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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↗

High-Efficiency Ka-Band Waveguide Two-Way Asymmetric Power Combiner

NASA is planning a number of Space Exploration, Earth Observation and Space Science missions where Ka-band solid-state power amplifiers (SSPAs) could have a role. Monolithic microwave integrated circuit (MMIC) based SSPAs with output powers on the order of 10 W at Ka-band frequencies would be adequate to satisfy the data transmission rate requirements at the distances involved. MMICs are a type of integrated circuit fabricated on a GaAs wafer, which operates at micro wave frequencies and performs the function of signal amplification. The highest power Ka-band (31.8 to 32.3 GHz) SSPA to have flown in space had an output power of 2.6 W with an overall efficiency of 14.3 percent. This SSPA was built around discrete GaAs pHEMT (high electron mobility transistor) devices and flew aboard the Deep Space One spacecraft. State-of-the-art GaAs pHEMT-based MMIC power amplifiers (PAs) can deliver RF power at Ka-band frequencies anywhere from 3 W with a power added efficiency (PAE) of 32 percent to 6 W with a PAE of 26 percent. However, to achieve power levels higher than 6 W, the output of several MMIC PAs would need to be combined using a high-efficiency power combiner. Conventional binary waveguide power combiners, based on short-slot and magic-T circuits, require MMIC PAs with identical amplitude and phase characteristics for high combining efficiency. However, due to manufacturing process variations, the output powers of the MMIC PAs tend to be unequal, and hence the need to develop unequal power combiners. A two-way asymmetric magic-T based power combiner for MMIC power amplifiers, which can take in unequal inputs, has been successfully designed, fabricated, and characterized over NASA s Deep Space Network (DSN) frequency range of 31.8 to 32.3 GHz. The figure is a transparent view of the a sym - metric combiner that shows the 4-port configuration and the internal structure. The rod, post, and iris are positioned by design to achieve the desired asymmetric power ratio, phase equality, and port isolation. Although the combiner was designed for an input power ratio of 2:1, it can be custom-designed for any arbitrary power ratio and frequency range. The manufactured prototype combiner was precision machined from aluminum and is less than 2 in.3 (32.8 cm3). Previously investigated rectangular waveguide unequal power combiners were based on shunt/series coupling slots, E-plane septums, or H-plane T-junctions. All the prior art unequal power combiners operated at or below X-band (10 GHz) frequencies and were primarily used in the feed network of antenna arrays. The only reported asymmetric magic-T was developed as a 2:1 power divider for operation at a much lower frequency, around 500 MHz. The measured power ratio when tested as a power divider was very close to 2 and the phase balance was within 2.6, resulting in near ideal performance. When tested as a combiner using two MMIC SSPAs with a 2:1 power output ratio, an efficiency greater than 90 percent was demonstrated over the 500 MHz DSN frequency range. The return loss at the combiner output port (1) was greater than 18 dB and the input port (2 and 3) isolation was greater than 22 dB. The results show the asymmetric combiner to be a good candidate for high-efficiency power combining of two or more SSPAs needed to achieve the 6 to 10 W required by space communications systems of future NASA missions.

Wintucky, E. G.↗

NASA Tech Briefs, November 2011

The topics include: 1) Flight Test Results from the Rake Airflow Gage Experiment on the F-15B; 2) Telemetry and Science Data Software System; 3) CropEx Web-Based Agricultural Monitoring and Decision Support; 4) High-Performance Data Analysis Tools for Sun-Earth Connection Missions; 5) Experiment in Onboard Synthetic Aperture Radar Data Processing; 6) Microfabrication of a High-Throughput Nanochannel Delivery/Filtration System; 7) Improved Design and Fabrication of Hydrated-Salt Pills; 8) Monolithic Flexure Pre-Stressed Ultrasonic Horns; 9) Cryogenic Quenching Process for Electronic Part Screening; 10) Broadband Via-Less Microwave Crossover Using Microstrip-CPW Transitions; 11) Wheel-Based Ice Sensors for Road Vehicles; 12) G-DYN Multibody Dynamics Engine; 13) Multibody Simulation Software Testbed for Small-Body Exploration and Sampling; 14) Propulsive Reaction Control System Model; 15) Licklider Transmission Protocol Implementation; 16) Core Recursive Hierarchical Image Segmentation; 17) Two-Stage Centrifugal Fan; 18) Combined Structural and Trajectory Control of Variable-Geometry Planetary Entry Systems; 19) Pressure Regulator With Internal Ejector Circulation Pump, Flow and Pressure Measurement Porting, and Fuel Cell System Integration Options; 20) Temperature-Sensitive Coating Sensor Based on Hematite; 21) Standardization of a Volumetric Displacement Measurement for Two-Body Abrasion Scratch Test Data Analysis; 22) Detection of Carbon Monoxide Using Polymer-Carbon Composite Films; 23) Substituted Quaternary Ammonium Salts Improve Low-Temperature Performance of Double-Layer Capacitors; 24) Sustainably Sourced, Thermally Resistant, Radiation Hard Biopolymer; 25) Integrated Lens Antennas for Multi-Pixel Receivers; 26) 180-GHz Interferometric Imager; 27) Maturation of Structural Health Management Systems for Solid Rocket Motors; 28) Validating Phasing and Geometry of Large Focal Plane Arrays; 29) Transverse Pupil Shifts for Adaptive Optics Non-Common Path Calibration; 30) Qualification of Fiber Optic Cables for Martian Extreme Temperature Environments; 31) Solid-State Spectral Light Source System; 32) Multiple-Event, Single-Photon Counting Imaging Sensor; 33) Surface Modeling to Support Small-Body Spacecraft Exploration and Proximity Operations; and 34) Achieving Exact and Constant Turnaround Ratio in a DDS-Based Coherent Transponder.

