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NASA NTRS2022

Atomic-Scale Structure and Non-Stoichiometry of Meteoritic Hibonite: A Transmission Electron Microscope Study

Hibonite (CaAl_12O_19) is a common refractory mineral in Ca-Al-rich inclusions (CAIs) in primitive meteorites. Transmission electron microscope (TEM) studies have identified enigmatic planar defects in different occurrences of hibonite in the Allende meteorite that give rise to strong streaking along c* in electron diffraction patterns. Atomic resolution high-angle annular dark-field (HAADF) imaging and energy-dispersive X-ray (EDX) analyses were used to determine the nature and origin of these planar features. HAADF images of hibonite grains reveal lamellar intergrowths of common 1.6 nm spacing, and less commonly 2.0 and 2.5 nm spacings, interspersed in stoichiometric hibonite showing 1.1 nm (002) spacing. Stoichiometric hibonite consists of alternating Ca-containing (“R”) and spinel-structured (“S”) blocks stacked in a sequence RS. In contrast, the 1.6 nm layers result from a doubled S block such that the stacking sequence is RSS, while in the widest defect observed, the stacking sequence is RSSSS. These intergrowths are epitaxial and have coherent, low-strain boundaries with the host hibonite Meteoritic hibonite shows common Ti and Mg substitution for Al in its structure. Atomic-resolution EDX maps of hibonite grains in the Allende CAI confirm the preferred site occupancy of Mg on tetragonal M3 sites in S blocks and of Ti on trigonal bipyramidal M2 and octahedral M4 sites in R blocks. Mg is highly concentrated, but Ti is absent in the planar defects where wider S blocks show Al-rich compositions compared to stoichiometric MgAl_2O_4 spinel. Therefore, Mg likely played the major role in the formation and metastability of planar defects in hibonite. Electron energy loss spectroscopy data from the Ti L_2,3 edge show the presence of mixed Ti oxidation states with ~ 15–20% of Ti as Ti^(3+) in hibonite, suggesting a direct substitution of Ti^(3+) ↔ Al^(3+) in hibonite. The remaining ~ 80–85% of Ti is present as Ti^(4+) and corresponding EDX analyses are consistent with the well-known coupled substitution 2Al^(3+) ↔ Ti^(4+) + Mg^(2+) being the major mechanism for Ti and Mg substitution in hibonite. The formation of planar defects in hibonite occurred during high-temperature nebular condensation or melting/crystallization processes. The occurrence of non-stoichiometric hibonite in the Allende CAI deviates from the mineral formation sequence predicted from equilibrium condensation models. Overall, our atomic resolution TEM observations signify non-equilibrium, kinetic-controlled crystal growth during the high-temperature formation of refractory solids in the early solar nebula.

hibonite↗
NASA NTRSDate not supplied

Micrometer to Atomic Scale Characterisation of Primitive Astromaterials Using A Novel Method, Metis-Fa: A Coordinated Atom Probe Tomography, Transmission Electron Microscopy and NanoSIMS Approach

