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All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Microstructural Evaluations of Baseline HSR/EPM Disk Alloys

Six alloys representing two classes of powder metallurgy nickel-based superalloys were examined by transmission electron microscopy (TEM) and phase extraction. Alloys KM4, CH98, IN-100 and 456 are based on a Ni-18Co-12Cr composition while alloys Rene' 88 DT and SR 3 have lower Al and Co and higher Cr contents. The lambda size distributions were determined from quantitative image analysis of the TEM images. The volume fraction of lambda and carbides and the composition of the phases were determined by a combination of phase extraction and TEM. The results showed many similarities in lambda size distributions, grain boundary serrations, and grain boundary carbide frequencies between alloys KM4, CH98, 456, Rene' 88 DT and SR 3 when heat treated to give an approximate grain size of ASTM 6. The density of grain boundary carbides in KM4 was shown to substantially increase as the grain size increased. IN-100 and 456 subjected to a serration cooling heat treatment had much more complex lambda size distributions with very large intergranular and intragranular secondary lambda as well as finer than average cooling and aging lambda. The grain boundary carbides in IN-100 were similar to the other alloys, but 456 given the serration cooling heat treatment had a more variable density of grain boundary carbides. Examination of the phases extracted from the matrix showed that there were significant differences in the phase chemistries and elemental partitioning ratios between the various alloys.

Gabb, Timothy P.↗
NASA NTRS1984

Structural characterizaiton and gas reactions of small metal particles by high-resolution, in-situ TEM and TED

The existing in-situ transmission electron microscopy (TEM) facility was improved by adding a separately pumped mini-specimen chamber. The chamber contains wire-evaporation sources for three metals and a specimen heater for moderate substrate temperatures. A sample introduction device was constructed, installed, and tested, facilitating rapid introduction of a specimen into the mini-chamber while maintaining the background pressure in that chamber in the 10(-9) millibar range. Small particles and clusters of Pd, grown by deposition from the vapor phase in an in-situ TEM facility on amorphous and crystalline support films of alumina and on ultra-thin carbon films, were analyzed by conventional high-resolution TEM and image analysis in terms of detectability, number density, and size distribution. The smallest particles that could be detected and counted contained no more than 6 atoms; size determinations could be made for particles 1 nm in diameter. The influence of various oxygen plasma treatments, annealing treatments, and of increasing the substrate temperature during deposition was investigated. The TEM technique was employed to demonstrate that under otherwise identica l conditions the lattice parameter of Pd particles in the 1 to 2 nm size range and supported in random orientation on ex-situ prepared mica films is expanded by some 3% when compared to 5 nm size particles. It is believed that this expansion is neither a small-particle diffraction effect nor due to pseudomorphism, but that it is due to a annealing-induced transformation of the small as-deposited particles with predominantly composite crystal structures into larger particles with true f.c.c. structure and thus inherently smaller lattice parameter.

Source record↗
NASA NTRS2016

Transmission Electron Microscopy of Magnetite Plaquettes in Orgueil

Magnetite sometimes takes the form of a plaquette - barrel-shaped stack of magnetite disks - in carbonaceous chondrites (CC) that show evidence of aqueous alteration. The asymmetric nature of the plaquettes caused Pizzarello and Groy to propose magnetite plaquettes as a naturally asymmetric mineral that can indroduce symmetry-breaking in organic molecules. Our previous synchrotron X-ray computed microtomography (SXRCT) and electron backscatter diffraction (EBSD) analyses of the magnetite plaquettes in fifteen CCs indicate that magnetite plaquettes are composed of nearly parallel discs, and the crystallographic orientations of the discs change around a rotational axis normal to the discs surfaces. In order to further investigate the nanostructures of magnetite plaquettes, we made two focused ion beam (FIB) sections of nine magnetite plaquettes from a thin section of CI Orgueil for transmission electron microscope (TEM) analysis. The X-ray spectrum imaging shows that the magnetite discs are purely iron oxide Fe3O4 (42.9 at% Fe and 57.1 at% O), which suggest that the plaquettes are of aqueous origin as it is difficult to form pure magnetite as a nebular condensate. The selected area electron diffraction (SAED) patterns acquired across the plaquettes show that the magnetite discs are single crystals. SEM and EBSD analyses suggest that the planar surfaces of the magnetite discs belong to the {100} planes of the cubic inverse spinel structure, which are supported by our TEM observations. Kerridge et al. suggested that the epitaxial relationship between magnetite plaquette and carbonate determines the magnetite face. However, according to our TEM observation, the association of magnetite with porous networks of phyllosilicate indicates that the epitaxial relationship with carbonate is not essential to the formation of magnetite plaquettes. It was difficult to determine the preferred rotational orientation of the plaquettes due to the symmetry of the cubic structure, however, we are able to observe small but consistent rotational orientation across several discs within a plaquette.

