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At least 325 records · Page 18

Processing of laser formed SiC powder

Processing research was undertaken to demonstrate that superior SiC characteristics could be achieved through the use of ideal constituent powders and careful post-synthesis processing steps. Initial research developed the means to produce approximately 1000 A uniform diameter, nonagglomerated, spherical, high purity SiC powders. Accomplishing this goal required major revision of the particle formation and growth model from one based on classical nucleation and growth to one based on collision and coalescence of Si particles followed by their carburization. Dispersions based on pure organic solvents as well as steric stabilization were investigated. Test parts were made by the colloidal pressing technique; both liquid filtration and consolidation (rearrangement) stages were modeled. Green densities corresponding to a random close packed structure were achieved. After drying, parts were densified at temperatures ranging from 1800 to 2100 C. This research program accomplished all of its major objectives. Superior microstructures and properties were attained by using powders having ideal characteristics and special post-synthesis processing procedures.

Haggerty, J. S.↗

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↗

An unusual layered mineral in chondrules and aggregates of the Allende carbonaceous chondrite

Transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy dispersive X ray (EDS) and electron energy loss (EELS) spectroscopy examinations of the microstructures and phase relationships of minerals in opaque spherules in the Allende chondrules and aggregates are reported. The studies were carried out on petrographic thin sections which were ion-thinned. A significant metasomatic effect was observed in a highly oxidizing condition of a later cooled stage. An unusually layered Fe-, Ni-, and O-rich mineral related to serpentine was found to occur in the opaque specimen, and was judged to occur by alteration of olivine. It is noted that low temperature and a hydrous condition would have been required for the formation of the serpentine in the spherules, the first observed in Allende. It is suggested that the aqueous conditions occurred before the final stage of the meteorite formation, and proceeded in a nonterrestrial manner.

Tomeoka, K.↗

Microstructural Record of Evolving Condensation Processes in Fine-Grained Ca-Al-Rich Inclusions from the Reduced CV3 Chondrites

Fine-grained, spinel-rich Ca-Al-rich inclusions (FGIs) in carbonaceous chondrites consist of numerous layered nodules having cores of spinel, hibonite, and/or perovskite surrounded by multiple thin layers of melilite, anorthite, diopside, and/or olivine. They are interpreted as aggregates of direct high-temperature condensates from an 16O-rich nebular gas that escaped significant melting. However, FGIs are very complex objects composed of intimate intergrowths of fine-grained refractory phases and show extremely large variations in mineralogy, modal abundance, and textures. Thus, detailed FIB/TEM analyses of FGIs are required to fully characterize their micro-to-nanometer scale textures, mineralogy, and chemical compositions and hence elucidate their formation processes and conditions in the early solar nebula. Here, we present our on-going study of pristine FGIs from the reduced CV3 chondrites Efremovka and Thiel Mountains (TIL) 07003 and 07007 that have minimal evidence for secondary parent body alteration.

Han, J.↗

Liquid crystalline order in mucus

Mucus plays an exceptionally wide range of important biological roles. It operates as a protective, exchange, and transport medium in the digestive, respiratory, and reproductive systems of humans and other vertebrates. Mucus is a polymer hydrogel. It is secreted as discrete packages (secretory granules) by specialized secretory cells. Mucus hydrogel is stored in a condensed state inside the secretory granules. Depending upon the architecture of their constituent macromolecules and on the composition of the solvent, polymer gels can form liquid crystalline microstructures, with orientational order being exhibited over optically resolvable distances. Individual mucin molecules consist of alternating rigid segments (heavily glycosylated; hydrophilic) and flexible segments (nonglycosylated; hydrophobic). Polymer molecules consisting of rigid units linked by flexible spacers are frequently associated with liquid crystalline behavior, which again raises the possibility that mucus could form anisotropic fluid phases. Suggestions that mucins may be self-associating in dilute solution have previously been challenged on the basis of sedimentation-equilibrium studies performed on mucus in which potential sites of association were competitively blocked with inhibitors. However, the formation of stable liquid crystalline phases does not depend on the existence of inter- or intramolecular associations; these phases can form on the basis of steric considerations alone.

