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Plasticity and Damage Modeling of Stress Asymmetry and Dynamic Behavior of AFS Additive Manufactured Aluminum Alloy 2219

The Solid State Additive Manufacturing (AM) process referred as MELD that fabricated the samples in this study, provides a new path for repairing, coating, joining and additive manufacturing metals and metal matrix composites. This research will be the first application of a physics-based microstructure dependent internal state variable (ISV) plasticity and damage material model to capture the mechanical response of an AM Aluminum Alloy (AA) 2219 via the MELD process. In this research, a microstructure-based internal state variable (ISV) plasticity-damage model was used to capture the mechanical behavior of AFS 2219 aluminum alloy. Aeroprobe Corporation, creator and patent holder for the MELD process, fabricated the material by pushing a solid filler rod of AA2219-T861 material through a hollow rotating tool onto an AA2219 T851 plate substrate. As feedstock, solid or powder precursor metals are pushed through a nonconsumable rotating cylindrical tool. Herein, added layers are deposited and metallurgically bonded to substrate material or previously deposited layers by the heat generated from the rotating tool through plastic deformation of the filler material. Once a layer has been added, the tool height increases, and starts the deposition of the next layer. This process results in beneficial properties such as grain refinement, homogenization and reduced porosity (fully dense). This process will experience temperatures similar to those in the weld nugget zone (WNZ) in friction stir welding (FSW), ranging from 0.6-0.9 Tm, with Tm being the melting point of the material. MELD is highly scalable with AA deposition rates reaching over 1000 cm3/hr, which allows for MELD being used for repairs, coatings, and building components. A motivating factor driving the research for physics-based history dependent material modeling of MELD components is the ability to accurately capture the stress-state and strain rate dependence in the material caused by variations in material microstructure from the MELD processing of new or repaired components. The ISV model incorporates microstructural content and is consistent with continuum level kinematics, kinetics, and thermodynamics. These features allow the ISV model to capture large deformations at the structural scale using the kinematic and isotropic hardening, while microscale damage is obtained from the microstructural features. The benefits of the ISV model arise from the inclusion of structure-property relationships identified from microstructural characterization and experimentation. The Bauschinger effect (BE) is an important concept, vital in the accurate prediction of cyclic stress-strain response of ductile materials such as metals. The ISV model has been successfully used to capture the behavior and damage, and the BE of different aluminum alloys and steels. The ISV model uses kinematic and isotropic hardening to help capture deformations of the material at the macro scale. To understand this hardening relationship, calculating the kinematic and isotropic hardening relationship in the material is warranted for a high-fidelity model. Electron Backscattered Diffraction (EBSD) was used to characterize the as-fabricated microstructure, where a fully-dense equiaxed grain morphology with average grain size of 2.5 μm was observed. Microhardness mapping of the as-built structures, monotonic tension and compression experiments at both quasi-static (0.001/s) strain rates, tension-followed-by-compression and compression-followed-by-tension experiments were performed to obtain the set of plasticity and damage constants necessary to capture strain rate and stress state behavior of this additive material. To calibrate the plasticity-damage model, a single set of constants were determined to capture the different stress states the MELD AA2219. One set of the constants was determined from experimental true stress-strain curves for the tension and compression data. Additionally, microstructural information and data from the open literature were used as the other model constants. This research is a first of its kind for AFS AA2219, includes correlating the ISV model to the monotonic experimental results that capture the isotropic and kinematic plasticity mechanical response.

Rivera, O. G.↗

Novel Shock Microstructures in Accessory Minerals from the Haughton Dome, Devon Island, Nunavut, Canada

The 23 km-diameter, ca. 24 Ma Haughton Dome impact structure in the Canadian Arctic on Devon Island, Nunavut (89deg41′W, 75deg22′N) occurred within a two layered target composed of a shallowly-dipping ~1700 m thick succession of Paleozoic limestones and evaporates overlying ca.1.9 Ga high grade gneisses [1, 2]. Within the structure a well preserved impact melt bearing breccia unit contains a variety of shocked clasts from the pre-impact sediments and basement gneisses [3]. Due to their high level of preservation a variety of studies have been undertaken on the clast population of the melt bearing breccia, including characterization of shock within the accessory minerals of the basement lithologies [4, 5]. This study presents high resolution electron backscatter diffraction (EBSD) microstructural data for zircon and monazite from historic samples of the basement gneiss, in which bulk shock pressures have been previously constrained based on major phases [4, 6]. Shocked zircon and monazite grains have been investigated from shock stage 1b (sample 72110), 2 (7273) and 3 (7192, Dig-9) [4, 6]. At lower shock levels zircon displays planar microstructures consistent with mechanical shock {112} twin formation [7] and deviatoric transformation to the high pressure polymorph reidite [8]. Zircon grains from shock stage three show a more chaotic microstructure with multiple orientations of tightly spaced sets of reidite that are variably recrystallized to zircon neoblasts. Monazite from lower shock stages contains a number of mechanical twin orientations that are indicative of shock deformation [9]. At higher shock pressures a lath like structure of interlocking twin orientations has been identified. This microstructure is suggestive of a reversion transformation from a high pressure polymorph [10] and is the first evidence for the transformation of monazite during shock.