Source record↗

Determination of Interfacial Energy for Solid-State Precipitation

Precipitation of strengthening phases from solid state is a critical process for many materials. For example, the high-temperature creep resistance of Ni-based superalloys is governed by ’ precipitates. However, the interfacial energy which controls the precipitation is expensive to determine experimentally. For simulations, the atomic nature of precipitation events necessitates using Molecular Dynamics (MD) so relying on fitting to a-priori experimental behavior is not required. However, the solid-state precipitation takes orders of magnitude longer time than is accessible for traditional MD simulation. Taking inspiration from Kinetic Monte-Carlo (KMC) methods for simulating diffusion on a rigid lattice, we have developed a hybrid KMC-MD approach to enable simulation of solid-state precipitation (and determination of the interfacial energy). Implementing these methods in LAMMPS, we calculated the interfacial energy for the ’ precipitation out of a super-saturated  phase in Ni-based superalloys. The resulting interfacial energy value for the Ni-Al system is well within the accuracy of experimental values, demonstrating the capability of this method. Enabling the calculation of the interfacial energy without a-priori experimental knowledge of the precipitation unlocks a more efficient ICME-based approach for guiding annealing protocols in Ni-based superalloys and other solid-state precipitation systems.

Precipitation↗

Overview of NASA's Microgravity Materials Research Program

The NASA microgravity materials program is dedicated to conducting microgravity experiments and related modeling efforts that will help us understand the processes associated with the formation of materials. This knowledge will help improve ground based industrial production of such materials. The currently funded investigations include research on the distribution of dopants and formation of defects in semiconductors, transitions between columnar and dendritic grain morphology, coarsening of phase boundaries, competition between thermally and kinetically favored phases, and the formation of glassy vs. crystalline material. NASA microgravity materials science investigators are selected for funding either through a proposal in response to a NASA Research Announcement or by participation in a team proposing to a foreign agency research announcement. In the latter case, a US investigator participating in a successful proposal to a foreign agency can then apply to NASA for funding of an unsolicited proposal. The program relies on cooperation with other aerospace partners from around the world. The ISS facilities used for these investigations are provided primarily by partnering with foreign agencies and in most cases the US investigators are working as a part of a larger team studying a specific area of materials science. The following facilities are to be utilized for the initial investigations. The ESA provided Low Gradient Facility and the Solidification and Quench Inserts to the Materials Research Rack/Materials Science Laboratory are to be used primarily for creating bulk samples that are directionally solidified or quenched from a high temperature melt. The CNES provided DECLIC facility is used to observe morphological development in transparent materials. The ESA provided Electro-Magnetic Levitator (EML) is designed to levitate, melt and then cool samples in order to study nucleation behavior. The facility provides conditions in which nucleation of the solid is not triggered from the wall and in which fluid flows in the sample can be controlled and manipulated. These conditions allow scientists ideal conditions for understanding the relative amounts and distribution of different phases that form in the solid. Finally, the Coarsening of Solid Liquid Melts hardware allows quenching of low temperature samples in the Microgravity Science Glovebox.

