsion components, hypersonic vehicles, and aircraft brakes. In particular, more attention is focused on 3D braided C/Cs due to their mesh-work structure. Research on the properties of C/Cs has shown that the strength of composites is strongly affected by the fiber-matrix interfacial bonding, and that weakening interface realizes pseudo-plastic behavior with significant increase in the tensile strength. The investigation of high-temperature strength of C/Cs under high-rate heating (critical for thrust chambers) shows that tensile and compression strength increases from 70 MPa at room temperature to 110 MPa at 1,773 K, and up to 125 MPa at 2,473 K. Despite these unique properties, the use of C/Cs is limited by its high oxidation rate at elevated temperatures. Lining carbon/carbon chambers with a thin layer of iridium or iridium and rhenium is an innovative way to use proven refractory metals and provide the oxidation barrier necessary to enable the use of carbon/ carbon composites. Due to the lower density of C/Cs as compared to SiC/SiC composites, an iridium liner can be added to the C/C structure and still be below the overall thruster weight. Weight calculations show that C/C, C/C with 50 microns of Ir, and C/C with 100 microns of Ir are of less weight than alternative materials for the same construction.

Holmes, Richard↗
NASA NTRS2009

Micro-Horn Arrays for Ultrasonic Impedance Matching

Thin-layered structures containing arrays of micromachined horns, denoted solid micro-horn arrays (SMIHAs), have been conceived as improved means of matching acoustic impedances between ultrasonic transducers and the media with which the transducers are required to exchange acoustic energy. Typically, ultrasonic transducers (e.g., those used in medical imaging) are piezoelectric or similar devices, which produce small displacements at large stresses. However, larger displacements at smaller stresses are required in the target media (e.g., human tissues) with which acoustic energy is to be exchanged. Heretofore, efficiencies in transmission of acoustic energy between ultrasonic transducers and target media have been severely limited because substantial mismatches of acoustic impedances have remained, even when coupling material layers have been interposed between the transducers and the target media. In contrast, SMIHAs can, in principle, be designed to effect more nearly complete acoustic impedance matching, leading to power transmission efficiencies of 90 percent or even greater. The SMIHA concept is based on extension, into the higher-frequency/ lower-wavelength ultrasonic range, of the use of horns to match acoustic impedances in the audible and lower-frequency ultrasonic ranges. In matching acoustic impedance in transmission from a higher-impedance acoustic source (e.g., a piezoelectric transducer) and a lowerimpedance target medium (e.g., air or human tissue), a horn acts as a mechanical amplifier. The shape and size of the horn can be optimized for matching acoustic impedance in a specified frequency range. A typical SMIHA would consist of a base plate, a face plate, and an array of horns that would constitute pillars that connect the two plates (see figure). In use, the base plate would be connected to an ultrasonic transducer and the face plate would be placed in contact with the target medium. As at lower frequencies, the sizes and shapes of the pillars could be tailored for impedance matching in a specified ultrasonic frequency range. In a design that would be simplest to implement by micromachining, the horns would have constant cross-sectional areas as shown in the upper part of the figure. In this case, the dimensions of the horns could be chosen on the basis of a Mason equivalent-circuit model (a simplified model, well-known in the piezoelectric-transducer art, in which the electrical and mechanical dynamics, including electromechanical couplings, are expressed as electrical circuit elements that can include inductors, capacitors, and lumped-parameter complex impedances.) In a more complex, more nearly optimum design, the cross-sectional area of each horn would be either stepped or made to vary as a continuous function of through-the thickness position, as shown in the lower part of the figure.

Rao, Shanti↗
NASA NTRS2018

Relative Sputtering Rates of FeS, MgS, and Mg Silicates: Implications for ISM Gas Phase Depletions of Rock-Forming Elements