Erickson, Timmons M.↗

Microstructural Characterization of TiO2-II in the Chicxulub Peak Ring

The peak ring of the approximately 180 kilometer-diameter Chicxulub impact crater on the Yucatan Peninsula, Mexico, was recently drilled during IODP-ICDP (International Ocean Discovery Program-International Continental Scientific Drilling Program) Expedition 364, producing core M0077A. The new core provides insights into the anatomy, composition, tectonic deformation, shock metamorphism, and post-impact overprint of crater-filling impactites and crystalline basement rocks. The basement rocks were shocked to approximately 12.5-17.5 gigapascals, uplifted, and hydrothermally altered. This study presents a combined Raman spectroscopic and electron backscatter diffraction (EBSD) study of TiO2-II, a high-pressure polymorph of TiO2 with an alpha-PbO2 structure (orthorhombic; space group Pbcn; density 4.34 grams per cubic centimeter, in shocked granitoid rock of the Chicxulub peak ring.

Schmieder, Martin↗

Quantifying the Influence of Redox Conditions on the Seismic Properties of Olivine

A series of eight olivine specimens were fabricated by hot-pressing at 1200 degrees Celsius and 300 megapascals (MPa). Each hot-pressed specimen was then wrapped in Pt, Ni or NiFe foil to vary oxygen fugacity (fO2), and interrogated via forced torsional oscillation. Mechanical testing was conducted at 10 oscillation periods between 1 and 1000 seconds, at a confining pressure of 200 MPa, during a slow staged-cooling from a maximum temperature of 1200 degrees Celsius to room temperature. After mechanical testing, each specimen was axially sectioned and EBSD (Electron BackScatter Diffraction) was used for the determination of the representative grain size, and grain size distribution of each sample. In addition, each longitudinal section was mapped via FTIR (Fourier Transform InfraRed spectroscopy) to determine the spatial distribution and concentrations of chemically bound and molecular water. Amongst these specimens, chemically bound ‘water’ contents were observed to vary between 0 and 1150 atom ppm (parts per million) H/Si, and molecular water concentrations varied between 0 and 245 atom ppm H/Si. Our forced-oscillation results demonstrate that the measured magnitude of anelastic relaxation within the experimental ‘window’ of oscillation periods is unrelated to the water content. Rather, a relationship was observed between the magnitude of anelastic relaxation and the prevailing redox conditions, which is influenced by the choice of metal sleeving used during the mechanical test. Further, regardless of water content or metal sleeving, each specimen exhibits coupled variations in shear modulus and dissipation within the observational window, indicative of ‘high-temperature background’ behavior, that can be described by a Burgers-type model. During initial fitting of the Burgers models, the unrelaxed shear modulus at a reference temperature of 900 degrees Celsius (G (sub UR)) and the temperature derivative of the unrelaxed shear modulus (dG (sub U)/dT), were treated as adjustable parameters. For all Fe-bearing olivine samples (but not a hydrous and oxidized Fe-free sample) we observe deficits of G (sub UR), and increased values of dG (sub U)/dT, relative to the expected elastic (anharmonic) behavior of Fo90 olivine. This behavior is indicative of anelastic relaxation occurring at shorter periods than observable within the ‘window’ of oscillation periods used in the mechanical test. Moving towards a comprehensive seismologically applicable Burgers model, which includes this newly observed effect of redox conditions on anelastic relaxation, we will present our progress in reconciling truly anharmonic and elastic behavior of Fo (sub 90) olivine with our observed forced-oscillation data.

