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A New Coordinated NanoSIMS, Transmission Electron Microscopy and Atom Probe Tomography Approach For the Characterization of Primitive Astromaterials

Presolar grains are remnants of evolved stellar systems preserved within primitive extraterrestrial materials. They are important for studying physical and chemical processing, and formation mechanisms occurring within the interstellar medium, Solar Nebula and their parent stellar environments [1]. Our recent work has shown coordinated nano-scale Secondary Ion Mass Spectrometry (NanoSIMS) and Atom Probe Tomography (APT) can show isotopic and chemical signatures at major to trace levels, morphological signatures, and regional contextual relationships [2,3]. Previous studies have shown Transmission Electron Microscopy (TEM) of Focus Ion Beam (FIB) TEM lamella, can provide localized contextual relationships, crystallographic information and chemical information [1]. Coordinating NanoSIMS, TEM, and APT could gain access to almost all contextual, structural and geochemical signatures within each presolar grain. However, this has proved challenging owing to the preparation requirements for TEM and APT. For example, studying specimen prepared as APT needles in TEM removes the local context, the higher degree of surface exposure can alter the chemistry of beam sensitive materials, and the shank angle of the needle can impact the quality of TEM diffraction images. We designed a new FIB method which takes a 100 nm thick FIB-TEM lamella and sandwiches it between two indium slices (5 μm x ~300 nm x 3 μm). The indium is melted onto the lamella surface using the electron beam (Fig 1). This process adds bulk to the lamella, making it more amenable to APT needle formation (Fig 2). Consequently, samples can be prepared per the optimal requirements for each technique improving data quality, acquisition stability, and access to the signatures and relationships summarised earlier. This technique can be used for measuring multiple phases across a TEM lamella and targeting an individual phase. For example, a presolar grain identified in NanoSIMS could be targeted, studied in TEM and then indium sandwiched with its precise location in the TEM lamella marked using a Pt button for preparation of an APT needle and atomic scale acquisition. [1] A. M. Davis (2014) Meteorites and cosmochemical processes, 1. [2] Nevill N. et al. (2023) LPSC, 54, #1707. [3] Nevill N. et al. (2023) LPSC, 54, #1714.

NanoSIMS↗
NASA NTRS2003

Capabilities of the Materials Contamination Team at Marshall Space Flight Center

The Materials Contamination Team at the Marshall Space Flight Center (MSFC) has been recognized for its contributions supporting the National Aeronautics and Space Administration (NASA) spacecraft development programs. These programs include the Reusable Solid Rocket Motor (RSRM), Chandra X-Ray Observatory, and the International Space Station (ISS). The Environmental Effects Group, with the Materials Contamination Team and the Space Environmental Effects Team has been an integral part of NASA's success by the testing, evaluation, and qualification of materials, hardware, and processes. This paper focuses on the capabilities of the Materials Contamination Team. The Materials Contamination Team's realm of responsibility includes establishing contamination control during all phases of hardware development, including design, manufacturing, assembly, test, transportation, launch site processing, on-orbit exposure, return, and refurbishment. The team continues its mission of reducing the risk of equipment failure due to molecular or particulate contamination. Contamination is a concern in the Space Shuttle with sensitive bond-lines and reactive fluid (liquid oxygen) compatibility as well as for spacecraft with sensitive optics, such as Hubble Space Telescope and Chandra X-ray Observatory. The Materials Contamination Team has a variety of facilities and instrumentation capable of contaminant detection, identification, and monitoring. The team addresses material applications dealing with environments, including production facilities, clean rooms, and on-orbit exposure. The optically stimulated electron emission (OSEE) system, the Ultraviolet (UV) fluorescence (UVF) surface contamination detection, and the Surface Optics Corporation 400 (SOC 400) portable hand-held Fourier Transform Infrared (FTIR) spectrometer are state-of-the-art tools for in-process molecular contamination detection. The team of engineers and technicians also develop contamination calibration standards and evaluate new surface cleanliness inspection technologies. The team utilizes facilities for on-orbit simulation testing of materials for outgassing and molecular film deposition characteristics in the presence of space environmental effects, such as Atomic Oxygen (AO) and UV radiation exposure. The Materials Contamination Team maintains databases for process materials as well as outgassing and optical compatibility test results for specific environments.