Chan, Q. H. S.↗
NASA NTRS1994

Application of an alkylammonium method for characterization of phyllosilicates in CI chondrites

Many meteorites and interplanetary dust particles (IDP's) with primitive compositions contain significant amounts of phyllosilicates, which are generally interpreted as evidence of protoplanetary aqueous alteration at an early period in the solar system. These meteorites are chondrites of the carbonaceous and ordinary varieties. Characterization of phyllosilicates in these materials is important because of the important physico-chemical information they hold, e.g., from well characterized phyllosilicates, thermodynamic stability relations and hence the conditions of formation of phyllosilicates in the parent body of the meteorite can be predicted. Although we are at a rudimentary level of understanding of the minerals resulting from the aqueous alteration in the early solar nebula, we know that the most common phyllosilicates present in chondritic extraterrestrial materials are serpentines, smectites, chlorites, and micas. The characterization of fine grained minerals in meteorites and IDP's rely heavily on electron beam instruments, especially transmission electron microscopy (TEM). Typically, phyllosilicates are identified by a combination of high resolution imaging of basal spacings, electron diffraction analysis, and chemical analysis. Smectites can be difficult to differentiate from micas because the smectites loose their interlayer water and the interlayers collapse to the same basal spacing as mica in the high vacuum of the TEM. In high-resolution TEM (HRTEM) images, smectite basal spacings vary from 1 nm up to 1.5 nm, while micas show 1 or 2 nm basal spacings. Not only is it difficult to differentiate smectites from micas, but there is no way of identifying different classes of smectites in meteorites and IDP's. To differentiate smectites from micas and also to recognize the charge differences among smectites, an alkylammonium method can be employed because the basal spacings of alkylammonium saturated smectites expand as a function of alkylamine chain length and the layer-charge density of the 2:1 expanding phyllosilicate, and the final product is significantly more stable under electron beam examination. Such a method was tested on standard clays and several meteorite samples using four alkylammonium salts.

Golden, D. C.↗
NASA NTRS1990

Defect Clustering and Nano-Phase Structure Characterization of Multi-Component Rare Earth Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

Advanced oxide thermal barrier coatings have been developed by incorporating multi- component rare earth oxide dopants into zirconia-yttria to effectively promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nano-scale phases within the coating systems. The presence of these nano-sized defect clusters has found to significantly reduce the coating intrinsic thermal conductivity, improve sintering resistance, and maintain long-term high temperature stability. In this paper, the defect clusters and nano-structured phases, which were created by the addition of multi-component rare earth dopants to the plasma- sprayed and electron-beam physical vapor deposited thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The defect cluster size, distribution, crystallographic and compositional information were investigated using high-resolution TEM lattice imaging, selected area diffraction (SAD), and energy dispersive spectroscopy (EDS) analysis techniques. The results showed that substantial defect clusters were formed in the advanced multi-component rare earth oxide doped zirconia-yttria systems. The size of the oxide defect clusters and the cluster dopant segregation was typically ranging fiom 5 to 50 nm. These multi-component dopant induced defect clusters are an important factor for the coating long-term high temperature stability and excellent performance.

Zhu, Dongming↗
NASA NTRS1991

Clay minerals in primitive meteorites and interplanetary dust 2. Smectites and micas

The classification is briefly summarized of stony meteorites and cosmic dust, and the mineralogy and chemistry is described of serpentine group minerals. The occurrence of smectites and micas in extraterrestrial materials is examined. The characterization of fine grained minerals in meteorites and IDPs relies heavily on electron beam instruments, especially the transmission electron microscope (TEM). Typically, phyllosilicates are identified by a combination of high resolution imaging of basal spacings, electron diffraction, and chemical analysis. Smectites can be difficult to differentiate from micas because the smectites lose their interlayer water and the interlayer partly collapse in the high vacuum of the TEM.