Cline, Christopher, II↗

3d Crystallographic Orientation of Olivine in Bjurböle Chondrules

The crystallographic orientations of chondrule minerals can provide important insights into their formation and deformational history. For example, the orientations of the olivine bars and surrounding rim in barred olivine chondrules provide information and on the conditions of crystallization and the orientations and shapes of olivines within porphritic chondrules can record the reactions with the surrounding nebular gas during chondrule formation. Later deformation on the parent body can cause crystal-plastic deformation of chondrule minerals that is evident through their intracrystalline lattice misorientations. Typically these crystal orientations and lattice misorientations are determined using electron backscatter diffraction (EBSD) on thin sections but this gives only a 2D picture for what is actually a 3D texture. While it is possible to combine EBSD with serial sectioning to build a 3D dataset of texture, this is a destructive, time-intensive process. A recent technological development that enables non-destructive, 3D crystallographic orientation measurement is X-ray diffraction contrast tomography (DCT), which uses the X-ray diffraction of the crystal lattice to determine orientation. Originally only possible using monochromatic X-ray beams at 3rd generation synchrotron light sources, DCT has been recently adapted to polychromatic sources of laboratory X-ray microscopes (referred to as Lab-DCT). Up to this point LabDCT has only been applied to large, well-formed crystals of high symmetry (i.e., metals), but we recently acquired DCT datasets for a pair Bjurböle chondrules to determine the applicability of the technique to natural, mutlimineralic samples composed predominately of olivine (i.e., chondrules).

Hanna, R. D.↗

The Influence of Redox Conditions on the Seismic Properties of Polycrystalline Olivine

Eight olivine specimens were fabricated by use of a solgel method and hot-pressing at 1200 degrees Centigrade and 300 megapascals (MPa) inside of welded Pt capsules. Each hot-pressed specimen was then recovered, precision ground, and wrapped in Pt, Ni or NiFe foil to vary oxygen fugacity (fO2) during the subsequent forced torsional oscillation measurements. Mechanical testing was conducted at 10 oscillation periods between 1 and 1000 seconds, at a confining pressure of 200 MPa, during a slow staged-cooling from a maximum temperature of 1200 degrees Centigrade down to room temperature. After mechanical testing, each specimen was axially sectioned and EBSD (Electron BackScatter Diffraction) was used for the determination of the representative grain size, and grain size distribution of each sample. In addition, each longitudinal section was mapped via FTIR (Fourier Transform Infrared Spectroscopy) to determine the spatial distribution and concentrations of chemically bound and molecular water. Amongst these eight specimens, chemically bound ‘water’ contents were observed to vary between 0 and 1150 atom parts per million (ppm) H/Si, and molecular water concentrations varied between 0 and 245 atom ppm H/Si. Our forced-oscillation results demonstrate that the measured magnitude of anelastic relaxation within the experimental ‘window’ of oscillation periods is unrelated to the water content. Rather, a relationship was observed between the magnitude of anelastic relaxation and the prevailing redox conditions, which is influenced by the choice of metal sleeving used during the mechanical test. Further, regardless of water content or metal sleeving, each specimen exhibits coupled variations in shear modulus and dissipation within the observational window, indicative of ‘high-temperature background’ behavior, that can be described by a Burgers-type model. During initial fitting of the Burgers models, the unrelaxed shear modulus at a reference temperature of 900°C (elastic unloading/reloading shear modulus G (sub UR)) and the temperature derivative of the unrelaxed shear modulus (dGU/dT), were treated as adjustable parameters. For all Fe-bearing olivine samples we observe deficits of G (sub UR) and increased values of dGU/dT, relative to the expected elastic (anharmonic) behavior for Fo (Forsterite content percentage) (sub 90) olivine. This behavior is indicative of anelastic relaxation occurring at shorter periods than observable within the ‘window’ of oscillation periods used in the mechanical test. Moving towards a comprehensive and seismologically applicable Burgers model, which includes this newly observed effect of redox conditions on anelastic relaxation, we will present our progress on reconciling truly anharmonic and elastic behavior of Fo (sub 90) olivine with our observed forced-oscillation data.

Cline, C. J., II↗

New Levels of High Angular Resolution EBSD Performance via Inverse Compositional Gauss-Newton Digital Image Correlation

Conventional high angular resolution electron backscatter diffraction (HREBSD) uses cross-correlation to track features between diffraction patterns, which are then related to the relative elastic strain and misorientation between the diffracting volumes of material. This paper adapts inverse compositional Gauss Newton (ICGN) digital image correlation (DIC) to be compatible with HREBSD. ICGN works by efficiently tracking not just the shift in features, but also the change in their shape. Modeling a shape change as well as a shift results in greater accuracy. This method, ICGN HREBSD, is applied to a simulated data set, and its performance is compared to conventional cross-correlation HREBSD, and cross-correlation HREBSD with remapping. ICGN HREBSD is shown to have about half the strain error of the best cross-correlation method with a comparable computation time.

T. J. Ruggles↗

Capturing an Evolving Nebular Environment: A Petrographic and Geochemical Study of a Type A, B & C CAI

Calcium, Aluminum-rich Inclusions (CAIs) were the first formed solids in our Solar System, with mineral assemblages reflecting the first phases predicted to condense out of a hot nebular gas of Solar composition. Geochemical, textural and crystallographic information in CAIs can be used to constrain the temperature, pressure, and composition (e.g., oxygen fugacity) of the gaseous reservoir(s) from which they formed, as well as any secondary (nebular and parent body) processes they underwent. Coordinated geochemical and textural analyses provide information on nebular conditions (i.e., astrophysical environments and dynamics of nebular gas reservoirs) in which these CAIs formed. In order to better understand the evolution of nebular reservoirs at the time of CAI formation, we analyzed a Type A, B and C CAI using Electron Probe Micro-Analyzer (EPMA) and Electron BackScatter Diffraction (EBSD) at NASA Johnson Space Center (JSC).