Downey, James Patton↗

Dynamics in Layer Models of Solid Flame Propagation

Self-propagating high-temperature synthesis (SHS) is a process in which combustion waves, e.g., "solid flames", which are considered here, are employed to synthesize desired materials. Like many other systems, SHS is a pattern forming system. The problem of describing experimentally observed patterns and of predicting new, as yet unobserved, patterns continues to attract the attention of scientists and mathematicians due to the fundamental significance of the phenomena in combustion in particular, and in nonlinear science in general. Here, we analyze the dynamics of solid flame propagation in a 2D region by considering the region to be composed of parallel, identical layers aligned along the direction of propagation and having thermal contact. Each layer is then described by wave propagation in 1D, with the transverse Laplacian replaced by a term describing heat exchange between neighboring layers. This configuration is the simplest model of a 2D system because it accounts, in a simple way, for the principal feature of the problem, i.e., heat exchange between neighbors in the transverse direction. For simplicity, we describe the situation for two layers. Because the layers are identical, uniformly propagating waves in each layer must be identical, independent of the heat exchange rate alpha. When the Zeldovich number Z exceeds a critical value Z(sub c), which depends on alpha, uniformly propagating waves become unstable. The stability diagram for the two coupled layers reproduces that for the full 2D problem after appropriate identification of parameters in the two problems. Depending on parameter values, we determine three different steady-state dynamical behaviors (though additional behaviors are also expected to occur). The three behaviors are: (i) waves in each layer which pulsate in phase as they propagate, so that together they form a single pulsating propagating wave; (ii) the waves in each layer are no longer identical, and antiphase pulsations occur, with the two waves alternately advancing and receding as they propagate. This wave is the analog of the spinning wave on the surface of a circular cylinder; (iii) finally, there is a region of bistability between the in phase and antiphase waves. with each having its own domain of attraction, so that which of the two behaviors occur depends on the condition of initiation of the wave. The results of our computations indicate a qualitative similarity in the behavior of combustion waves in the layer model and in the full 2D model. Specifically, due to the similarity between the small alpha wave behavior in the layer model and the large diameter behavior in the model of waves on the surface of a cylinder, we are able to predict the behavior of the mean velocity for the waves on the cylinder, where computations of the full problem can be rather difficult. We also compute solutions for three or more layers. The results of our computations prompt us to predict that, while planar uniformly propagating waves are unstable, the wave will be quasiplanar, i.e., the resulting spinning waves have very low amplitude hot spots, and travel with the velocity close to that of the uniformly propagating wave. Such waves may be difficult to distinguish from uniformly propagating waves in experiments. We also find that for both the layer model and full 2D problem, steady-state time-dependent waves, e.g., pulsating and spinning wave, have a conserved quantity H which characterizes the excess energy in the wave, just as in the case of uniformly propagating waves. The quantity H, which is generated by dissipation, does not vary in time and is proportional to the diffusivity and caloricity of the system, and inversely proportional to the mean wave velocity.

Aldushin, A. P.↗

NASA Tech Briefs, January 2013

Topics include: Single-Photon-Sensitive HgCdTe Avalanche Photodiode Detector; Surface-Enhanced Raman Scattering Using Silica Whispering-Gallery Mode Resonators; 3D Hail Size Distribution Interpolation/Extrapolation Algorithm; Color-Changing Sensors for Detecting the Presence of Hypergolic Fuels; Artificial Intelligence Software for Assessing Postural Stability; Transformers: Shape-Changing Space Systems Built with Robotic Textiles; Fibrillar Adhesive for Climbing Robots; Using Pre-Melted Phase Change Material to Keep Payloads in Space Warm for Hours without Power; Development of a Centrifugal Technique for the Microbial Bioburden Analysis of Freon (CFC-11); Microwave Sinterator Freeform Additive Construction System (MS-FACS); DSP/FPGA Design for a High-Speed Programmable S-Band Space Transceiver; On-Chip Power-Combining for High-Power Schottky Diode-Based Frequency Multipliers; FPGA Vision Data Architecture; Memory Circuit Fault Simulator; Ultra-Compact Transputer-Based Controller for High-Level, Multi-Axis Coordination; Regolith Advanced Surface Systems Operations Robot Excavator; Magnetically Actuated Seal; Hybrid Electrostatic/Flextensional Mirror for Lightweight, Large-Aperture, and Cryogenic Space Telescopes; System for Contributing and Discovering Derived Mission and Science Data; Remote Viewer for Maritime Robotics Software; Stackfile Database; Reachability Maps for In Situ Operations; JPL Space Telecommunications Radio System Operating Environment; RFI-SIM: RFI Simulation Package; ION Configuration Editor; Dtest Testing Software; IMPaCT - Integration of Missions, Programs, and Core Technologies; Integrated Systems Health Management (ISHM) Toolkit; Wind-Driven Wireless Networked System of Mobile Sensors for Mars Exploration; In Situ Solid Particle Generator; Analysis of the Effects of Streamwise Lift Distribution on Sonic Boom Signature; Rad-Tolerant, Thermally Stable, High-Speed Fiber-Optic Network for Harsh Environments; Towed Subsurface Optical Communications Buoy; High-Collection-Efficiency Fluorescence Detection Cell; Ultra-Compact, Superconducting Spectrometer-on-a-Chip at Submillimeter Wavelengths; UV Resonant Raman Spectrometer with Multi-Line Laser Excitation; Medicine Delivery Device with Integrated Sterilization and Detection; Ionospheric Simulation System for Satellite Observations and Global Assimilative Model Experiments - ISOGAME; Airborne Tomographic Swath Ice Sounding Processing System; flexplan: Mission Planning System for the Lunar Reconnaissance Orbiter; Estimating Torque Imparted on Spacecraft Using Telemetry; PowderSim: Lagrangian Discrete and Mesh-Free Continuum Simulation Code for Cohesive Soils; Multiple-Frame Detection of Subpixel Targets in Thermal Image Sequences; Metric Learning to Enhance Hyperspectral Image Segmentation; Basic Operational Robotics Instructional System; Sheet Membrane Spacesuit Water Membrane Evaporator; Advanced Materials and Manufacturing for Low-Cost, High-Performance Liquid Rocket Combustion Chambers; Motor Qualification for Long-Duration Mars Missions.