Introduction: Presolar grains preserve isotopic, chemical and microstructural records of physical and chemical processing, and formation mechanisms within a vast range of evolved stellar systems, the interstellar medium, solar nebula and their parent bodies. These evolutionary records are preserved at the micrometric to atomic scale, requiring coordinated studies to expand our understanding of evolutionary processes occurringthroughout ours and external stellar systems [1]. NanoSIMS enabled rapid in situ identification and isotopic characterisation of presolar grains and their stellar origins using 17O/16O and 18O/16O, and 13C/12C isotopic ratios [1]. Coordination with transmission electron microscopy (TEM) revealed crystallographic and localised contextual relationships and quantitively constrained their major and minor compositions [1]. However, trace elements cannot be quantified, the most sensitive geochemical tracers of environmental conditions, essential to unravelling the chemical record of their evolutionary pathway and parent stellar systems [2-3] . Furthermore, owing to the combination of technical limitations (only 5 – 7 isotopes can be measured per NanoSIMS run) and their small grain sizes of 100 nm < 3 μm (with rare exceptions in nanodiamonds (2 nm ≤) and SiC (< 40 μm)), the number of measurable isotopes per grain volume is limited [1,3] . Through more comprehensive isotopic studies of presolar grains, NanoSIMS studies have shown the importance of the latter, identifying Fe and Mg as important indicators of nuclear synthetic processing and their stellar origins, respectively [4- 5]. Coordination of NanoSIMS and Atom Probe Tomography (APT) revealed morphological signatures, and isotopic and chemical signatures at major to trace levels without requirements for preselection of elements [6]. However, crystallographic signatures in localized contextual relationships cannot be measured. Consequently, coordination of NanoSIMS, TEM and APT is essential to gain access to almost all contextual, structural and geochemical signatures within each presolar grain.Transmission electron microscopy requires a 100 nm thin lamella which is unstable in APT and would not produce any viable data. Atom probe tomography requires a needle-shaped specimen which when measured in TEM removes the local context, impacts the quality of the TEM diffraction images due to the shank angle of the needle, and can alter the chemistry of beam sensitive materials from the higher degree of surface exposure at the tip. To address these issues, we developed METIS-Fa (Multi-technical measurements of Electron Transparent materials using an Indium Sandwich - a FIB approach). A novel method which enables coordination of NanoSIMS, TEM and APT for generalized and targeted studies of individual grains, including beam sensitive materials, without compromising sample preparation requirements for TEM and APT. This method requires only indium and a Focus Ion Beam (FIB), minimizing the movement of fragile materials while still enabling preparation of TEM lamella into APT needles. Samples: Initial experimental development and testing of the method occurred at Astromaterials Research and Exploration Science (ARES), Johnson Space Centre (JSC), NASA and APT measurements and needle preparation occurred at JdLC, Curtin University. Synthetic silicate samples were used as analogs for presolar silicates when performing a trial run of the method. Samples were extracted from a polished thin section created at JSC, NASA, comprised of 38 wt.% Si, 17 wt.% FeO, 13 wt.% MgO, 12 wt.% Al, 11 wt.% Ca based on electron microprobe analysis (EMPA) [8] . Experimental details, pressure and temperature conditions were presented in [8] and references therein. Testing of the capability to target individual grains in mineral matrices using this method for acquisition in APT, measured matrix regions in meteoritic thin sections of primitive meteorites. These meteorites and their identified presolar grains for future targeted studies are detailed in [9]. Techniques: The TEM-FIB lamella were prepared using a FIB. An e-beam assisted pt deposition was used as a protective coating for the synthetic and meteoritic samples. When targeting individual grains, a secondary e-beam assisted pt deposition button is placed over the desired grain before the protective coating to denote its location. A JEOL 2500SE field-emission TEM was used for high-resolution imaging, energy-dispersive X-ray (EDX) and electron diffraction data.TheMETIS-Fa method was experimentally designed, tested and executed using a FIB at ARES, JSCNASA. Needles for APT were prepared using the Tescan Lyra3 GM Dual Beam Focus Ion Beam (FIB) Field Emission SEM (FE-SEM) at the JdLC, Curtin University. Atom probe tomography measurements were conducted using a CAMECA Local Electrode Atom Probe, LEAP 4000X HR. Two pure indium needles were analyzed initially to constraining acquisition parameters and stability under the beam. Manual acquisition was required to maintain evaporation of specimen’s at the apex and monitor interactions with measurement parameters. Experimental Design: Indium foil is pressed onto an Al stub with a pneumatic press and mounted into the FIB adjacent to the TEM-FIB lamella of interest. Using a FIB, two indium slices (5 μm x ~300 nm x 3 μm) are extracted from indium foil and aligned with the TEM-FIB lamella before touching the TEM-FIB lamella. Each slice is then attached through cold welding to the FIB-TEM lamella. This approach eliminates the need for chemical treatments and proved effective for aligning the Indium within the region of interest for APT, holding it in place for up to 4 days during testing.Once both indium slices are attached within their pre-determined region per grain targeting requirements, they are gradually melted onto the FIB-TEM lamella.When targeting a specific grain, measurements should be taken of the pt button and its distance from edge to edge of the lamella before and after sandwiching. A secondary button should be placed over the same region after the Indium slices have been attached to improve precision when preparing APT needles. Results: Figure 1 shows two indium slices melted onto a FIB-TEM lamella, adding additional bulk for preparation into APT needles as shown in Figure 2 [7] . The latter was essential so samples could be measured in TEM and APT without compromising sample preparation requirements and consequently data quality and acquisition stability. METIS-Fa proved effective forimproving geometry. Figure 3 shows a successful APTrun of the synthetic silicate. EMPA, TEM and APTshowed no chemical alterations. During targetingtesting, a solar silicate grain was successfully identifiedand measured in TEM, and prepared into an APTneedle. However, the indium was melted too long during sample preparation, causing expansion andformation of internal porosity leading to sample loss.Conclusion: METIS-Fa greatly expands the number of isotopic and chemical signatures measured per grain volume, and enables measurements of contextual, structural, crystallographic, isotopic and geochemical signatures within individual grains. Gaining access to such a vast range of evolutionary signatures required for expanding our understanding of external stellar and planetary systems and the evolution of our solar system. This method was designed for application to a vast range of phases including being sensitive materials and thus provides a way for coordination of NanoSIMS, TEM and APT not just for the study of presolar grains and by extension primitive astromaterials, but studies in a vast range of other fields including the geosciences and material sciences.Acknowledgments: Thankyou to ARES, JSC, NASA; JdLC Curtin University and Space Science Technology Centre for the use of laboratory facilities and funding [confirm].