Comins, M. B.↗

TPSAS-NF1676L-31381-DND

- Accumulation of excess negative charge generates potential differences between spacecraft ground and space (frame potential), between two points on the spacecraft surface or within materials (differential potential) - An electrostatic discharge (ESD) results when electric fields associated with potential differences (E = -∇Φ) exceed the dielectric breakdown strength of materials allowing charge to flow in an arc - Magnitude of damage depends on energy available to an arc E = ½CV^2 - Charging to a potential V depends on electrical properties of materials - Surface and volume resistivity - Dielectric constant - Secondary and backscattered electron yields, photoemission yields - Dielectric breakdown strength

Joseph I. Minow↗

Spatial U-Pb Age Distribution in Shock-Recrystallized Zircon – A Case Study from the Rochechouart Impact Structure, France

Age determination of impact structures via the zircon U–Pb system remains challenging and often ambiguous due to highly variable effects of shock metamorphism on U-Pb geochronology. It is, therefore, crucial to link the observed zircon microtextures, including their temperature and pressure conditions associated with their formation, directly to the U–Pb ages preserved. Here, we analyzed three recrystallized zircon grains and one plastically deformed zircon crystal from the medium-sized Rochechouart impact structure in the northwestern Massif Central of France. For the Rochechouart impact structure the impact age (206.92 ± 0.32 Ma [40Ar/39Ar]) as well as the 2 tectono-themal history is well established making this study site ideal to test concepts about U-Pb systematics in shocked zircon and to differentiate between shock-driven age resetting and preimpact crystallization and metamorphic overprinting. Zircon microstructures were studied using scanning electron imaging, cathodoluminescence imaging, and electron backscatter diffraction (EBSD) mapping. Further, we conducted U–Pb Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) depth-profiling analysis, allowing us to interpret the resultant age data in discrete steps with increasing ablation time/depth. The U–Pb depth profiling data demonstrate that plastically strained grains are incompletely reset and preserve rim and interior age domains reflecting typical pre-impact (pre-Variscan and Variscan) regional tectonic ages. Our results also reveal that the granular crystals encountered contain microstructural evidence for “former reidite in granular neoblastic” (FRIGN) zircon, reflecting both high-pressure (⩾30GPa) and high temperature (⩾1200℃) conditions. This signifies that FRIGN zircon is now known from an additional, medium sized, impact structure further supporting the hypothesis that this impact induced microstructure is commonly preserved. In addition, FRIGN zircon has a high potential to preserve completely impact-reset crystal domains (~204 to 207 Ma) that can be identified by our combined analytical approach of U–Pb depth profiling and EBSD mapping, and thus are suitable for determining reliable impact ages

U-Pb depth profiling↗

Zircon (U-TH)/He Impact Crater Thermochronometry and the Effects of Shock Microstructures on Helium Diffusion Kinetics

Accurate age determinations of hyper-velocity impact and cratering events remains difficult and often controversial, while less than half of all known impact craters are regarded as accurately and precisely dated. Besides 40Ar/39Ar and U-Pb methods, zircon (U-Th)/He dating of impactites is a burgeoning technique to date large- to medium-sized impact structures. Zircon (U-Th)/He ages can be fully reset in minutes at 1000°C, T commonly reached in and directly adjacent to impact melt domains, whereas complete resetting of zircon (U-Th)/He at <300°C, which might be encountered near the crater margins or persist in post-impact hydrothermal systems, may take >103-4 years. However, there is a critical need to test the reliability of (U-Th)/He impact dating in shock deformed zircon, and to quantify helium diffusion kinetics in well-characterized grains with a broad spectrum of shock-induced defect substructures. For this purpose, we investigated samples from two impact structures, the 66 Ma Chicxulub multi-ring basin and the 15 Ma Ries complex crater, to compare zircon diffusion kinetics from impact structures with varying parameters, including size, age, and hydrothermal system longevity. Shock microstructures were characterized by backscattered-electron (BSE) imaging prior to determination of diffusion step-heating fractional release experiments using light-bulb furnace with prograde and retrograde incrementally 10°C steps from 300°C to 600°C. We find that zircon with low-level shock microstructures exhibit no significant deviation from helium diffusion kinetics of undamaged zircon. In contrast, zircon grains with planar deformation features and granular textures classified by SEM are characterized by a dramatic decrease in helium retentivity, similar to radiation damage, due to the reduction in the effective domain size and the introduction of fast diffusion pathways. This likely renders shocked grains more susceptible to impact-induced hydrothermal resetting. Hence, characterization of impact microstructure is critical for determining accurate impact ages, but also offers the opportunity to determine the magnitude and duration of post-impact hydrothermal circulation.