Source record↗

Updates on the Predictive Materials Modeling Software Tools

Updates on NASA‘s efforts to build a Predictive Material Modeling (PMM) framework from the micro-scale to the macro-scale are presented in this abstract. The PMM effort is part of the Entry Systems Modeling (ESM) project under NASA’s Game Changing Development (GCD) program. To reduce the need for extensive testing and accelerate the design cycle process, ESM is developing simulation and modeling tools that enable the characterization of the properties of thermal protection materials and their response to extremely hot plasma. The Porous Microstructure Analysis (PuMA) software has been developed to compute effective material properties and perform material response simulations on digitized microstructures of porous media. PuMA is able to import three-dimensional digital images obtained from X-ray microtomography or to generate artificial microstructures that mimic real materials. PuMA also provides a module for interactive 3D visualizations. Version 3, which was recently released as open-source, includes modules to compute simple morphological properties such as porosity, volume fractions, pore diameter, and specific surface area. Additional capabilities include the determination of effective thermal and electrical conductivity (both radiative and solid conduction - including the ability to simulate local anisotropy for the latter); effective diffusivity and tortuosity from the continuum to the rarefied regime; techniques to determine the local material orientation, as well as mechanical properties (elasticity coefficients), and permeability. Computed properties are then used to inform a macro-scale material response model, such as those implemented in the Porous material Analysis Toolbox based on OpenFOAM (PATO) software developed within ESM. The computational model in PATO is a generic heat and mass transfer model for porous reactive materials containing several solid phases and a single gas phase. The detailed chemical interactions occurring between the solid phases and the gas phase are modeled at the pore scale, assuming Local Thermal Equilibrium. Recent efforts include the development of a mechanical erosion model as well as a unified model allowing an intrinsic coupling between fluid and material. Comparison to flight data (Mars Science Laboratory [MSL] Entry Descent and Landing Instrument [MEDLI] and Mars 2020 MEDLI2) is critical in order to validate these computational tools. Examples of ablative material response using the code will be presented, including 3D simulations of the full-scale heatshield of the MSL capsule. The simulations demonstrated the ability of the modern material response code, PATO, to handle the material response of geometrically complex and large domains through the use of massively parallel computations.

material modeling↗

Bounding the Role of Black Carbon in the Climate System: a Scientific Assessment

Black carbon aerosol plays a unique and important role in Earth's climate system. Black carbon is a type of carbonaceous material with a unique combination of physical properties. This assessment provides an evaluation of black-carbon climate forcing that is comprehensive in its inclusion of all known and relevant processes and that is quantitative in providing best estimates and uncertainties of the main forcing terms: direct solar absorption; influence on liquid, mixed phase, and ice clouds; and deposition on snow and ice. These effects are calculated with climate models, but when possible, they are evaluated with both microphysical measurements and field observations. Predominant sources are combustion related, namely, fossil fuels for transportation, solid fuels for industrial and residential uses, and open burning of biomass. Total global emissions of black carbon using bottom-up inventory methods are 7500 Gg/yr in the year 2000 with an uncertainty range of 2000 to 29000. However, global atmospheric absorption attributable to black carbon is too low in many models and should be increased by a factor of almost 3. After this scaling, the best estimate for the industrial-era (1750 to 2005) direct radiative forcing of atmospheric black carbon is +0.71 W/sq m with 90% uncertainty bounds of (+0.08, +1.27)W/sq m. Total direct forcing by all black carbon sources, without subtracting the preindustrial background, is estimated as +0.88 (+0.17, +1.48) W/sq m. Direct radiative forcing alone does not capture important rapid adjustment mechanisms. A framework is described and used for quantifying climate forcings, including rapid adjustments. The best estimate of industrial-era climate forcing of black carbon through all forcing mechanisms, including clouds and cryosphere forcing, is +1.1 W/sq m with 90% uncertainty bounds of +0.17 to +2.1 W/sq m. Thus, there is a very high probability that black carbon emissions, independent of co-emitted species, have a positive forcing and warm the climate. We estimate that black carbon, with a total climate forcing of +1.1 W/sq m, is the second most important human emission in terms of its climate forcing in the present-day atmosphere; only carbon dioxide is estimated to have a greater forcing. Sources that emit black carbon also emit other short-lived species that may either cool or warm climate. Climate forcings from co-emitted species are estimated and used in the framework described herein. When the principal effects of short-lived co-emissions, including cooling agents such as sulfur dioxide, are included in net forcing, energy-related sources (fossil fuel and biofuel) have an industrial-era climate forcing of +0.22 (0.50 to +1.08) W/sq m during the first year after emission. For a few of these sources, such as diesel engines and possibly residential biofuels, warming is strong enough that eliminating all short-lived emissions from these sources would reduce net climate forcing (i.e., produce cooling). When open burning emissions, which emit high levels of organic matter, are included in the total, the best estimate of net industrial-era climate forcing by all short-lived species from black-carbon-rich sources becomes slightly negative (0.06 W/sq m with 90% uncertainty bounds of 1.45 to +1.29 W/sq m). The uncertainties in net climate forcing from black-carbon-rich sources are substantial, largely due to lack of knowledge about cloud interactions with both black carbon and co-emitted organic carbon. In prioritizing potential black-carbon mitigation actions, non-science factors, such as technical feasibility, costs, policy design, and implementation feasibility play important roles. The major sources of black carbon are presently in different stages with regard to the feasibility for near-term mitigation. This assessment, by evaluating the large number and complexity of the associated physical and radiative processes in black-carbon climate forcing, sets a baseline from which to improve future climate forcing estimates.