NASA Discipline Number 40-20↗

Experimental Insights into the Origin of Defect-Structured Hibonites Found in Meteorites

Hibonite (CaAl12O19) is a primary, highly refractory phase occurring in many Ca-Al-rich inclusions (CAIs). Previous microstructural studies of hibonite in CAIs and their Wark-Lovering (WL) rims showed the presence of numerous stacking defects in hibonites. These defects are interpreted as the modification of the stacking sequences of spinel and Ca-containing blocks within the ideal hexagonal hibonite structure due to the presence of wider spinel blocks [3], as shown by experimental studies of reaction-sintered compounds in the CaO-Al2O3 system. We performed a series of experiments in the CaO-Al2O3-MgO system in order to provide additional in-sights into the formation processes and conditions of defect-structured hibonites found in meteorites.

Han. J.↗

A study of aluminum-lithium alloy solidification using acoustic emission techniques

Physical phenomena associated with the solidification of an aluminum lithium alloy was characterized using acoustic emission (AE) techniques. It is shown that repeatable patterns of AE activity may be correlated to microstructural changes that occur during solidification. The influence of the experimental system on generated signals was examined in the time and frequency domains. The analysis was used to show how an AE signal from solidifying aluminum is changed by each component in the detection system to produce a complex waveform. Conventional AE analysis has shown that a period of high AE activity occurs in pure aluminum, an Al-Cu alloy, and the Al-Li alloy, as the last fraction of solid forms. A model attributes this to the internal stresses of grain boundary formation. An additional period of activity occurs as the last fraction of solid forms, but only in the two alloys. A model attributes this to the formation of interdendritic porosity which was not present in the pure aluminum. The AE waveforms were dominated by resonant effects of the waveguide and the transducer.

Henkel, Daniel P.↗

Microstructural Study of an 18-O-Poor Presolar Silicate Grain from The Meteorite Hills 00426 Cr2 Chondrite

The majority of presolar silicate and oxide grains derive from low-mass red giant and asymptotic giant branch (AGB) stars of approximately solar metallicity (Z). A small subclass of presolar O-rich grains (less than 7%) is thought to originate from stars having lower-than-solar Z. These "Group 3" [1] grains have depletions in 18O and 17O that typically fall along or above the Galactic chemical evolution (GCE) line. Other Group 3 grains show greater 17O than 18O depletions and most likely have supernova (SN) origins. Owing to their rarity, only two Group 3 silicates have been mineralogically examined in detail [2, 3]. Here we present a mineralogical study of a Group 3 presolar silicate to explore its formation conditions and interstellar history.

Nguyen, A. N.↗

The effect of zinc additions on the environmental stability of Alloy 8090 (Al-Li-Cu-Mg-Zr)

Stress corrosion cracking (SCC) remains a problem in both Al-Li and conventional Al heat treatable alloys. It has recently been found that relatively small additions (less than or approximately 1 wt-percent) of Zn can dramatically improve the SCC performance of alloy 8090 (Al-Li-Cu-Mg-Zr). Constant load time to failure experiments using cylindrical tensile samples loaded between 30 and 85 percent of TYS indicate improvements of orders of magnitude over the baseline 8090 for the Zn-containing alloys under certain aging conditions. However, the toughnesses of the alloys were noticeably degraded due to the formation of second phase particles which primarily reside on grain and subgrain boundaries. EDS revealed that these intermetallic particles were Cu and Zn rich. The particles were present in the T3 condition and were not found to be the result of quench rate, though their size and distribution were. At 5 hours at 160 C, the alloys displayed the greatest susceptibility to SCC but by 20 hours at 160 C the alloys demonstrated markedly improved TTF lifetimes. Aging past this time did not provide separable TTF results, however, the alloy toughnesses continued to worsen. Initial examination of the alloys microstructures at 5 and 20 hours indicated some changes most notably the S' and delta' distributions. A possible model by which this may occur will be explored. Polarization experiments indicated a change in the trend of E(sub BR) and passive current density at peak aging as compared to the baseline 8090. Initial pitting experiments indicated that the primary pitting mechanism in chloride environments is one occurring at constituent (Al-Fe-Cu) particles and that the Cu and Zn rich boundary precipitates posses a breakaway potential similar to that of the matrix acting neither anodic or cathodic in the first set of aerated 3.5 w/o NaCl experiments. Future work will focus on the identification of the second phase particles, evaluation of K(sub 1SCC) and plateau da/dt via both DCB and slow strain rate techniques. A lower Zn content variant will be examined in the near future in hopes of optimizing toughness, density and SCC performance.