Catherine Ross↗

Deciphering Extreme Mineral Records; Microstructural Phase Heritage of Shocked Materials

High-pressure minerals such as coesite, stishovite, and reidite are often used as indicators of shock metamorphism. However, high-pressure and high-temperature phases are metastable at ambient conditions and, therefore, often revert to a more energetically favorable phase. During solid-state transformations, the crystallographic orientations of the stable polymorph are controlled by the transformation pathway from the parent. Microstructural orientation analysis using electron backscatter diffraction (EBSD) of the stable phase can reveal systematic intercrystalline orientation relationships (OR) diagnostic of solid-state transformations from these high-pressure or high-temperature polymorph phases (Cayron et al., 2006). Knowledge of polymorph stability fields for a given system can thus be used to infer minimum shock P and/or T conditions that rocks have experienced, which are otherwise unavailable using traditional thermobarometers such as element partition coefficients. Using orientation relationships to infer the former presence of mineral phases has been termed microstructural “phase heritage”, and has successfully been used to probe for evidence of extreme pressures and temperatures resulting from hypervelocity impacts. The reconstruction of polymorphs of ZrSiO4 (zircon, reidite) and ZrO2 (baddeleyite) have further elucidated the behavior of these phases under hypervelocity impact conditions (Timms et al., 2017a; White et al., 2018), and OR analysis of shocked monazite has identified a previously unrecognized tetragonal high-P polymorph (Erickson et al., 2019). Zircon will convert to the low tetragonal polymorph reidite at shock stresses above ~21 GPa. However, upon decompression at temperatures above 1200 °C reidite will revert to zircon (Kusaba et al., 1985). Recrystallized zircon neoblasts encased in impact melt often show systematic misorientation relationships of 90° about <110> indicative of reversion from the reidite (Fig. 1), and preserving cryptic evidence of the high-P history that is often erased by the post shock thermal spike (Cavosie et al., 2016). Microstructural OR analysis of a dissociated zircon corona composed of baddeleyite (monoclinic-ZrO2) has identified the former presence of cubic zirconia within impact melt glass from the Mistastin Lake impact structure, Labrador, CA. Based on stability fields in the ZrO2-SiO2 binary phase diagram, cubic zirconia records thermal conditions in excess of 2370 °C at ambient P, indicating that the Mistastin impact melt is the hottest rock identified on Earth’s surface (Timms et al., 2017b). Shock-deformed monazite (monoclinic La,Ce,ThPO4) containing lamellae comprised of interlocking laths has been identified from the Haughton Dome impact structure, Nunavut, Canada and Nördlinger-Ries Crater, southern Germany. The lath-structured lamellae are composed of four systematic orientation variants, which OR analyses indicate originate from a tetragonal parent whereby the [010]monoclinic aligns with either [100] or [010]tetragonal (Erickson et al., 2019). These results highlight utility of microstructural phase heritage analyses for the identification of unstable high-P or high-T polymorphs that uniquely record the extremely transient shock conditions produced by hypervelocity impacts.

Timmons Erickson↗

Zircon (U-Th)/He Impact Crater Thermochronometry and the Effects of Shock Microstructures on Helium Diffusion Kinetics

Accurate and precise age determination of impact cratering events remains challenging and often contentious; less than half of all known craters are regarded as accurately and precisely dated. Zircon (U-Th)/He (ZHe) dating of impactites can be employed to date medium to large impact structures as ZHe ages can be fully reset in minutes at T >1000°C, a plausible scenario in the central melt pool. In contrast, complete resetting of ZHe at 200-300°C, encountered near the crater margins or due to post-impact hydrothermal overprinting, may take >103-6 years. To test the reliability of ZHe impact dating, we have quantified the effects of shock-induced microstructures on helium diffusion kinetics in well-characterized variably shocked zircon. We investigated samples from two impact structures, the Chicxulub multi-ring crater and Ries complex crater, to compare diffusion kinetics from structures with different size, age, and hydrothermal system longevity. Shock microstructures were characterized by backscattered-electron imaging prior to determining the He diffusion kinetics by prograde and retrograde fractional-release experiments via light-bulb furnace with incremental step-heating (10°C) from 300°C to 600°C. Next, we examine the internal interconnectivity and sizes of the diffusion domains by EBSD. While we found that zircon with few shock microstructures exhibited no marked deviation from helium diffusion kinetics of undamaged zircon, zircon grains with planar microstructures and granular textures are characterized by a dramatic decrease in helium retentivity due to the reduction in the effective domain size and the introduction of interconnected fast diffusion pathways. A subset of grains were ZHe dated and showed that less deformed grains yielded a weighted mean age within error of the accepted impact ages, while the grains with planar microstructures or granular textures gave systematically younger ages. These new diffusion data and ZHe ages demonstrate that highly shocked grains are unsuitable for ZHe impact crater dating. Therefore, detailed characterization of impact-induced microstructures is critical for determining accurate ZHe impact ages and offers the possibility of investigating post-impact hydrothermal circulation.