Keller, L. P.↗
NASA NTRS2014

Coordinated Mineralogical and Isotopic Analysis of a Cosmic Symplectite Identified in a Stardust Terminal Particle

Comet Wild-2 samples returned by the Stardust spacecraft contain a chemically diverse mixture of material, underscoring the complex nature of comets. Studies of entire Stardust aerogel tracks afford the opportunity to examine the fine-grained particle fragments distributed along the length of the track as well as the terminal particles. Previous TEM characterization of a terminal particle (TP) in track #147 revealed a symplectically intergrown iron sulfide and oxide assemblage. Mineralogically similar assemblages, known as cosmic symplectites (COS, formerly termed "new-PCP"), have only been identified in the primitive carbonaceous chondrite Acfer 094. Meteoritic COS have isotopically heavy O compositions (delta (sup 17), O-18 = 180per mille) that point to interactions with early solar system primordial water. In this study we report mineralogical and O isotopic measurements of the Wild-2 COS assemblage. Experimental: Track #147 is a "bulbous"-type track (4600 microns long) containing 7 terminal particles. The TPs were removed from the track, embedded in epoxy, and ultramicrotomed. A JEOL 2500SE 200 keV field-emission scanning-transmission electron microscope was used to obtain quantitative elemental maps and detailed mineralogical characterization. Following TEM analysis, two thin sections of TP4 (12 microns) were analyzed for O isotopes by raster ion imaging with the JSC NanoSIMS 50L. All three O isotopes were measured simultaneously using electron multipliers. San Carlos olivine grains were used as isotopic standards. Results and Discussion: The COS in the Wild-2 track #147 TP4 sample consists of symplectically intergrown pentlandite and nanocrystalline maghemite which coexists with high-Ca pyroxene with Na and Cr (kosmochlor component). This kosmochlor component could have a nebular origin and be precursors to type II chondrules in ordinary chondrites. Yet pentlandite is not a stable phase in the nebula. The COS in Acfer 094 also consists of pentlandite, but contains magnetite [4] rather than the more oxidized maghemite observed in the Wild-2 COS. The Acfer 094 COS display heavy O isotopic compositions that are the result of sulfidization and oxidation of Fe, Ni-metal grains and sulfides by O-17- and O-18-rich water in the solar nebula or possibly on the parent body. The O isotopic composition of the Wild-2 COS, however, is indistinguishable from terrestrial, indicating it was not altered by the same primordial aqueous reservoir as the Acfer 094 COS. The alteration could have occurred on the parent body by isotopically equilibrated ice. The mineralogy and petrography of Wild-2 samples suggests an incomplete or nascent hydration process. In future work we will analyze S isotopes in the track #147 TP4 COS and search for additional COS in Stardust samples.

Nguyen, A. N.↗
NASA NTRS2003

Defect Clustering and Nano-Phase Structure Characterization of Multi-Component Rare Earth Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

Advanced oxide thermal barrier coatings have been developed by incorporating multi-component rare earth oxide dopants into zirconia-yttria to effectively promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nano-scale phases within the coating systems. The presence of these nano-sized defect clusters has found to significantly reduce the coating intrinsic thermal conductivity, improve sintering resistance, and maintain long-term high temperature stability. In this paper, the defect clusters and nano-structured phases, which were created by the addition of multi-component rare earth dopants to the plasma-sprayed and electron-beam physical vapor deposited thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The defect cluster size, distribution, crystallographic and compositional information were investigated using high-resolution TEM lattice imaging, selected area diffraction (SAD), electron energy-loss spectroscopy (EELS) and energy dispersive spectroscopy (EDS) analysis techniques. The results showed that substantial defect clusters were formed in the advanced multi-component rare earth oxide doped zirconia- yttria systems. The size of the oxide defect clusters and the cluster dopant segregation was typically ranging from 5 to 50 nm. These multi-component dopant induced defect clusters are an important factor for the coating long-term high temperature stability and excellent performance.

