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Digital image processing of nanometer-size metal particles on amorphous substrates

The task of differentiating very small metal aggregates supported on amorphous films from the phase contrast image features inherently stemming from the support is extremely difficult in the nanometer particle size range. Digital image processing was employed to overcome some of the ambiguities in evaluating such micrographs. It was demonstrated that such processing allowed positive particle detection and a limited degree of statistical size analysis even for micrographs where by bare eye examination the distribution between particles and erroneous substrate features would seem highly ambiguous. The smallest size class detected for Pd/C samples peaks at 0.8 nm. This size class was found in various samples prepared under different evaporation conditions and it is concluded that these particles consist of 'a magic number' of 13 atoms and have cubooctahedral or icosahedral crystal structure.

Soria, F.↗

The Evolution of the Deformation Substructure in a Ni-Co-Cr Equiatomic Solid Solution Alloy

The equiatomic NiCoCr alloy exhibits an excellent combination of strength and ductility, even greater than the FeNiCrCoMn high entropy alloy, and also displays a simultaneous increase in strength and ductility with decreasing the testing temperature. To systemically investigate the origin of the exceptional properties of NiCoCr alloy, which are related to the evolution of the deformation substructure with strain, interrupted tensile testing was conducted on the equiatomic NiCoCr single-phase solid solution alloy at both cryogenic and room temperatures at five different plastic strain levels of 1.5%, 6.5%, 29%, 50% and 70%. The evolution of deformation substructure was examined using electron backscatter diffraction (EBSD), transmission Kikuchi diffraction (TKD), conventional transmission electron microscopy (CTEM), diffraction contrast imaging using STEM (DCI-STEM) and atomic resolution scanning transmission electron microscopy. While the deformation substructure mainly consisted of planar dislocation slip and the dissociation of dislocations into stacking faults at small strain levels (≤6.5%), at larger strain levels, additional substructures including nanotwins and a new phase with hexagonal close packed (HCP) lamellae also appeared. The volume fraction of the HCP lamellae increases with increasing deformation, especially at cryogenic temperature. First principles calculations at 0 K indicate that the HCP phase is indeed energetically favorable relative to FCC for this composition. The effects of the nanotwin and HCP lamellar structures on hardening rate and ductility at both cryogenic and room temperature are qualitatively discussed.

Twinning↗

Biomolecular Analysis Capability for Cellular and Omics Research on the International Space Station

International Space Station (ISS) assembly complete ushered a new era focused on utilization of this state-of-the-art orbiting laboratory to advance science and technology research in a wide array of disciplines, with benefits to Earth and space exploration. ISS enabling capability for research in cellular and molecular biology includes equipment for in situ, on-orbit analysis of biomolecules. Applications of this growing capability range from biomedicine and biotechnology to the emerging field of Omics. For example, Biomolecule Sequencer is a space-based miniature DNA sequencer that provides nucleotide sequence data for entire samples, which may be used for purposes such as microorganism identification and astrobiology. It complements the use of WetLab-2 SmartCycler"TradeMark", which extracts RNA and provides real-time quantitative gene expression data analysis from biospecimens sampled or cultured onboard the ISS, for downlink to ground investigators, with applications ranging from clinical tissue evaluation to multigenerational assessment of organismal alterations. And the Genes in Space-1 investigation, aimed at examining epigenetic changes, employs polymerase chain reaction to detect immune system alterations. In addition, an increasing assortment of tools to visualize the subcellular distribution of tagged macromolecules is becoming available onboard the ISS. For instance, the NASA LMM (Light Microscopy Module) is a flexible light microscopy imaging facility that enables imaging of physical and biological microscopic phenomena in microgravity. Another light microscopy system modified for use in space to image life sciences payloads is initially used by the Heart Cells investigation ("Effects of Microgravity on Stem Cell-Derived Cardiomyocytes for Human Cardiovascular Disease Modeling and Drug Discovery"). Also, the JAXA Microscope system can perform remotely controllable light, phase-contrast, and fluorescent observations. And upcoming confocal microscopy capability will allow for optical sectioning of biological tissues to determine microanatomical localization of biomarkers. Furthermore, NASA's geneLAB effort addresses integration of genomic, epigenomic, transcriptomic, proteomic and metabolomic datasets, by applying an innovative open source science platform for multi-investigator high throughput utilization of the ISS. In sum, the expanding ISS capability for analysis of biomolecules is enabling innovative research in a broad spectrum of areas such as cellular and molecular biology, biotechnology, tissue engineering, biomedicine, and Omics, providing manifold benefits for humanity.

Guinart-Ramirez, Y.↗

Studies on Auditory and Vestibular End Organs and Brain Stem Nuclei

Cats were exposed to tones of 125, 1000, 2000, and 4000 Hz at sound pressure levels in the range 120 to 157.5 db, and for durations of one hour (1000, 2000, 4000 Hz) or four hours (125 Hz). Pure tone audiograms were obtained for each animal before and after exposure. Cochleas of animals were examined by phase-contrast microscopy. Extent of inner ear damage and range of frequencies for which hearing loss occurred increased as exposure tone was decreased in frequency. For example, exposure to 4000 Hz produced damage in a restricted region of the cochlea and hearing loss for a relatively narrow range of frequencies; exposure to 125 Hz produced wide-spread inner ear damage and hearing loss throughout the frequency range 125 to 6000 Hz.