Zircon↗

Empirical Constraints on Progressive Shock Metamorphism of Magnetite from the Siljan Impact Structure, Sweden

Little is known about the microstructural behavior of magnetite during hypervelocity impact events, even though it is a widespread accessory mineral and important magnetic carrier in terrestrial and extraterrestrial rocks. We report systematic electron backscatter diffraction crystallographic analysis of shock features in magnetite, from a transect across the 52-km diameter ~380 Ma Siljan impact structure in Sweden. Magnetite grains in granitoid samples contain brittle fracturing, crystal-plasticity, and lamellar twins. Deformation twins along {111} with shear direction of <112> are consistent with spinel-law twins. Inferred bulk shock pressures for investigated samples, as constrained by planar deformation features (PDFs) in quartz and shock twins in zircon, range from 0–20 GPa; onset of shock-induced twinning in magnetite is observed at >5 GPa. These results highlight the utility of magnetite to record shock deformation in rocks that experience shock pressures >5 GPa, which may be useful in quartz-poor samples. Despite significant hydrothermal alteration, and variable transformation of host magnetite to hematite, shock effects are preserved, demonstrating that magnetite is a reliable mineral for preserving shock deformation over geologic time.

magnetite↗

Zircon, Baddeleyite, and Reidite Found in Ries Crater Suevite

Introduction: Impact events can generate superheated impact melts and even vapor [1]. In the past decade, evidence of the high temperatures and high pressures of the impact process has been found in the impact melt from terrestrial craters (e.g., Mistastin Lake [2], Meteor Crater [3]) and even on the Moon [4–5]. Often, these studies involve zircon or zirconium-bearing phases. Zircon is a particularly useful mineral, due to its robustness and durability against weathering. It is used principally for chronology, but it has a multitude of geologic applications, including geothermometry and fingerprinting magma sources. Here we focus on its capability of recording impact conditions. Grains of zircon (ZrSiO4) are converted at high temperature and/or pressure during an impact event to reidite (a high-pressure polymorph of ZrSiO4) or to tetragonal-ZrO2 + SiO2 [6]. Reidite and tertragonal-ZrO2 leave identifying relicts in the rocks, markers of the high pressures and/or temperatures these rocks underwent. Ries Crater is a 26-km-diameter peak ring crater in southern Germany that formed approximately 15 Ma [7–9]. Ries is the type locality of the polymict impact breccia known as suevite. Here, we report a microanalytical study of suevite from the Ries impact structure. These analyses are used to inform our understanding of the pressure and temperature conditions involved in creating a polymict impact breccia such as suevite in a peak ring crater. Sample Description: The sample, denoted 16RS08, originates from Otting Quarry, at 48.8777° N, 10.7921° E, approximately 17 km from the center of the Ries Crater in Germany (approximately 4 km outside the crater rim). The material recorded in sample 16RS08 is therefore considered an outer suevite. The outer suevite is a discontinuous layer of polymict impact breccia that occurs outside the central ring of Ries, up to 22 km from the center of the crater [9]. Lithic clasts in the outer suevite consist primarily of crystalline basement rocks (gneiss, granite, amphibolite), with less than 5% of lithic clasts being overlying sedimentary rocks (limestone, sandstone, shale) [9]. The thin section studied contains variably shocked lithic and mineral clasts, impact glass, and interstitial minerals that make up the matrix of the breccia (Fig. 1) [9]. Methods: We used a Cameca SX100 electron probe microanalyzer (EPMA) located in the Kuiper Materials Imaging and Characterization Facility (KMICF) at the University of Arizona to obtain 15 elemental X-ray maps of 16RS08. We next used the JEOL 7900F SEM at the Astromaterials Research & Exploration Science (ARES) at NASA Johnson Space Center (JSC) to obtain electron backscatter diffraction (EBSD) maps and energy dispersive X-ray spectroscopy (EDS) maps of select portions of the section. The EBSD data were collected under beam conditions of 20 kV, and ~9 μA, with step sizes varying from 0.05 to 2 μm. Following EBSD data collection, we processed the data using AZtecCrystal and MTEX, a free MATLAB toolbox. Results: We used the elemental X-ray maps to identify the areas of interest in the section, particularly phosphates and Zr-bearing grains. These areas of interest were then targeted for follow up EBSD and EDS analyses. We have identified, through combined EBSD and EDS analysis, the presence of zircon, reidite, and monoclinic-ZrO2 (baddeleyite) in 16RS08. In 16RS08, we have found singular grains of zircon, zircon with a vermicular baddeleyite halo (Fig. 2a), and granular zircon with reidite (Fig. 2b). The different Zr-rich phases and their corresponding textures signifies that this sample underwent a broad spectrum of pressure and temperature conditions during the impact event. For example, zircons surrounded by a vermicular baddeleyite and SiO2 intergrowth (i.e., Fig. 2a) have been shown to preserve evidence of the extremely high temperatures of impact melt, upwards of 2370 °C [2, 6]. Similarly, reidite and granular zircon (i.e., Fig. 2b) have been shown to preserve evidence of high pressure, as the transition to reidite occurs >30 GPa [3, 6]. Future Work: Next, we will process the EBSD and EDS data for these Zr-rich grains, specifically looking for indicators of cubic- or tetragonal-ZrO2 in the baddeleyite remnants and of shock-precursors to the reidite. To further inform our work, we will also obtain BSE images of these grains using a Hitachi S-4800 SEM in KMICF at the University of Arizona, as well as geochemical spot analyses via EPMA. The data collected will be used to constrain the formation conditions of the Ries Crater outer suevite. Acknowledgments: We thank Ken Domanik and Jerry Chang for their support with data collection. This work was supported by a University of Arizona RII Core Facilities Pilot Program grant and start-up funds to JJB. TME thanks A. Cavosie and N. Timms for assistance during field sampling. We acknowledge support from NASA’s Planetary Science Research program for analysis performed at JSC. References: [1] Melosh H. J. (1989) Oxf. U. Press. [2] Timms et al. (2017) EPSL 477, 52–58. [3] Cavosie et al. (2016) Geology 44:9, 703–706. [4] White et al. (2020) Nature Astr. 4, 974–978. [5] Crow C. A. et al. (2017) GCA 202, 264–284. [6] Timms et al. (2017) Earth-Sci. Rev. 165, 185–202. [7] Schmieder M. et al. (2018) GCA 220, 146–157. [8] Schwarz W. H. et al. (2020) M&PS 55:2, 312–325. [9] Stöffler et al. (2013) M&PS 43:4, 515–589.