Kilmer, Raymond J.↗

Microdosimetry and the radiation danger of cosmic rays

The radiation danger of space flights is due primarily to intensive proton fluxes accompanying solar flares and heavy multiple charged ions in galactic cosmic radiation. Evaluation of the biological effect of these kinds of rays is based on calculations of tissue dose, taking into account the formation of secondary radiation in shielding and tissue. The essential role in such calculations is played by the dependence of the factor of quality on linear energy transfer (LET) of these charged particles. Recommendations concerning the dependence of the quality factor on LET are based on radiobiological experiments carried out on many biological systems using various kinds of rays, including heavy ions with energies in the 1-10 Mev/nucleon range. Justification of the results of these experiments, as well as their extrapolation to other energies, requires development of a model description of the radiation effect of charged particles on biological microstructures.

Gunter, K.↗

Prebiotic Synthesis of Autocatalytic Products From Formaldehyde-Derived Sugars as the Carbon and Energy Source

Our research objective is to understand and model the chemical processes on the primitive Earth that generated the first autocatalytic molecules and microstructures involved in the origin of life. Our approach involves: (a) investigation of a model origin-of-life process named the Sugar Model that is based on the reaction of formaldehyde- derived sugars (trioses and tetroses) with ammonia, and (b) elucidation of the constraints imposed on the chemistry of the origin of life by the fixed energies and rates of C,H,O-organic reactions under mild aqueous conditions. Recently, we demonstrated that under mild aqueous conditions the Sugar Model process yields autocatalytic products, and generates organic micropherules (2-20 micron dia.) that exhibit budding, size uniformity, and chain formation. We also discovered that the sugar substrates of the Sugar Model are capable of reducing nitrite to ammonia under mild aqueous conditions. In addition studies done in collaboration with Sandra Pizzarrello (Arizona State University) revealed that chiral amino acids (including meteoritic isovaline) catalyze both the synthesis and specific handedness of chiral sugars. Our systematic survey of the energies and rates of reactions of C,H,O-organic substrates under mild aqueous conditions revealed several general principles (rules) that govern the direction and rate of organic reactions. These reactivity principles constrain the structure of chemical pathways used in the origin of life, and in modern and primitive metabolism.

Weber, Arthur L.↗

Undercooling and solidification behavior in the InSb-Sb system

Use of the droplet emulsion technique has been successful in studying the undercooling and crystallization behavior of Sb, InSb, and an InSb-Sb eutectic alloy. Both droplet size and imposed cooling rate were influential in controlling the extent of liquid undercooling. The droplet surface coating was of significant importance in determining the resultant solidification product structure through its effect on nucleation kinetics. The maximum undercooling for pure Sb was extended from 0.08 to 0.23 T sub m. While simple crushing techniques provided a dramatic increase in droplet undercooling over the bulk material, emulsification treatments both enhanced this undercooling and allowed successful formation of a metastable simple cubic Sb phase. This phase was stable to temperatures approaching the melting point. The simple cubic phase was detected in droplet samples processed using DTA, air and water quenching, and drop tube processing under a helium gas atmosphere. A deviation in the InSb parent ingot composition limited interpretation of the line compound results, however, emulsification techniques extended the undercooling of this material to 0.17 T sub L and provided a stable, protective surface coating for the droplets. Emulsification of the eutectic alloy was effective at producing various levels of undercooling from 0.1 to 0.2 T sub E. Microstructural examination revealed a normal-type eutectic structure in the undercooled droplets indicating that solidification occurred within the coupled zone and that this zone is somewhat symmetric about the eutectic composition.