Zhu, Dongming↗
NASA NTRS2021

Understanding the Space Weathering of Mercury Through Laboratory Experiments

Introduction: Airless surfaces across the solar system are continually modified by energetic particles from solar wind and micrometeoroid bombardment [1,2]. This process is known as space weathering, and it alters the chemical, microstructural, and optical properties of surface regoliths on airless bodies, including Mercury. On the Moon and S-type asteroids, the reflectance spectral signatures of space weathering include reddening (increasing reflectance with increasing wavelength), darkening (lowering of reflectance), and the attenuation of characteristic absorption bands [2]. Such spectral changes are driven by the production of Fe-bearing nanoparticles(npFe) through both solar wind irradiation and micrometeoroid bombardment. While our understanding of space weathering for the Moon and near-Earth S-types asteroids is advanced, insight into how these processes operate on other planetary bodies is limited. In particular, Mercury experiences a uniquely intense space weathering environment than planetary counterparts at 1 AU, including a moreintense solar wind flux and higher velocity micrometeoroid impacts [4]. Additionally, Mercury has a surface composition unique in the inner solar system, including regions of the surface with very low albedo known as the low reflectance material (LRM), which is enriched in carbon, likely graphite, up to 4wt.% [5].In addition, the concentration of Fe across Mercury’s surface islow (<2 wt.%) compared to the Moonor S-type asteroids asteroids[6]. Our understanding of the effects of space weathering on C-rich and Fe-poor phases is limited. Since Fe plays a critical role inthe development of space weathering characteristicson other airless surfaces(e.g., npFe), its limited availability may significantly affect the development of space weathering features in Mercury surface materials. We can simulate space weathering processes in the laboratory to explore their effects on the microstructural, chemical, and spectral characteristics of Mercury surface materials[7]. Here we used pulsed laser irradiation to simulate the short duration, high-temperature events associated with micrometeoroid impacts. We performed coordinated analyses including reflectance spectroscopy and electron microscopy to investigate the spectral, chemical, and microstructural changes in these mercurian analog samples. Methods: For these experiments, we usedforsteritic olivine with varying FeOcontents, a mineral phase proposed to be abundant on the surface of Mercury. We mixed each sample with graphite to simulate LRM regions of the surface. Wesynthesized the olivinesamplesat 1-bar at NASA’s Johnson Space Centerand prepared pressed powder pellets for laser irradiation [8].We prepared three samples, each with a base layer of olivineto maintain structural integrity and topped witha surface layer containing the graphite-olivine mixture: 1) Sample SC-001 San Carlos olivine(Fo90.91),2)Sample F-S-002 with0.05 wt.% FeO olivine, and 3) F-T-004 with 0.53 wt.% FeO olivine. Each sample was mixed with 5 wt.% powdered graphite and had grain sizes ranging from 45to 125μm. We irradiated each sample usinga pulsed Nd-YAG laser, (l=1064 nm, ~6 ns pulse duration, energy of 48 mJ/pulse) while undervacuumat Northern Arizona University. The laser was rastered1x and then 5x over the surfaceof each sample to simulate progressive space weathering. We collected in situreflectance spectra from the samples after each laser pulse witha Nicolet IS50 Fourier-Transform Infrared spectrometer (lfrom 0.65-2.5 μm). We used an FEI Nova NanoSEM200scanning electron microscope (SEM) and a Hitachi TM4000 Plus benchtop SEM at Purdue University to image the surface morphology and topography of the samples. We extracted thin sections for analysis in the transmission electron microscope(TEM)using the FEI Helios NanoLab 660 