Nicole D Nevill↗
NASA NTRS2021

Understanding the Space Weathering of Mercury Through Laboratory Experiments

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

M S Thompson↗
NASA NTRS1972

Microscopic observations of X-ray and gamma-ray induced decomposition of ammonium perchlorate crystals

The X-ray and gamma-ray induced decomposition of ammonium perchlorate was studied by optical, transmission, and scanning electron microscopy. This material is a commonly used oxidizer in solid propellents which could be employed in deep-space probes, and where they will be subjected to a variety of radiations for as long as ten years. In some respects the radiation-induced damage closely resembles the effects produced by thermal decomposition, but in other respects the results differ markedly. Similar radiation and thermal effects include the following: (1) irregular or ill-defined circular etch pits are formed in both cases; (2) approximately the same size pits are produced; (3) the pit density is similar; (4) the c face is considerably more reactive than the m face; and (5) most importantly, many of the etch pits are aligned in crystallographic directions which are the same for thermal or radiolytic decomposition. Thus, dislocations play an important role in the radiolytic decomposition process.

Herley, P. J.↗
NASA NTRS1993

Organometallic chemical vapor deposition and characterization of ZnGe(1-x)Si(x)P2-Ge alloys on GaP substrates

The epitaxial growth of ZnGe(1-x)Si(x)P2-Ge alloys on GaP substrates by open tube organometallic chemical vapor deposition (OMCVD) is reported. The chemical composition of the alloys characterized by energy dispersive X-ray spectroscopy shows that alloys with x up to 0.13 can be deposited on (001) GaP. Epitaxial growth with mirror smooth surface morphology was achieved for x less than or equal to 0.05. Transmission electron microscopy (TEM) micrographs of these alloys show specular epitaxy and the absence of microstructural defects indicating a defect density of less than 10(exp 7) cm(sup -2). Selected area electron diffraction pattern of the alloy shows that the epitaxial layer crystallizes in the chalcopyrite structure with relatively weak superlattice reflections indicating certain degree of randomness in the cation sublattice. Hall measurements show that the alloys are p-type, like the unalloyed films; the carrier concentration, however, dropped about 10 times from 2 x 10(exp 18) to 2 x 10(exp 17) cm(sup -3). Absorption measurements indicate that the band tailing in the absorption spectra of the alloy was shifted about 0.04 eV towards shorter wavelength as compared to the unalloyed material. Diodes fabricated from the n(+)-GaP/p-ZnSiP2-ZnGeP2-Ge heterostructure at x = 0.05 have a reverse break-down voltage of -10.8 V and a reverse saturation current density of approximately 6 x 10(exp -8) A/sq cm.

Xing, G. C.↗
NASA NTRS2003

High Resolution, Single-Step Patterning of Silica Aerogels

Three-dimensional metallic structures are fabricated with high spatial resolution in silica aerogels. In our method, silica hydrogels are prepared with a standard base-catalyzed route, and exchanged with an aqueous solution typically containing Ag' ions (1 M) and 2-propanol (0.2 M). The metal ions are reduced photolytically with a table-top ultraviolet lamp, or radiolytically, with a focused X-ray beam. We fabricated dots and lines as small as 30 x 70 km, protruding for several mm into the bulk of the materials. The hydrogels are eventually supercritically dried to yield aerogels, without any measurable change in the shape and spatial resolution of the lithographed structures. Transmission electron microscopy shows that illuminated regions are composed of Ag clusters with a size of several pm, separated by thin layers of silica.