black carbon↗

Vapor Growth of ZnSe-based Compound Semiconductors in Low Gravity environment on International Space Station

Six low-gravity experiments of crystal growth of ZnSe-based compound semiconductors by physical vapor transport (PVT) are scheduled to be processed inside Low Gradient Furnace (LGF) on Materials Science Research Rack (MSRR) in Material Science Laboratory (MSL) on International Space Station (ISS) starting from February 27th, 2023. The flight samples consist of three unseeded growths of ZnSe, Cr-doped ZnSe and ZnSeTe as well as growth of ZnSe on top of three single crystal ZnSe seeds with orientation of (100), (110) and (111). The main scientific objective of the flight experiments is to establish the effects of gravity-driven fluid flows on Earth to (i) the non-uniform incorporation of impurities and defects and (ii) the deviation from stoichiometry observed in the grown crystals caused by growth interface fluctuations and evolution as the results of buoyancy-driven convection and irregular fluid-flows. The investigation will also evaluate the effects of gravity on the PVT process by examining (i) the growth kinetics on various seed orientations, (ii) the dopant segregation and distribution in the Cr doped ZnSe, and (iii) the compositional segregation and distribution in the ternary ZnSeTe crystal grown by PVT. Additionally, from X-ray diffraction/topography and by measuring the density and distribution of various crystalline defects it will assess the self-induced strain effects developed during processing at elevated temperatures caused by the weight of the crystals. During the ground-based preparations, the following tasks have been accomplished: • Establish the thermodynamic properties of the ZnSe binary and related ternary systems by measuring the partial pressures of the vapor phase coexisting with the condensed phases and perform phase diagram calculations for comparison. • Evaluate the effects of gravity-driven convection in the growth process by performing experiments under various vapor transport orientations relative to gravity vector, i.e., horizontal, vertically stabilized and destabilized configurations. • Establish a quantitative correlation between growth parameters and the characteristics and properties of the grown crystals by characterizing the crystals using a variety of techniques. • Evaluate the fundamentals of the current theories on vapor transport and crystal growth kinetics by performing in-situ and real-time monitoring techniques during growth. • Develop a one-dimensional diffusion limited theory of mass transport and two- and three-dimensional numerical simulations of both mass transport and heat transfer and thus establish the microgravity requirements for the flight experiments and to predict the characteristics of the grown crystals such as the solid-vapor interface shapes… etc. and establish a fundamental understanding of the crystal growth process from the comparison with experimental results.

ZnSe↗

Multi-Anvil Experimentation Applied to Planetary Differentiation

Planets undergo differentiation that includes segregation of metal from silicate at high temperatures and pressures ranging from deep planetary core pressures (>300 GPa for Earth)to very shallow conditions of asteroids (<100 MPa).The multi-anvil solid media apparatus accesses the middle part of this range from 3 to 30 GPa –pressure relevant to the interior of Mercury, Venus, Earth, Earth’s Moon, and Mars. Early planets are thought to have experienced high temperatures from a combination of heat sources including radioactive decay, gravitational and accretional heating, and impact processes. These heating events led to melting of mantles and cores, thus requiring an understanding of solid-liquid equilibria in metal-silicate systems. In 2006 we established a multi-anvil facility at NASA-JSC combining an 880 ton press and a Kawai/Walker type module from Rockland Research. Our high PT work has been greatly facilitated by use of the COMPRES multi-anvil assemblies (1). Our recent work has included studies of element partitioning between liquid metal and liquid silicate(e.g., 2), as well as between minerals and melts(e.g., 3), both of which have led to better constraints on the timing and conditions of planetary differentiation(e.g. 4). Several examples involving sustained efforts will be summarized below and for the presentation. The distribution of siderophile (iron-loving) elements between core and mantle is controlled by metal-silicate equilibrium across a wide range of pressures. Therefore, experimentation across this pressure range helps to calibrate elemental partitioning models that can be applied to planets, and used to predict mantle chemistry and composition during planetary differentiation. Our studies have focused on a wide range of siderophile elements (refractory Ni, Co, W, Mo; volatile P, Ga, Cu, Sn, Sb; highly siderophile Au, Pd) that have constrained partitioning, valence, and isotopic fractionation, and applied to Earth, Moon, and Mars. When molten mantles (magma oceans) cool enough to initiate crystallization, the solids precipitate at depth and in large planets this involves high pressure phases like garnet, majorite, akimotoite, and ringwoodite. As these solids precipitate they can segregate from liquid by density contrasts, thus causing elemental fractionation which can be used to decipher timing of differentiation. Mineral/melt and metal/silicate equilibria in our lab have helped to better understand high pressure fractionation of isotopic parent/daughter pairs Hf/W, Mn/Cr, Pd/Ag, Pt/Os, Re/Os, and U/Pb, and their application to Earth, Moon and Mars. There remains great potential for multi-anvil experimentation to shed light on many pressure–dependent aspects of planetary evolution such as core formation, high pressure phase equilibria, redox equilibria, and volatile evolution and storage. References1. Leinenweber, K., et al.(2012) American Mineralogist,97, 353–368. 2.Righter, K., et al.(2020) Geochem. Persp. Lett.15, 1-6.3. Righter, K., et al.(2020) Met. Planet. Sci 55, 2741-2757.4. Righter, K., et al.(2020)Earth and Planetary Science Letters,552, 116590.