focused ion beam (FIB) SEM at the University of Arizona.We performed analysis of the microstructural and chemical characteristics of the samples using the 200 keV JEOL 2500 scanning TEM at Johnson Space Center. Reflectance Spectroscopy Results:Reflectance spectra for each sample are shown in Fig. 1.SC-001:The spectrum of the unirradiated sample exhibits a weak 1.0 μm absorption feature, associated with Fe2+in the olivine,and low overall reflectance (Fig. 1a). Thereflectance and the depth of the absorption band increases after 1x laser raster but are at their lowest after 5x laser rasters.F-T-004:The unirradiated sample has a blue-sloped spectrum with low reflectance without identifiable absorption features (Fig. 1b). With progressive laser irradiation, the sample reflectance increases and becomes strongly red-sloped.F-S-002:The unirradiated sample exhibits a dark, blue-slopedspectrum. The brightness of the sample increases significantly from <0.2average reflectance over >0.8 reflectance in the most irradiated sampleand thespectral slope also becomesslightly reddened (Fig. 1c). Microstructural and Chemical Analysis: Two primary alteration textures were observed in the samples exposed to simulated space weathering: 1) fluffy C-rich,and 2) vesiculated melt. The fluffy C-rich texture is composed oflow-densitydeposits distributed across the surface of the sample(Fig. 2A). Analysis of a FIB section extracted from a low-density C-rich region in sample SC-001 reveals multiple globule-type deposits, discrete from stacked graphite, likely produced via melting from the laser irradiation [9].The vesiculated melt textureis smooth and uniformly distributed across isolated regions of the sample surface. The vesicles measure up to 100s of nmin diameter. Analysis of a FIB section from this texture was extracted from sample F-T-004 reveals a layer of amorphous melt material, close to 100 nm thick and uniform across the FIB section (Fig. 2B). Isolated regions of this melt layer contain small nanoparticles, <5 nm in diameter. Chemical analysis through energy dispersive X-ray spectroscopy reveals the composition of this layer is enriched in Si and depleted in Mg and O compared to the underlying sample. Implications for Space Weathering on Mercury: Previous experiments simulating space weathering of Mercury have showndarkening and reddening of spectra[7,10].However, our use of low-Fe materials and graphite to create a sample set more analogous to the mercurian surface. Our results indicate that sample composition plays a significant and important role in the space weathering of Mercury. In particular, our spectral data demonstrates a strong correlation between spectral slope, Fe content, and simulated space weathering. While the variation in FeO content between samples F-S-002 and F-T-004 is <0.6 wt.%, the spectra deviate from flat to strongly red-sloped(F-T-004). This reddeningmay be linked to the presence of very small nanoparticles observed in the melt textures extracted from sample F-T-004. For the SC-001 sample, the fluffy C-rich textures may be developed by the amalgamation of small graphite particles into these unique morphologies. Such observations indicate that space weathering on Mercury may result in both familiar and new microstructural and chemical characteristics. References: [1]Hapke B. (2001) J. Geophys. Res.-Planet.,106,10039–10073. [2]Pieters C.M. and Noble S.K. (2016) J. Geophys. Res-Planet., 121, 1865–1884. [3] Lucey P.G., and Riner, M.A. (2011) Icarus,212, 451-462.[4]CintalaM.J.(1992)J. Geophys. Res.-Planet.,97,947–973.[5]Klima R.L.et al.(2018)Geophys.Res.Letters, 45, 2945–2953. [6]Nittler L.R., et al. (2011) Science 333, 1847-1850.[7]Sasaki S. and Kurahashi E. (2004) Space weathering on Mercury, Adv.Space Res., 33, 2152-2155.[8] Vander KaadenK.E., et al. (2018) LPSCXLIX, Abstract 1230. [9] McGlaun M.L. et al. (2019) LPSCL, Abstract 2019. [10] TrangD.et al. (2018)LPSCXLIX,Abstract2083