Ades, H. W.↗

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↗

Fundamental Studies of Solidification in Microgravity Using Real-Time X-Ray Microscopy

This research applies a state of the art X-ray Transmission Microscope, XTM, to image (with resolutions up to 3 micrometers) the solidification of metallic or semiconductor alloys in real-time. We have successfully imaged in real-time: interfacial morphologies, phase growth, coalescence, incorporation of phases into the growing interface, and the solute boundary layer in the liquid at the solid-liquid interface. We have also measured true local growth rates and can evaluate segregation structures in the solid; a form of in-situ metallography. During this study, the growth of secondary phase fibers and lamellae from eutectic and monotectic alloys have been imaged during solidification, in real-time, for the first time in bulk metal alloys. Current high resolution X-ray sources and high contrast X-ray detectors have advanced to allow systematic study of solidification dynamics and the resulting microstructure. We have employed a state-of-the-art sub-micron source with acceleration voltages of 10-100 kV to image solidification of metals. One useful strength of the XTM stems from the manner an image is formed. The radiographic image is a shadow formed by x-ray photons that are not absorbed as they pass through the specimen. Composition gradients within the specimen cause variations in absorption of the flux such that the final image represents a spatial integral of composition (or thickness). The ability to image these features in real-time enables more fundamental and detailed understanding of solidification dynamics than has previously been possible. Hence, application of this technique towards microgravity experiments will allow rigorous testing of critical solidification models.

Curreri, Peter A.↗

Basalt Alteration in a CO 2 -SO 2 Atmosphere: Implications for Surface Processes on Venus

Venus’ surface and interior dynamics remain largely unconstrained, due in great part to the major obstacles to exploration imposed by its 470°C, 90 bar surface conditions and its thick, opaque atmosphere. Orbiter-based thermal emission data provide opportunities to characterize the surface composition of Venus. However, interpretations of such spectra depend on understanding interactions between the planet’s surface basaltic rocks and its caustic, sulfur dioxide (SO 2 )-bearing carbon dioxide (CO 2 ) atmosphere. Several studies, using remote sensing, thermodynamic modeling, and laboratory experiments, have placed constraints on basaltic alteration mineralogies and rates. Yet constraint with respect to SO 2 -mediated reactions with basalts of contrasting compositions remains incomplete. Here, we present new data from a series of gas-solid reaction experiments, in which samples of two basalt compositions were reacted in an SO 2 -bearing CO 2 atmosphere, at relevant Venus temperatures, pressure, and oxygen fugacity. We subjected reacted specimens to scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM) analyses using sample cross-sections produced with focused ion beam (FIB) milling. Surface alteration products were characterized, and their abundances estimated; subsurface cation concentrations were mapped to show depth of alteration. We demonstrate that the initial rate of reaction in our experiments is very rapid. Alkaline basalt samples are coated by (meta)thenardite (Na 2 SO 4 ) and amorphous calcium carbonate (CaCO 3 ) alteration products, and tholeiitic basalt samples are primarily covered by anhydrite (CaSO 4 ), Fe-oxide (Fe x O y : likely magnetite, Fe 3 O 4 ), and other minor phases.

Venus↗

Convergent properties of vestibular-related brain stem neurons in the gerbil

Three classes of vestibular-related neurons were found in and near the prepositus and medial vestibular nuclei of alert or decerebrate gerbils, those responding to: horizontal translational motion, horizontal head rotation, or both. Their distribution ratios were 1:2:2, respectively. Many cells responsive to translational motion exhibited spatiotemporal characteristics with both response gain and phase varying as a function of the stimulus vector angle. Rotationally sensitive neurons were distributed as Type I, II, or III responses (sensitive to ipsilateral, contralateral, or both directions, respectively) in the ratios of 4:6:1. Four tested factors shaped the response dynamics of the sampled neurons: canal-otolith convergence, oculomotor-related activity, rotational Type (I or II), and the phase of the maximum response. Type I nonconvergent cells displayed increasing gains with increasing rotational stimulus frequency (0.1-2.0 Hz, 60 degrees /s), whereas Type II neurons with convergent inputs had response gains that markedly decreased with increasing translational stimulus frequency (0.25-2.0 Hz, +/-0.1 g). Type I convergent and Type II nonconvergent neurons exhibited essentially flat gains across the stimulus frequency range. Oculomotor-related activity was noted in 30% of the cells across all functional types, appearing as burst/pause discharge patterns related to the fast phase of nystagmus during head rotation. Oculomotor-related activity was correlated with enhanced dynamic range compared with the same category that had no oculomotor-related response. Finally, responses that were in-phase with head velocity during rotation exhibited greater gains with stimulus frequency increments than neurons with out-of-phase responses. In contrast, for translational motion, neurons out of phase with head acceleration exhibited low-pass characteristics, whereas in-phase neurons did not. Data from decerebrate preparations revealed that although similar response types could be detected, the sampled cells generally had lower background discharge rates, on average one-third lower response gains, and convergent properties that differed from those found in the alert animals. On the basis of the dynamic response of identified cell types, we propose a pair of models in which inhibitory input from vestibular-related neurons converges on oculomotor neurons with excitatory inputs from the vestibular nuclei. Simple signal convergence and combinations of different types of vestibular labyrinth information can enrich the dynamic characteristics of the rotational and translational vestibuloocular responses.

Non-NASA Center↗