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A View of the Lunar Interior Through Lunar Laser Range Analysis

Laser ranges between observatories on the Earth and retroreflectors on the Moon started in 1969 and continue to the present. Recent range accuracies are 2 cm while earliest ranges are an C, order of magnitude less certain. Four retroreflectors are ranged: three located at the Apollo 11, 14, and 15 sites and one on the Lunakhod 2 rover. Accurate analysis of the range data determines a number of lunar science parameters. The lunar interior variables include a fluid core parameter. The Lunar Laser Ranging effort is reviewed elsewhere. Many parameters are detected through their influence on rotation. Also detected are solid-body tides and accurate selenocentric reflector locations. Determined through the rotation are moment-of-inertia differences, gravitational harmonics, potential Love number, and dissipation effects due to tides and molten core. The rotation of the Moon is not at its minimum energy state; some recently active process has caused free librations. The moment differences contributed to the recent improvement of the Moon's moment of inertia from the Lunar Prospector gravity field. The Love numbers provide bulk elastic properties. Future possibilities for measurement include oblateness of the core-mantle boundary and core moment. A study of dissipation signatures in the rotation determines tidal Q vs. frequency and concludes that the Moon has a molten core. At 1 month the tidal Q is 37 and at 1 yr it is 60. The core radius is < or = 352 km for Fe and < or = 374 km for the Fe-FeS eutectic. The core detection exceeds 3x its uncertainty. The spin of the core is not aligned with the spin of the mantle and torque arises from the velocity difference at the boundary. Yoder's turbulent boundary layer theory is used to compute the radii. The present heat generation from tides and core interaction is minor compared to radiogenic heating. The heating for ancient times is more interesting. Peale and Cassen investigated lunar tidal heating while the lunar orbit expanded due to tides on Earth. Their calculations predate the measurement of Q and should be multiplied by 3.45 to match the lunar-laser-determined Love number and monthly Q. Tidal-heating computations depend on how fast the lunar orbit evolved and whether the tidal dissipation is localized. Neither is known, but plausible assumptions lead to early central region temperature increases of several hundred degrees. Most of the energy is deposited early in the Moon's history. The turbulent boundary layer theory allows a prediction of energy dissipated at the core-mantle boundary during orbit evolution. Under the assumption that the properties of the early core are the same as at present, the energy dissipated by core-mantle interaction is about the same as for tidal dissipation, but it is deposited in a smaller volume. This source of energy is capable of promoting convection in an early fluid core and driving a dynamo. This is a transient phase with a duration depending on the rate of orbit evolution. Plausible assumptions lead to a duration of a few hundred million years. Thus, the remnant magnetization of many lunar rocks is compatible with a brief global magnetic field powered by dynamical energy dissipation. Analysis of the lunar laser ranges is providing information on lunar geophysics. Future data will improve accuracies of present solution parameters, and several more interior effects should be detectable.