M S Thompson↗
NASA NTRSDate not supplied

SURFACE EXOSURE TIMESCALES OF APOLLO CORE SAMPLE 73002 SPACE WEATHERED GRAINS

Introduction: Space weathering causes the surface regolith on airless bodies like the Moon to be morphologically, microstructurally, and chemically altered due to micrometeoroid bombardment and solar wind irradiation[1]. These processes produce a multitude of microstructural and chemical changes in individual soil grains that accumulate as grains are exposed on the surface over time. One microstructural feature produced by exposure to the solar wind is the development of ion-damaged rims on regolith grains via H+ and He+ ion irradiation. Also present are solar energetic particle (SEP) tracks, which are nanoscale lineations of ionization damage within grain interiors formed by high energy solar flare ions(primarily Fe group nuclei) which penetrate millimeters below the surface [2]. Recent work has confirmed that the thickness of solar wind-damaged amorphous rims on anorthite grains, nanocrystalline rims on olivine grains, and their respective SEP track densities are correlated with their surface exposure ages [3].Core sample 73002, recently released under the Apollo Next Generation Sample Analysis (ANGSA) Program, has provided an opportunity to study material collected from the light mantle formation during Apollo 17. The light mantle is thought to have been deposited via a landslide originating from the neighboring South Massif [4]. Spectral profiles and ferromagnetic resonance measurements of bulk soils sampled at cm-intervals from 73002 indicate the existence of mature regolith extending ~8 cm below the surface, suggesting the presence of an in-situ reworking zone in the core[5,6].Here we present the distribution of SEP track densities, solar wind damaged rim widths, and the corresponding surface exposure ages of grains residing in the proposed in-situ reworking zone of core 73002. Methods: Bulk samples of regolith from the first eight intervals and every following fourth interval down the core (dissection Pass 2) were delivered to Purdue University as <45 μm size fractions. The first eight0.5 cm intervals, representing the top 4cmof regolith, were individually dry sieved to a<20 μm size fraction, and grains were prepared by ultramicrotomy for analysis in the scanning transmission electron microscope (STEM). Bright field (BF) and dark field (DF) STEM images of solar flare tracks and solar wind damaged rims were acquired on a JEOL 2500SE TEM, equipped with a 60 mm2ultra-thin window silicon drift energy dispersive X-ray (EDX) spectrometer at NASA John-son Space Center. Grain compositions were determined by EDX compositional spectrum imaging. SEP track densities and amorphous rim thicknesses were measured on BF and DF images. Results: The fraction of grains with discernable space weathering features decreased with depth, with 100% in the first interval exhibiting space weathering features as opposed to ~60% in Interval 8.BF and DF STEM images show splash-melt and vapor deposited rims on outermost grain margins with embedded Fe-bearing nanoparticles ranging in size up to ~10 nm in diameter. Images also show solar-wind damaged rims below the vapor deposits, and SEP tracks present in grain interiors. The rim thicknesses and SEP track densities were determined using the methods of [3] for 54grains spanning the top 4 cm. ~80% of the grains analyzed were anorthite and ~20% were olivine. The track production rate from[3] was used to estimate the surface exposure times of the grains in this study. The majority of exposure times are in the 1 -5 MY range for all intervals. The lowest value was 3.8x 10¬5years in Interval 8and the highest value was1.1x 107years in Interval 6. Grains with the highest solar wind damage rim thicknesses and SEP track densities are found in Interval 6.The highest rim thickness and track density observed for anorthiteis126.5 nm and4.7 x 1011tracks/cm2, while for olivine they are 98.6 nm and 1.83 x 1011tracks/cm2, respectively. Discussion: Intervals from the top 4 cm of 73002 show similar SEP track density and solar wind damaged rim thickness distributions. Spectral and ferromagnetic resonance measurements of 73002 indicate an in-situ reworking zone up to~8 cm below the surface[5,6].The depth analyzed in this work is within the core’s uppermost in-situ reworking zone and may serve as an explanation to the homogenous distribution of exposure ages. The decreasing abundance of space weathered features with depth is consistent with regolith mixing models showing an exponential decay in regolith maturity with depth over time[7].A maximum surface exposure age determined via SEP track density is approximately 10million years. This timescale is consistent with the lower estimate of surface exposure ages of the light mantle determined in previous studies, which can range from 10s to over 100 Ma [4].It also falls within the core regolith reworking development timescale of ~17 Ma [5,6]. Additional analysis will be performed for a further seven intervals in 73002.

J A McFadden↗
NASA NTRSDate not supplied

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↗
NASA NTRS2017

Evidence of Collisional Histories of Asteroids, Comets and Meteorites: Comparisons with Shocked Minerals

Evidence of the collisional history of comets and asteroids has been emerging from analyses of cometary forsterite and enstatite returned from Comet Wild 2 by the Stardust mission (Keller et al.Geochim. Cosmochim. Acta 72, 2008; Tomeoka et al. MAPS 43, 2008; Jacobs et al. MAPS 44, 2009). Likewise, shock metamorphism is observed in many meteoritic forsterites and enstatites (McCausland et al. AGU, 2010), suggesting similar collisional histories for asteroids. Further exploration of the effects of collisions is slated for the upcoming Asteroid Impact Mission/Double Asteroid Redirection Test (AIM/DART) mission, expected for launch in 2020. DART will impact Didymoon, the companion of the larger 65803 Didymos (1996 G2) asteroid, and AIM will use its instrumentation to characterize the impact. A suite of relevant impact experiments have been carried out in the Experimental Impact Laboratory at the NASA Johnson Space Center at velocities ranging from approx. 2.0 - 2.8 km/s and temperatures from 25 C to -100 C. Targets include a suite of minerals typically found in cometary dust and in asteroids and meteorites: Mg-rich forsterite (olivine), enstatite (orthopyroxene), diopside (clinopyroxene), magnesite (Mg-rich carbonate), and serpentine (phyllosilicate). Transmission Electron Microscope (TEM) imaging indicates evidence of shock similar to that seen in forsterite and enstatite from Comet Wild 2. Fourier Transform Infrared (FTIR) Spectroscopy will also be used for comparisons with meteorite spectra. A quantitative analysis of the shock pressures required to induce planar dislocations and spectral effects with respect to wavelength will also be presented.