Burns, Howard↗
NASA NTRS1995

Interstellar Grain Surface Chemistry

Chemistry on grain surfaces plays an Important role in the formation of interstellar Ices, It can also influence the composition of the gas phase through outgassing near luminous, newly formed stars. This paper reviews the chemical processes taking place on Interstellar grain surfaces with the emphasis on those transforming CO into other hydrocarbons. At low, molecular cloud temperatures (approximately equal to 10K), physisorption processes dominate interstellar grain surface chemistry and GO is largely hydrogenated through reactions with atomic H and oxidized through reactions with atomic O. The former will lead to the formation of H2CO and CH3OH ices, while the latter results in CO2 ice. The observational evidence for these ices in molecular clouds will be discussed. Very close to protostars, the gas and grain temperatures are much higher (approximately equal to 500K) and chemisorption processes, including catalytic surface reactions, becomes important. This will be illustrated based upon our studies of the Fischer-Tropsch Synthesis of CH4 from CO on metallic surfaces. Likely, this process has played an important role in the early solar nebula. Observational consequences will be pointed out.

Tielens, Alexander G. G. M.↗
NASA NTRS1973

Rocket observations of the extreme ultraviolet dayglow.

The ultraviolet dayglow in the wavelength region 750-1050 A was investigated over the altitude range 100-800 km using a thin film filter photometer. From the airglow spectrum obtained by Carruthers and Page, one of the dominant features in this wavelength range is OII 834 A. It is pointed out that the major excitation mechanism for this transition is photoionization excitation of atomic oxygen. Solution of the radiative transfer problem for this excitation process shows good agreement with the observed dayglow in the 300-800 km region. At lower altitudes additional componets are present and are interpreted as the N2, OI and possibly HI emissions observed by Carruthers and Page.

Carlson, R. W.↗
NASA NTRS1973

Formation mechanism for interstellar molecules

The major ions in the region of the interstellar clouds include H(+) and H2(+). The ions may be formed by photo ionization, cosmic rays, or other processes. The chemistry of H2(+) is considered and reactions involving carbon atoms are described. The formation of nitrogen-containing molecules may occur mainly on interstellar grains. Reactions involving negative ions may also contribute to the production of certain species.

Harteck, P.↗
NASA NTRS1974

Ion-molecule reactions and vibrational deactivation of H2/+/ ions in mixtures of hydrogen and helium

Use of ion cyclotron resonance methods to measure the thermal energy rate constants for a number of ion-molecule reactions involving hydrogen and hydrogen-helium mixtures. Assuming that the distribution of initial vibrational states in the H2(+) ion is a near-Franck-Condon distribution, the occurrence of collisional deactivation of vibrationally excited H2(+) ions by He atoms is identified, and an approximate rate constant for the deactivation process and its dependence on vibrational energy are given.

Theard, L. P.↗
NASA NTRS1975

Studies of the use of high-temperature nuclear heat from an HTGR for hydrogen production

The results of a study which surveyed various methods of hydrogen production using nuclear and fossil energy are presented. A description of these methods is provided, and efficiencies are calculated for each case. The process designs of systems that utilize the heat from a general atomic high temperature gas cooled reactor with a steam methane reformer and feed the reformer with substitute natural gas manufactured from coal, using reforming temperatures, are presented. The capital costs for these systems and the resultant hydrogen production price for these cases are discussed along with a research and development program.

Peterman, D. D.↗
NASA NTRS1980

Smoke and dust particles of meteoric origin in the mesosphere and stratosphere

A height profile of ablated mass from meteors is calculated, assuming an incoming mass of 10 to the -16th g/sq cm/s (44 metric tons per day) and the velocity distribution of Southworth and Sekanina, which has a mean of 14.5 km/s. The profile peaks at 84 km. The fluxes of micrometeorites and residual meteoroids are also calculated. The coagulation of the evaporated silicates into 'smoke' particles is then followed by means of a model adapted from a previous study of the stratospheric sulfate layer. Numerous sensitivity tests are made. Features of the results are a sharp cutoff of the particle distribution above 90 km, and a surface area close to 10 to the -9th sq cm/cu cm all the way from 30 to 85 km. Some confirmation is obtained from balloon studies of condensation nuclei, although the various measurements differ greatly. The optical scattering and extinction are shown to be undetectable. Several potential applications are suggested: nucleation of sulfate particles and noctilucent clouds, scavenging of metallic ions and atoms, and perhaps other aeronomical effects. The latter are limited to processes that can be influenced by a collision time of the order of a day.