Zircon↗

Machiite, Al2Ti3O9, A New Oxide Mineral from the Murchison Carbonaceous Chondrite: A New Ultra-refractory Phase From the Solar Nebula

Machiite (IMA 2016-067), Al2Ti3O9, is a new mineral that occurs as a single euhedral crystal, 4.4 mm in size, in contact with an euhedral corundum grain, 12 mm in size, in a matrix of the Murchison CM2 carbonaceous chondrite. The mean chemical composition of holotype machiite by electron probe microanalysis is (wt%) TiO2 59.75, Al2O3 15.97, Sc2O3 10.29, ZrO2 9.18, Y2O3 2.86, FeO 1.09, CaO 0.44, SiO2 0.20, MgO 0.10, total 99.87, giving rise to an empirical formula (based on 9 oxygen atoms pfu) of (Al1.17Sc0.56Y0.10Ti4+0.08Fe0.06Ca0.03Mg0.01)(Ti4+2.71Zr0.28Si0.01)O9. The general formula is (Al,Sc)2(Ti4+,Zr)3O9. The end-member formula is Al2Ti3O9. Machiite has the C2/c schreyerite-type structure with a = 17.10 Å, b = 5.03 Å, c = 7.06 Å, b = 107°, V = 581 Å3, and Z = 4, as revealed by electron backscatter diffraction. The calculated density using the measured composition is 4.27 g/cm3. The machiite crystal is highly 16O-depleted relative to the coexisting corundum grain (D17O = –0.2 ± 2.4‰ and –24.1 ± 2.6‰, respectively; where D17O = d17O – 0.52 × d18O). Machiite is a new member of the schreyerite (V2Ti3O9) group and a new Sc,Zr-rich ultrarefractory phase formed in the solar nebula, either by gas-solid condensation or as a result of crystallization from a Ca,Al-rich melt having solar-like oxygen isotopic composition (D17O ~ –25‰) under high-temperature (~1400–1500 °C) and low-pressure (~10-4–10-5 bar) conditions in the CAI-forming region near the protosun. The currently observed disequilibrium oxygen isotopic composition between machiite and corundum may indicate that machiite subsequently experienced oxygen isotopic exchange with a planetary-like 16O-poor gaseous reservoir either in the solar nebula or on the CM chondrite parent body. The name machiite is in honor of Chi Ma, mineralogist at California Institute of Technology, for his contributions to meteorite mineralogy and discovery of many new minerals representing extreme conditions of formation.