Lederer, Susan M.↗
NASA NTRS1987

Structural characterization and gas reactions of small metal particles by high resolution in-situ TEM (Transmission Electron Microscopy) and TED (Transmission Electron Diffraction)

The detection and size analysis of small metal particles supported on amorphous substrates becomes increasingly difficult when the particle size approaches that of the phase contrast background structures of the support. An approach of digital image analysis, involving Fourier transformation of the original image, filtering, and image reconstruction was studied with respect to the likelihood of unambiguously detecting particles of less than 1 nm diameter on amorphous substrates from a single electron micrograph.

Heinemann, K.↗
NASA NTRS1975

Direct observation of small cluster mobility and ripening

Direct evidence is reported for the simultaneous occurrence of Ostwald ripening and short-distance cluster mobility during annealing of discontinuous metal films on clean amorphous substrates. The annealing characteristics of very thin particulate deposits of silver on amorphized clean surfaces of single crystalline thin graphite substrates were studied by in-situ transmission electron microscopy (TEM) under controlled environmental conditions (residual gas pressure of 10 to the minus 9th power torr) in the temperature range from 25 to 450 C. Sputter cleaning of the substrate surface, metal deposition, and annealing were monitored by TEM observation. Pseudostereographic presentation of micrographs in different annealing stages, the observation of the annealing behavior at cast shadow edges, and measurements with an electronic image analyzing system were employed to aid the visual perception and the analysis of changes in deposit structure recorded during annealing. Slow Ostwald ripening was found to occur in the entire temperature range, but the overriding surface transport mechanism was short-distance cluster mobility.

Heinemann, K.↗
NASA NTRS2015

Characterization of Meteorites by Focused Ion Beam Sectioning: Recent Applications to CAIs and Primitive Meteorite Matrices

Focused ion beam (FIB) sectioning has revolutionized preparation of meteorite samples for characterization by analytical transmission electron microscopy (TEM) and other techniques. Although FIB is not "non-destructive" in the purest sense, each extracted section amounts to no more than nanograms (approximately 500 cubic microns) removed intact from locations precisely controlled by SEM imaging and analysis. Physical alteration of surrounding material by ion damage, fracture or sputter contamination effects is localized to within a few micrometers around the lift-out point. This leaves adjacent material intact for coordinate geochemical analysis by SIMS, microdrill extraction/TIMS and other techniques. After lift out, FIB sections can be quantitatively analyzed by electron microprobe prior to final thinning, synchrotron x-ray techniques, and by the full range of state-of-the-art analytical field-emission scanning transmission electron microscope (FE-STEM) techniques once thinning is complete. Multiple meteorite studies supported by FIB/FE-STEM are currently underway at NASA-JSC, including coordinated analysis of refractory phase assemblages in CAIs and fine-grained matrices in carbonaceous chondrites. FIB sectioning of CAIs has uncovered epitaxial and other overgrowth relations between corundum-hibonite-spinel consistent with hibonite preceding corundum and/or spinel in non-equilibrium condensation sequences at combinations of higher gas pressures, dust-gas enrichments or significant nebular transport. For all of these cases, the ability of FIB to allow for coordination with spatially-associated isotopic data by SIMS provides immense value for constraining the formation scenarios of the particular CAI assemblage. For carbonaceous chondrites matrix material, FIB has allowed us to obtain intact continuous sections of the immediate outer surface of Murchison (CM2) after it has been experimentally ion processed to simulate solar wind space weathering. The surface amorphization and loss of OH produced by the irradiation provides important clues regarding space weathering on primitive asteroids such as the OSIRIS-Rex target 101955 Bennu.