Hunten, D. M.↗
NASA NTRS1982

An electrochemical study of Ni/2+/, Co/2+/, and Zn/2+/ ions in melts of composition CaMgSi2O6

Results are reported for a study of the behavior of Ni(2+), Co(2+), and Zn(2+) in molten diopside, determined by cyclic voltametry, as a first step in adapting electrochemical methods for use in experimental geochemistry. The techniques used are described, the theory is briefly discussed, and it is demonstrated that Ni(2+), Co(2+), and Zn(2+) can be reduced, then reoxidized in an uncomplicated case of reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain undissolved in the melt. The kinetics of the reduction process, the effects of concentration, the standard reduction potentials, and the diffusion coefficients are discussed in detail. The observations are consistent with the mechanism of Ni(2+) diffusion by transport from site to site. As the proportion of SiO2 in the melt increases, a higher activation energy is required for Ni(2+) to move, and the rate of diffusion is lowered.

Semkow, K. W.↗
NASA NTRS1986

N(+)-N and O(+)-O interaction energies, dipole transition moments, and transport cross sections

Complete sets of ion-atom interaction energies have been computed for nitrogen and oxygen with accurate large scale structure calculations. The computed energies agree well with the accurate potential curves available from spectroscopic measurement. The state functions from the nitrogen calculations have been applied to determine the transition moment for all allowed dipole transitions. These results can be combined to compute a detailed radiation spectrum such as that required to define the highly nonequilibrium environment of aeroassisted orbital transfer vehicle (AOTV). The long-range interaction energies have been used to determine the ion-atom resonance charge exchange cross sections that are important for transport processes such as diffusion. A calculation to determine reliable transport properties for energies that include the AOTV temperature range from these computed properties is described.

Partridge, H.↗
NASA NTRS1987

Interstellar processes; Proceedings of the Symposium, Grand Teton National Park, WY, July 1-7, 1986

The conference presents papers on the Milky Way as a galaxy; observations of components of the interstellar medium; interstellar magnetic properties; interstellar processes on a galactic scale; dynamical processes in interstellar clouds; interstellar dust grains; interstellar chemical processes; and heating, cooling, and radiative processes. Attention is given to H2 in the Galaxy, hot interstellar gas in the Galactic disk and halo, interstellar magnetic fields, cloud formation and destruction, theoretical approaches to interstellar turbulence, and infrared absorption and emission characteristics of interstellar PAHs. Other topics include gas phase chemical processes in molecular clouds, the chemical evolution of galaxies, and the atomic and molecular physics of interstellar heating and cooling.

Hollenbach, David J.↗
NASA NTRS1990

Perspectives on high temperature superconducting electronics

The major challenges in making high temperature superconducting (HTSC) electronics viable are predominantly materials problems. Unlike their predecessors the metal oxide-based superconductors are integratable with other advanced technologies such as opto-electronics and micro-electronics. The materials problems to be addressed relate to the epitaxial growth of high quality films, highly oriented films on non-lattice matched substrates, heterostructures with atomically sharp interfaces of junctions and other novel devices, and the processing of these films with negligible deterioration of the superconducting properties. These issues are illustrated with results based on films prepared in-situ by a pulsed laser deposition process. Films with zero-transition temperatures of 90 K and critical current densities of 5 x 10(exp 6) A/sq cm at 77 K have been prepared by this technique. Ultra-thin films, less than 100 A show T(sub c) is greater than 80 K, supporting the idea of two-dimensional transport in these materials. By the use of appropriate buffer layers, films with T(sub c) of 87 K and J(sub c) of 6 x 10(exp 4) A/sq cm were fabricated on silicon substrates. Submicron structures with J(sub c) is greater than 2 x 10(exp 7) at 10 K were fabricated. Results on nonlinear switching elements, IR detectors, and microwave studies will be briefly summarized.