Astronomical measurements of S abundances in the diffuse interstellar medium (ISM) indicate ionized S is a dominant species with little (< 5%) S residing in grains (e.g. Jenkins 2009). This is an enigmatic result, given that abundant Fe-sulfide grains are observed in dust around pre- and post-main sequence stars and are also observed as major components of primitive meteoritic and cometary samples. These disparate observations suggest that the lifetime of sulfide grains in the ISM is short because of destruction processes. Our previous work has shown that FeS and MgS retain their crystallinity and do not amorphize during radiation processing, whereas enstatite and forsterite are readily amorphized. We have extended this study to measure the relative sputtering rates of FeS and MgS compared to enstatite and forsterite. Irradiation of FeS with 4 keV He+ results in preferential sputtering of S and the formation of a thin 2-3 nm, compact Fe metal layer that armors the surface. The zone of S loss extends to a depth of ~8-10 nm below the exposed surface. Despite this S loss, the FeS retains its crystallinity and shows no sign of incipient amorphization. Irradiation of FeS with 5kV Ga+ in a focused ion beam (FIB) instrument resulted in preferential sputtering of S and the formation of a 5-8-nm thick surface layer of nanophase Fe metal. X-ray mapping shows that the zone of S sputtering extends to a depth of nearly 20 nm, but there is no evidence for FeS amorphization, consistent with our previous work. The irradiation experiments show that the relative sputtering rate of FeS and MgS are much higher than olivine or enstatite. Sputtering experiments utilizing 30 kV and 5 kV Ga ions in the FIB produced volume loss in troilite that was ~4X greater than in enstatite or forsterite. The sputter yield under these conditions is such that for every Si atom sputtered from enstatite, ~14 S atoms are sputtered from FeS. We have performed similar sputtering experiments on Fe-bearing niningerite (MgS) and co-existing enstatite from the ALH 84170 EH3 chondrite. MgS also sputters much more rapidly than enstatite with a relative Si:S sputter yield of 1:8. For MgS, sulfur is highly depleted at the surface and the S-depletion zone extends to a depth of ~15 nm (using 5 kV Ga+). There is a corresponding zone of Mg and especially Fe enrichment that extends from 5 to ~10 nm below the surface, respectively. The dominant grain destruction mechanism in the ISM is sputtering from passage of supernova-generated shock waves. This process also results in the amorphization of crystalline silicates in the ISM. Our results indicate that FeS and MgS grains produced in evolved stars and injected into the ISM will be destroyed more rapidly than crystalline silicates. This process may account for the lack of significant depletion of S from the gas phase in the ISM. However, rare nanophase FeS grains occur as inclusions in circumstellar amorphous silicate grains found in comet dust particles analyzed in the laboratory. These results show that a finite amount of S in the ISM is sequestered in solid grains.

SPUTTERING RATES↗
NASA NTRSDate not supplied

Mineralogical Analysis of Calcium-Aluminum-Rich Inclusions Provides Insight Into Post-Formation Processes