Christoffersen, Roy↗
NASA NTRS1996

Soot Precursor Material: Visualization Via Simultaneous LIF-LII and Characterization Via TEM

Simultaneous combined laser-induced fluorescence and laser-induced incandescence (LIF-LII) images are presented for both a normal and inverse diffusion flame. The excitation wavelength dependence distinguishes the LIF and LII signals in images from the normal diffusion flame while the temporal decay distinguishes the signals in images of the inverse diffusion flame. Each flame presents a minimum in the combined LIF-LII intensity in a region separating the fuel pyrolysis and soot containing regions. Opacity, geometric in definition, and extent of crystallinity measured through both bright and dark field Transmission Electron Microscopy (TEM) characterizes the thermophoretically sampled material from within this minimal LIF-LII intensity region. TEM analysis reveals rather different soot processes occurring within the normal and inverse diffusion flame. In the normal diffusion flame, rapid chemical and physical coalescence of PAHs results in initial formation of soot precursor particles that are highly crystalline and evolve toward fully formed soot. In the inverse diffusion flame, rapid coalescence of pyrolysis products occurs, producing tarlike, globular structures equivalent in size to fully formed soot aggregates but with markedly less crystallinity than normal-appearing soot. These different material properties are interpreted as reflecting different relative rates of chemical and physical coalescence of fuel pyrolysis products versus carbonization. Significantly, these TEM images support qualitative photophysical arguments suggesting that, in general, this 'dark' region observed in the LIF-LII images demarcates a transitional region in which a fundamental change in the material the material chemical/physical properties occurs between solid carbonaceous soot and condensed or gaseous molecular growth material.

VanderWal, Randall L.↗
NASA NTRS1998

Effect of Pigmentation in Particulate Formation from Fluoropolymer Thermodegradation in Microgravity

Fires aboard spacecraft have occurred as a result of overheated electrical wires and thermodegradation of their insulation, which is composed of fluoropolymers. The particulate products of polymer thermodegradation are only 20-50 run in diameter and are thought to play a role in "polymer fume fever". Therefore an experimental study of the particulates produced by intense ohmic heating of various fluoropolymer-insulated 20 AWG copper wire (representative of spacecraft materials) was undertaken in normal gravity and in microgravity. The 2.2 s drop facility at NASA LeRC and 1.5 s drop facility at the Colorado School of Mines were used to achieve low gravity conditions. Thermophoretic sampling was used for particulate collection. Transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) were used to characterize the smoke particulates. It was found that the color of PTFE (Polytetrafluoroethylene) insulation has an overwhelming effect on the size, shape, morphology and, composition of the particulates. Size distributions and shape analyses using computerized image analysis showed that particle size distributions were also dependent on the pigment of the fluoropolymer insulation. The influence of pigment was observed in experiments under both normal and microgravity. Under microgravity conditions, owing to the lack of natural convective transport of particulates, much more particle aggregation was observed, and the nature of the aggregates was dependent on the color of the insulation.

Srivastava, Rajiv↗
NASA NTRS2003

Three-Dimensional Morphological Analysis of ALH84001 Magnetite Using Electron Tomography

We report here the crystal morphologies of MV-1 and ALH84001 magnetites as calculated by back-projection using electron tomography. In the present study, we used a 300 keV TEM with a field emission gun (Tecnai F-30 from FEI Inc.), equipped with a 2048 x 2048 pixel CCD camera from Gatan Inc. to image magnetite crystals over tilt ranges of approx. +/- 72 deg in 2 deg tilt intervals. The images were aligned for back-projection, either manually, or through the use of fiducial 5 nm Au spheres affixed to the specimen prior to microscopy. Three-dimensional (3-D) reconstructions were computed using weighted back-projection of the tilted views. The tomograms were viewed and analyzed as a series of slices 1.0 nm thick, taken parallel to the specimen-supporting grid, using the IMOD software package. The shape of each magnetite crystal was determined by defining the external contour of a given magnetite in each slice and assembling a stack of these contours in 3-D. To aid in visualization, the stacked contour array was reduced to an optimal mesh by Delaunay triangulation. The surface normal to each of the triangles in the mesh was calculated and the triangle faces colored according to the orientation of that surface normal relative to the principal crystallographic axis of magnetite. Green surfaces correspond to {111} orientations, blue surfaces to {100} orientations, and red surfaces to {110} orientations. Triangles whose surface normal did not correspond to one of the principal axes were colored gray. Within the experimental and numerical uncertainties of the deconvolution, the tomographic reconstruction of both MV-1 and ALH84001 magnetites are equivalent and correspond to a truncated hexa-octahedral morphology.

Thomas-Keprta, Kathie L.↗