Venkatesan, T.↗
NASA NTRS1990

The oxygen emission lines in Wolf-Rayet spectra

The statistical equilibrium of oxygen in the line-emitting regions of WR stars is studied using the one-representative point theory of Castor and van Blerkom (1970) for a wider range of the radiation temperature, electron temperature, and electron density. Radiative processes, collisional processes, and electronic recombination are studied for a 59-level model atom. The level populations depart by large factors from those expected for LTE at the electron temperature and electron density. When the parameters have the values found previously by Bhatia and Underhill to be representative for WR stars, the oxygen atoms are strongly concentrated in the lower levels of O(2+), O(3+), and O(4+). The predicted relative energies in typical lines of O III, O IV, and O V for a solar abundance ratio of O to H are compatible with what is observed in WC and WN spectra.

Bhatia, A. K.↗
NASA NTRS1990

Ignition and combustion characteristics of metallized propellants

Research designed to develop detailed knowledge of the secondary atomization and ignition characteristics of aluminum slurry propellants was started. These processes are studied because they are the controlling factors limiting the combustion efficiency of aluminum slurry propellants in rocket applications. A burner and spray rig system allowing the study of individual slurry droplets having diameters from about 10 to 100 microns was designed and fabricated. The burner generates a near uniform high temperature environment from the merging of 72 small laminar diffusion flames above a honeycomb matrix. This design permits essentially adiabatic operation over a wide range of stoichiometries without danger of flashback. A single particle sizing system and velocimeter also were designed and assembled. Light scattered from a focused laser beam is related to the particle (droplet) size, while the particle velocity is determined by its transit time through the focal volume. Light from the combustion of aluminum is also sensed to determine if ignition was achieved. These size and velocity measurements will allow the determination of disruption and ignition times as functions of drop sizes and ambient conditions.

Turns, S. R.↗
NASA NTRS1990

Research and technology, 1990

The annual report of the Marshall Space Flight Center for 1990 is presented. Brief summaries of research are presented for work in the fields of transportation systems, space systems, data systems, microgravity science, astronomy, astrophysics, solar physics, magnetospheric physics, atomic physics, aeronomy, Earth science and applications, propulsion technology, materials and processes, structures and dynamics, automated systems, space systems, and avionics.

Potter, P. Y.↗
NASA NTRS1991

Perspectives on high temperature superconducting electronics

The major challenges in making high temperature superconducting (HTSC) electronics viable are predominantly materials problems. Unlike their predecessors, the metal oxide-based superconductors are integratable with other advanced technologies such as opto-electronics and micro-electronics. The materials problems to be addressed relate to the epitaxial growth of high quality films, highly oriented films on non-lattice matched substrates, heterostructures with atomically sharp interfaces of junctions and other novel devices, and the processing of these films with negligible deterioration of the superconducting properties. These issues are illustrated with results based on films prepared in-situ by a pulsed laser deposition process. Films with zero-transition temperatures of 90 K and critical current densities of 5 x 10(exp 6) A/sq cm at 77 K have been prepared by this technique. Ultra-thin films, less than 100 A show T(sub c) is greater than 80 K, supporting the idea of two-dimensional transport in these materials. By the use of appropriate buffer layers, films with T(sub c) of 87 K and J(sub c) of 6 x 10(exp 4) A/sq cm were fabricated on silicon substrates. Submicron structures with J(sub c) is greater than 2 x 10(exp 7) at 10 K were fabricated. Results on nonlinear switching elements, IR detectors, and microwave studies will be briefly summarized.

Venkatesan, T.↗
NASA NTRS1994

Theoretical investigation of gas-surface interactions

The goal of this project was to develop computational tools for the calculation of the electronic structure of molecules containing heavy atoms, and to use these tools in the study of catalytic processes, with the overall objective of gaining an understanding of the catalytic process which could be used to design more efficient catalysts. The main catalytic system of interest was the combustion of hydrogen on platinum surfaces. Under this project, a flexible Dirac-Hartree-Fock (DHF) program has been developed, a code to calculate DHF correlation energies at the second-order Moeller-Plesset perturbation (PP2) level is almost complete, and code to include correlation at the MCSCF and MCSCF/MP2 level is planned. The tools so far developed have been validated and used to calibrate some more approximate methods, and applied to investigate the importance of relativistic effects in the bonding of hydrogen to platinum.

Dyall, Kenneth G.↗