Introduction: Calcium-aluminum inclusions (CAIs) are cm- to mm-sized intergrowths of refractory phases found in chondritic meteorites [1]. Their mineral compositions closely match the compositions of the solids thought to condense from an extremely hot (>1500K) gas with a bulk solar composition [2-4], suggesting that CAIs were the earliest solids within the Solar System [2-4]. These inclusions provide invaluable insights into the conditions and dynamics of the early Solar System. CAIs must be transported from their formation region near the protosun to the chondrite parent-body accretion region. The nature of their journey could affect how, when, and where the secondary processes recorded in these CAIs occurred [4]. Did these secondary processes occur in the solar nebula or during accretion with the parent body, or both? How were the CAIs affected by varying thermochemical processes? To better answer these questions, we have undertaken an in-depth, textural study of the secondary alteration of select CAI samples. Methods: We chose three CAIs that experienced a range of post-formation processing to gain better understanding of secondary alteration based on previous preliminary examination [5]. Representative CAIs were chosen from NWA 5508 (CV3), NWA 12772 (CV3), and Coolidge (CL4) carbonaceous chondrites. We used scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD) techniques for detailed chemical, mineralogical, and textural analysis of the CAIs. Backscattered electron (BSE) images and X-ray elemental maps were taken of Coolidge and NWA 5508 using the Lunar and Planetary Institute (LPI) Phenom SEM. The JEOL 7900F SEM at NASA Johnson Space Center (JSC) was used to obtain energy dispersive spectroscopy (EDS) chemical maps of all samples. High resolution EBSD analysis identified the mineral phases and textures, providing key information on their nature. Based on the SEM and EBSD data, minerals of interest were selected for quantitative chemical electron probe micro-analysis (EPMA) using the JEOL JXA-8530F at NASA JSC. Results and Discussion: The EDS maps show that the NWA 5508 and NWA 12772 CAIs designated “Saguaro” and “Hoopoe” respectively [5] are enriched in calcium while the Coolidge CAI designated “Cottonwood” is aluminum and magnesium rich. Saguaro. A ~1.5cm diameter igneous Type B CAI with a rounded shape. The dominant phases are melilite, spinel, and Al-Ti pyroxene with minor anorthite. Spinel is subhedral and occurs in clusters. Some of these clusters have a circular geometry which encloses other minerals, known as a palisade structure [6] (Fig. 1). Some palisades form near perfect circles while others are more irregular in shape. Melilite in Saguaro ranges in size from coarse (>250m) to fine-grained (5-7m) and forms intergrown laths. A third of the melilite grains exhibit simple twinning about their <001> axis. The spinel palisades and twinned melilite in Saguaro suggest an igneous history, and the lack of secondary minerals suggests minimal aqueous alteration. At some point in time after the initial condensation of the minerals and formation of the inclusion, the sample was remelted and quickly solidified. The formation of the palisades is still heavily debated. One hypothesis is that the palisades are the rims of smaller CAIs that accreted early on, essentially acting as xenoliths within the larger CAIs [7]. Another hypothesis suggests an igneous origin for palisade structures [6-8] wherein the melt traps gas bubbles, and the spinel nucleates on the surface of this bubble. Based on the WDS spot analyses of 41 melilite grains using EPMA, the data suggest that the composition inside and outside the palisades is nearly identical. This finding indicates that these palisades are likely not exogenous but rather formed from melt-vapor reactions. Our results are consistent with studies by Simon and Grossman,1997 [6] and Zhang et al. (2019) [8]. Hoopoe. A ~0.5cm compact Type A CAI with an irregular shape. The dominant mineral phases are melilite, spinel, and hibonite with minor amounts of anorthite, augite, and perovskite. The melilite ranges in size from ~500 to 50µm. The larger melilite grains have simple twinning along the <001> axis like melilite in Saguaro. Melilite in Hoopoe exhibits crystal-plastic strain with misorientation dominantly about the <010> and <110> axes. Spinel shows subhedral to euhedral morphology and appears in clusters. Hibonite grains are similar to spinel in habit and size but show more plastic strain. The two minerals are often found together with one appearing to replace the other. Perovskite appears in fine grained recrystallized regions alongside fine augite and spinel. The abundant strain and deformation features in the melilite and hibonite suggest that Hoopoe experienced shock. This shock could have occurred in the nebula [9] or from an impact of another body on the parent body asteroid. The appearance of fine-grained (<10m) areas of augite, perovskite, and spinel in the dominantly coarse-grained inclusion suggest recrystallization, possibly due to the sudden increase in pressure and temperature. Cottonwood. This ~0.5cm CAI exhibits distinct mineralogy and textures suggesting a high degree of alteration. It is irregular in shape. The dominant mineral phases are spinel and anorthite with minor amounts of augite and rutile. The two main texture types can be seen in Fig. 2. The first type consists of coarse euhedral to subhedral spinel and anorthite. The second includes fine grained spinel, anorthite, rutile, and iron sulfides. Within these fine-grained regions, the anorthite grains are clustered into domains exhibiting the same crystallographic orientation. Rutile exclusively occurs with fine anorthite indicating a potential relationship between the two. Cottonwood has a clear and unbroken Wark-Lovering [10] rim (Fig. 2) on one side that consists of a sequence of spinel followed by anorthite and an outer layer of augite. The abundance of the fine-grained regions containing iron oxides and iron sulfides, secondary phases such as rutile, and oriented anorthite grains is evidence for recrystallization associated with a high degree of thermal metamorphism. The EPMA analyses on both coarse- and fine-grained spinel show that the fine spinel grains are more enriched in Cr (1-2 wt. %) than their coarse counterparts (0.1-0.5 wt. %). The data suggest thermal metamorphism drove chemical exchange of the previously refractory inclusion, introducing chromium and iron as well as sulfur, which is moderately volatile. Conclusions: The three CAIs analyzed record distinct secondary nebular and parent body processes. Saguaro melted in the nebula as seen by the twinned melilite and spinel palisades. Hoopoe experienced intense shock which deformed its melilite and recrystallized perovskite, augite, and spinel in fine-grained regions. Cottonwood shows evidence of recrystallization and chemical changes consistent with thermal metamorphism occurring after accretion into the parent-body.

V E Burnette↗