Williams, J. G.↗

Venus Global Reference Atmospheric Model (Venus-GRAM) Upgrades

Introduction: The Venus Global Reference Atmospheric Model (Venus-GRAM) is one of the most widely used engineering models of Venus’ atmosphere. The Venus-GRAM upgrades are being developed by NASA Marshall Space Flight Center (MSFC) and NASA Langley Research Center (LaRC). This presentation will provide details regarding the upgrades that have been made to Venus-GRAM and the ongoing objectives, tasks, and milestones related to the GRAM upgrades funded by the NASA Science Mission Directorate (SMD). Venus-GRAM: Venus-GRAM is an engineering-oriented atmospheric model that estimates mean values and statistical variations of the atmospheric properties of Venus. Venus-GRAM provides mean values and variability for any point in the atmosphere as well as seasonal, geographic, and altitude variations. Venus-GRAM outputs include atmospheric density, temperature, pressure, winds, and chemical composition along a user-defined path. It is extensively used by the engineering community because of its ability to create realistic dispersions. GRAMs have been integrated into high fidelity flight dynamic simulations of launch, entry, descent and landing (EDL), aerobraking and aerocapture. GRAMs are currently available for Earth, Mars, Venus, Neptune, Titan, and Uranus. The lower atmosphere model in Venus-GRAM (up to 250 km) is based on the Venus International Reference Atmosphere (VIRA) [1]. The Venus-GRAM thermosphere (250 to 1000 km) is based on a MSFC-developed model [2] which assumes an isothermal temperature profile initialized using VIRA conditions at 250 km [3]. The VIRA version included in Venus-GRAM includes Pioneer Venus Orbiter and Probe data as well as Venera probe data, but it does not include a solid planet model or a high-resolution gravity model [4]. Venus-GRAM Upgrade Status: Code Modernization. Venus-GRAM has been rearchitected from Fortran to a common object-oriented C++ framework called the GRAM Suite. This new architecture creates a common GRAM library of data models and utilities. The first C++ release of the rearchitected Venus-GRAM is a straight conversion from the latest Fortran version. Model Upgrades. The focus of the model upgrade task is to improve the atmosphere models in the existing GRAMs and to establish a foundation for developing GRAMs for additional destinations. The GRAM ephemeris has been upgraded to the NASA Navigation and Ancillary Information Facility (NAIF) SPICE toolkit (version N0066). The calculation of the speed of sound has also been improved in the GRAMs. In FY20, the GRAM project established contracts to improve the model data within Venus-GRAM. Hampton University is developing an empirical global model for Venus. The University of Wisconsin is reanalyzing the Venus Express radio occultation observations and analyzing the Akatsuki thermal imaging data. Upgraded Venus-GRAM Release. GRAM Suite Version 1.3 will be released in September 2021 and will contain the rearchitected Venus-GRAM, including the common GRAM framework and planet–specific code. A User Guide and Programmer’s Manual are released with all GRAMs. Conclusions: GRAMs are frequently used toolsets and vital in assessing effects of atmospheres on interplanetary spacecraft during the program life cycle process. Releases of the GRAM Suite, upgrades of the existing planetary GRAMs, and development of new planetary GRAMs are ongoing. Venus-GRAM atmosphere model upgrades will be included in the next phase of GRAM tasks. References: [1] Kliore, A. J. et al. (1985) ASR, 5, 11, 1-304. [2] Justh, H. L. et al. (2006) AIAA/AAS Astrodynamics Specialist Conference & Exhibit, Abstract AIAA-2006-6394. [3] Guide to Reference and Standard Atmosphere Models, BSR/AIAA G-003-2010. [4] Limaye, S. S. (2012), LPSC VEXAG Townhall Meeting. Acknowledgments: The authors gratefully acknowledge support from the NASA SMD.