Bertino, M. F.↗
NASA NTRSDate not supplied

Unraveling Solar Wind Space Weathering of Carbon-Rich Asterods: Low-Flux VS. High-Flux Ion Irradiation of Murchison

Introduction: Space weathering processesalter the microstructural, compositional, and optical properties of airless planetary surfaces.Solar wind space weatheringforms ion-damaged rims within the outermost ~100 nm of regolith grains through atomic-displacements and implantation of energetic H+and He+ions[1]. Transmission electron microscope(TEM)studies of space weathered Itokawa and lunar olivine particles reveal predominantly nanocrystalline solar wind-damaged rims with only minor regions of amorphization[2-5]. This finding differs from laboratoryion irradiation experiments in which samples become amorphous at fluences 2-3 orders of magnitude lower than the independentlyconstrained fluences for still-crystalline natural samples [6-7].Ion flux is generally considered to have a secondaryeffectcompared to fluence in these irradiation experiments. However, solar wind irradiation of natural samples occurs at a flux that is ~4-5 orders of magnitude lower than whatisused inlaboratory simulations (e.g., [6,8-9]). Constraining how the very low ion flux of solar wind influences the microstructural, chemical, and spectral alteration of silicate minerals will improve our understanding of solar wind space weathering and aid in the analysis of returned samples from the Hayabusa2 and OSIRIS-REx missions. Here we report results from low-and high-flux ion irradiation experiments on the Murchison (CM2)meteoritewithcomparable total fluences. Methods: We performed low-flux and high-flux He+(4 keV) and H+(1 keV) irradiation experiments on separate, dry-cut Murchison slabs. Low-flux He+irradiation reached a total fluence of 2.1 x 1016ions/cm2(~400 years of exposure at Bennu) using a flux of 3.6 x 1011ions/cm2/s; low-flux H+irradiation reached a total fluence of 3.9 x 1016ions/cm2(~30 years) using a flux of 6.6 x 1011ions/cm2/s. High-flux He+irradiation reached a total fluence of 2.0 x 1016ions/cm2(~400 years)using a flux of 9.1 x 1012ions/cm2/s; high-flux H+irradiation reached a total fluence of 5.8 x 1016ions/cm2(~50 years)using flux of 8.4 x 1012ions/cm2/s. By irradiating to similar total fluences in both the low-flux and high-flux experiments, we can better isolate and evaluatethe effects of ion flux. Differences between unirradiatedand irradiated surfaces are determined using threeanalytical techniques:(1) in situX-ray photoelectron spectroscopy(XPS) reveals changes in surface chemistry,(2) visible to near-infrared spectroscopy (VNIR; 0.35-2.5 μm) highlights changes in spectraltrends, such as albedo and slope, and (3) TEM and energy-dispersive X-ray spectroscopy (EDS) identifieschanges in nanoscale structure and elemental composition within olivine and matrix electron-transparent thin sections prepared using focused ion beam scanning electron microscopy (FIB-SEM). Results and Discussion: XPS analyses of the low-fluxand high-fluxHe+-and H+-irradiated samples showa minorreduction in surface carbon contentand chemicalreduction ofFe3+to Fe2+. The latter result is consistent with the higher Fe2+/Fe3+ratios observed in phyllosilicate-rich space weathered rims of Ryugu grains [10].VNIR analyses suggest that the low-flux H+-irradiated spectrum has a slightly bluer slope (over 0.65-2.5 μm) compared to the unirradiated VNIR spectrum from [9] while the low-flux He+-irradiated spectral slope is comparable to the unirradiated surface. Both the high-flux He+-and H+-irradiated VNIR spectra exhibitslightlyhigheralbedos at shorter wavelengths relativeto their unirradiated counterparts, with He+irradiation yielding a greater change. Thus far, the low-flux He+-irradiated matrix and olivine FIBsections as well as the low-flux H+-irradiated olivine FIBsection have been examined with TEM. The surfaces of all three samplesshowless vesiculation than high-flux/high-fluenceirradiated matrix and olivine samples from [9]. The depth of phyllosilicate amorphization in thelow-fluxHe+-irradiated matrix FIBsection varieslaterally, with crystalline domains occurring as shallow as ~25 nm in some regions. Thelow-flux He+-irradiated olivine FIBsection has acontinuous,~40-90 nm thick ion-affected layer with polycrystalline and amorphous microstructures. The low-flux H+-irradiated olivine sampleexhibits a distinct, ~10-40 nm ion-affected layer whose uppermost ~20 nmin thicker regions is predominantly amorphous.Continuing to compare results from this work to those from [9] will provide a comprehensive understanding of how ion flux impacts the microstructural, chemical, and optical modification of various mineral phases and, in turn,help identify space weathering features from parent body alteration in Hayabusa2 and OSIRIS-REx returned samples.

D L Laczniak↗