Alexander N Krot↗

Adrianite, Ca12(Al4Mg3Si7)O32Cl6, a New Cl-rich Silicate Mineral From the Allende Meteorite: An Alteration Phase in a Ca-Al-rich Inclusion

Adrianite (IMA 2014-028), Ca12(Al4Mg3Si7)O32Cl6, is a new Cl-rich silicate mineral and the Si,Mg analog of wadalite. It occurs with monticellite, grossular, wadalite, and hutcheonite in altered areas along some veins between primary melilite, spinel, and Ti,Al-diopside in a Type B1 FUN (Fractionation and Unidentified Nuclear effects) Ca-Al-rich inclusion (CAI), Egg-3, from the Allende CV3 carbona-ceous chondrite. The mean chemical composition of type adrianite by electron probe microanalysis is (wt%) CaO 41.5, SiO2 27.5, Al2O3 12.4, MgO 7.3, Na2O 0.41, Cl 13.0, O=Cl –2.94, total 99.2, giving rise to an empirical formula of (Ca11.69Na0.21)(Al3.85Mg2.88Si7.23)O32Cl5.80. The end-member formula is Ca12(Mg5Si9)O32Cl6. Adrianite has the I43d wadalite structure with a = 11.981 Å, V = 1719.8 Å3, and Z = 2, as revealed by electron backscatter diffraction. The calculated density using the measured composition is 3.03 g/cm3. Adrianite is a new secondary mineral in Allende, apparently formed by alkali-halogen metasomatic alteration of primary CAI minerals such as melilite, anorthite, perovskite, and Ti,Al-diopside on the CV chondrite parent asteroid. Formation of secondary Cl-rich minerals sodalite, adrianite, and wadalite during metasomatic alteration of the Allende CAIs suggests that the metasomatic fluids had Cl-rich compositions. The mineral name is in honor of Adrian J. Brearley, mineralogist at the University of New Mexico, U.S.A., in recognition of his many contributions to the understanding of secondary mineralization in chondritic meteorites.

Chi Ma↗

Machiite, Al2Ti3O9, a New Oxide Mineral from the Murchison Carbonaceous Chondrite: A New Ultra-refractory Phase from the Solar Nebula

Machiite (IMA 2016-067), Al2Ti3O9, is a new mineral that occurs as a single euhedral crystal, 4.4 mm in size, in contact with an euhedral corundum grain, 12 mm in size, in a matrix of the Murchison CM2 carbonaceous chondrite. The mean chemical composition of holotype machiite by electron probe microanalysis is (wt%) TiO2 59.75, Al2O3 15.97, Sc2O3 10.29, ZrO2 9.18, Y2O3 2.86, FeO 1.09, CaO 0.44, SiO2 0.20, MgO 0.10, total 99.87, giving rise to an empirical formula (based on 9 oxygen atoms pfu) of (Al1.17Sc0.56Y0.10Ti4+0.08Fe0.06Ca0.03Mg0.01)(Ti4+2.71Zr0.28Si0.01)O9. The general formula is (Al,Sc)2(Ti4+,Zr)3O9. The end-member formula is Al2Ti3O9. Machiite has the C2/c schreyerite-type structure with a = 17.10 Å, b = 5.03 Å, c = 7.06 Å, b = 107°, V = 581 Å3, and Z = 4, as revealed by electron backscatter diffraction. The calculated density using the measured composition is 4.27 g/cm3. The machiite crystal is highly 16O-depleted relative to the coexisting corundum grain (D17O = –0.2 ±2.4‰ and –24.1 ± 2.6‰, respectively; where D17O = d17O – 0.52 ×d18O). Machiite is a new member of the schreyerite (V2Ti3O9) group and a new Sc,Zr-rich ultrarefractory phase formed in the solar nebula, either by gas-solid condensation or as a result of crystallization from a Ca, Al-rich melt having solar-like oxygen isotopic composition (D17O ~ –25‰) under high-temperature (~1400–1500 °C) and low-pressure (~10-4–10-5 bar) conditions in the CAI-forming region near the protosun. The currently observed disequilibrium oxygen isotopic composition between machiite and corundum may indicate that machiite subsequently experienced oxygen isotopic exchange with a planetary-like 16O-poor gaseous reservoir either in the solar nebula or on the CM chondrite parent body. The name machiite is in honor of Chi Ma, mineralogist at California Institute of Technology, for his contributions to meteorite mineralogy and discovery of many new minerals representing extreme conditions of formation.

Machiite↗