atmospheric models↗

Trace Elemental Abundances in Calcium-Aluminum-Rich Inclusions in CV Chondrites

Introduction: Calcium-aluminum-rich inclusions (CAIs), are the first formed solids that define the age of the Solar System [1,2]. CAIs are thought to have condensed from nebular gas [3,4] within the first <1 Ma of Solar System formation [5,6]. CAIs have experienced numerous early Solar System processes including condensation, evaporation, melting, recrystallization, and aqueous alteration [e.g., 7]. The chemical, mineralogical, and textural diversity among CAIs results from a range of chemical and physical processes recorded during nebular and parent body epoch. This study aims to explore the mineralogical, textural, and chemical compositions of CAIs including the trace elemental abundances in CAI phases to determine the early Solar System processes recorded in them. Samples and Analytical Methods: We analyzed one CAI each from CV3 chondrites Northwest Africa (NWA) 5508 designated as ‘Saguaro’, and Northwest Africa (NWA) 12772 designated as ‘Hoopoe’. Back-scatter electron (BSE) images were collected using a Phenom XL scanning electron microscope (SEM) at the Lunar and Planetary Institute (LPI) and the JEOL JXA-8530F electron probe microanalyzer (EPMA) at Johnson Space Center (JSC)-NASA. Additionally, energy dispersive X-ray spectrometry (EDS) elemental maps of select areas for these samples were collected using a 15.0kV beam energy and a 40µA emission current. Using the EPMA, wavelength-dispersive X-ray spectroscopy (WDS) quantitative data were collected. In-situ trace element measurements for both CAIs were determined at JSC-NASA using a Photon Machines 193nm laser ablation system and a Thermo-Scientific Element-XR inductively coupled plasma mass spectrometer (ICP-MS). Analyses consisted of 30s ablations at 10Hz, spot sizes of 20-25µm, and a fluence of 6.0 J/cm2 for anorthite and melilite, and a 3.5 J/cm2 fluence for all other phases. NIST612 was used to correct for instrument drift, while BHVO-2g was used as a primary calibration standard. BCR-2g and in-house mineral standards were regularly measured as unknowns to ensure accuracy. Results: Saguaro is a coarse-grained CAI, ~11 x 6 mm in dimensions. Saguaro contains spinel, Al-rich pyroxene, anorthite, Mg-rich melilite, and minor perovskite in its interior and is therefore classified as a Type B CAI. Individual melilite grains shows normal compositional zoning with an Ak content ranging from ~24 to 54 with no apparent trend from the core to the edge of the CAI. The spinel appears euhedral and occurs both as clusters and as spinel palisades [8]. Two rim sequences surround most of the sample: the inner rim being a Wark-Lovering (WL) rim (~10-35 µm) containing pyroxene, spinel, and melilite (or anorthite), and the outer rim is a finer-grained, thicker (~100 µm), accretionary rim (Fig. 1). The mineral phases in Saguaro record an overall flat REE pattern with an average negative Eu anomaly in pyroxene, and an average positive Eu anomaly in anorthite and melilite respectively. Anorthite, melilite, and pyroxene have a minor depletion in Tm (Fig. 2). The Hoopoe CAI is a compact, coarse-grained ~6 × 4 mm in size. The major mineralogy includes hibonite, spinel, melilite, anorthite, and perovskite. Therefore, it is classified as a compact transitional type A and B. (?)zoning was observed in some hibonites. Individual melilite grains show both reverse and normal zoning, where the Ak content ranges from ~6- to 28. Melilite shows two distinct textures. One texture consisted of smooth melilite that appeared homogenous, while the second appeared to consist of many fine fractures. The spinel also often appears clustered. The WL-rim sequence surrounding Hoopoe is ~25 µm thick and composed of spinel, perovskite, hibonite, and melilite/anorthite. It is then partially surrounded by an outer accretionary rim (~75µm). Like before, refractory metal nuggets appeared concentrated near the WL rims. Other metal assemblages rich in Fe and Ni were also observed. All major mineral phases in Hoopoe display relatively flat REE patterns, except for varying Eu and Tm between phases (Fig. 2). There is a prominent negative Eu anomaly in perovskite and an average positive Eu anomaly in spinel, anorthite, and hibonite respectively (Fig. 2, 3). The mixed phases along the rim of the CAI also display a negative Eu anomaly, and all phases the CAI were depleted in Pb. Discussion: The CV3 CAIs analyzed in this study were classified based on their mineralogy and textures into Type A versus Type B CAIs [10]. Hibonite appears to be pseudomorphically replacing the spinel, (i.e., is hibonite in composition, but appears in the shape of spinel). Spinel palisades. The presence of spinel palisades present in Saguaro are consistent with the melting and recrystallization experienced by this CAI. Trace elemental analyses. Saguaro and Hoopoe display similar trace element patterns to each other, with both appearing generally flat, with anomalies in Eu, and Tm. Melilite and anorthite display positive Eu anomalies in both CAIs, in addition to the hibonite in Hoopoe (Fig. 2). The phases that are depleted in Eu are pyroxene and perovskite in both Saguaro and Hoopoe, respectively (Fig. 3). Given that Eu is volatile in reducing environments [11], this could possibly indicate reducing conditions at the time anorthite and melilite crystallized, with the gas they formed from containing Eu. As these CAIs continued to form, this gas as a result would become depleted in Eu. This also could be supported by the propensity of anorthite and melilite to take up Eu from its surroundings and incorporate it into their structure [12]. In addition, analyzing the assemblage of the phases in the Saguaro, melilite and anorthite (Eu enriched) often surround the pyroxene (Eu depleted) as they are crystallized. This intergrowth of phases and the proximity of the phases would support that the Eu is being incorporated into some phases, preventing it from incorporating into other. Trace elemental analyses of the CAI rims will be evaluated in more detail, as they are complicated by the transient signal being composed of a mixture of mineral phases. Broadly, however, the patterns in the rims of both CAIs are comparable to each other, and for Hoopoe, to the mixed phase patterns in the core (Fig. 3). Other studies have found that CAI rims can be depleted in Ce and Yb [13], however we did not observe these anomalies in the two CAIs discussed here. Given their similarity, the trace elemental analyses of the mixed interior (i.e. core) and rim phases could be interpreted as forming from similar, if not the same, reservoirs. The REE abundance between the rim and core of Hoopoe are also similar, indicating they may have formed from a gas of the same or similar composition. Acknowledgments: We thank the ASU Center for Meteorite Studies for loaning the samples used in this work and Tabb Prissel for his assistance with the analysis. Mouti Al-Hashimi thanks Sam Crossley and Cyrena Goodrich for their help with the LPI SEM training. This work was supported by the LPI Summer Intern Program in Planetary Science and the LPI Cooperative Agreement. References: [1] Connelly J.N. (2012) Science, 338, 651-655. [2] MacPherson G. J. (2014) Treatise on Geochem., 2, 139-179. [3] Grossman L. (1972) GCA, 36, 597-619. [4] Ebel, D.S. (2006) Meteorites and the Early Solar System II (D. S. Lauretta & H. Y. McSween, Eds.) 253-277. [5] MacPherson G. J. (2012) Earth Planet. Sci. Lett., 331-332, 43-54. [6] MacPherson G.J. (2017) GCA, 201, 65-82. [7] Krot A.N. (1995) Meteoritics & Planet. Sci., 30, 748-775. [8] Wark and Lovering (1982) GCA, 46, 2595-2607. [9] Palme H. and Jones A. (2003) Treatise on Geochemistry (H. D. Holland and K. K. Turekian Eds.), 1, 41-61. [10] Grossman L. (1980) Ann. Rev. Earth Planet. Sci., 8, 559-608. [11] Floss C. et al. (1996) GCA, 60, 1975-1997. [12] Mason B. and Martin P. M. (1974) Earth Planet. Sci. Lett., 22, 141-144. [13] Wark B. and Boynton W. V. (2001) Meteoritics & Planet. Sci., 36, 1135-1166.

X Mouti↗