Graves, J. A.↗

Active Oxidation of SiC

The high temperature oxidation of silicon carbide occurs in either a passive or active mode, depending on temperature and oxygen potential. Passive oxidation forms a protective oxide film which limits attack of the SiC:SiC(s) + 3/2 O2(g) = SiO2(s) + CO(g.) Active oxidation forms a volatile oxide and leads to extensive attack of the SiC: SiC(s) + O2(g) = SiO(g) + CO(g). The transition points and rates of active oxidation are a major issue. Previous studies are reviewed and the leading theories of passive/active transitions summarized. Comparisons are made to the active/passive transitions in pure Si, which are relatively well-understood. Critical questions remain about the difference between the active-to-passive transition and passive-to-active transition. For Si, Wagner [2] points out that the active-to-passive transition is governed by the criterion for a stable Si/SiO2 equilibria and the passive-to-active transition is governed by the decomposition of the SiO2 film. This suggests a significant oxygen potential difference between these two transitions and our experiments confirm this. For Si, the initial stages of active oxidation are characterized by the formation of SiO(g) and further oxidation to SiO2(s) as micron-sized rods, with a distinctive morphology. SiC shows significant differences. The active-to-passive and the passive-to-active transitions are close. The SiO2 rods only appear as the passive film breaks down. These differences are explained in terms of the reactions at the SiC/SiO2 interface. In order to understand the breakdown of the passive film, pre-oxidation experiments are conducted. These involve forming dense protective scales of 0.5, 1, and 2 microns and then subjecting the samples with these scales to a known active oxidation environment. Microstructural studies show that SiC/SiO2 interfacial reactions lead to a breakdown of the scale with a distinct morphology.

Jacobson, Nathan S.↗

Characterization of the corrosion resistance of several alloys to dilute biologically active solutions

Sulfate reducing bacteria and acid producing bacteria/fungi detected in hygiene waters increased the corrosion rate in aluminum alloy. Biologically active media enhanced the formation of pits on metal coupons. Direct observation of gas evolved at the corrosion sample, coupled with scanning electron microscopy (SEM) and energy dispersive x-ray analysis of the corrosion products indicates that the corrosion rate is increased because the presence of bacteria favor the reduction of hydrogen as the cathodic reaction through the reaction of oxygen and water. SEM verifies the presence of microbes in a biofilm on the surface of corroding samples. The bacterial consortia are associated with anodic sites on the metal surface, aggressive pitting occurs adjacent to biofilms. Many pits are associated with triple points and inclusions in the aluminum alloy microstructure. Similar bacterial colonization was found on the stainless steel samples. Fourier transform Infrared Spectroscopy confirmed the presence of carbonyl groups in pitted areas of samples exposed to biologically active waters.

Walsh, Daniel W.↗

Coupled Growth in Hypermonotectics

The overall objective of this project is to obtain a fundamental understanding of the physics controlling solidification processes in immiscible alloy systems. The investigation involves both experimentation and the development of a model describing solidification in monotectic systems. The experimental segment was designed to first demonstrate that it is possible to obtain interface stability and steady state coupled growth in hypermonotectic alloys through microgravity processing. Microgravity results obtained to date have verified this possibility. Future flights will permit experimental determination of the limits of interface stability and the influence of alloy composition and growth rate on microstructure. The objectives of the modeling segment of the investigation include prediction of the limits of interface stability, modeling of convective flow due to residual acceleration, and the influence of surface tension driven flows at the solidification interface. The study of solidification processes in immiscible alloy systems is hindered by the inherent convective flow that occurs on Earth and by the possibility of sedimentation of the higher density immiscible liquid phase. It has been shown that processing using a high thermal gradient and a low growth rate can lead to a stable macroscopically planar growth front even in hypermonotectic alloys. Processing under these growth conditions can avoid constitutional supercooling and prevent the formation of the minor immiscible liquid phase in advance of the solidification front. However, the solute depleted boundary layer that forms in advance of the solidification front is almost always less dense than the liquid away from the solidification front. As a result, convective instability is expected. Ground based testing has indicated that convection is a major problem in these alloy systems and leads to gross compositional variations along the sample and difficulties maintaining interface stability. Sustained low gravity processing conditions are necessary in order to minimize these problems and obtain solidification conditions which approach steady state.

Andrews, J. Barry↗

Coupling Carbon Oxidation and Surface Recession in Direct-Simulation Monte Carlo Code, SPARTA

Ablative thermal protection system (TPS) materials for spacecraft are composites that are often made out of carbon-based reinforcement and a polymeric matrix. They endure high-temperature oxidation and surface recession when re-entering Earth’s atmosphere. Ablation is the result of many coupled and competing thermal, mechanical, and chemical phenomena, and it is difficult to isolate the role of each on the overall degradation of the TPS. Here we develop an ablation model for material recession coupled explicitly to finite rate carbon oxidation in complex microstructures. In this work, Stochastic PArallel Rarified-gas Time-accurate Analyzer (SPARTA), a direct-simulation Monte Carlo (DSMC) code, is modified to allow oxidation-driven ablation of implicitly defined carbon surfaces. In SPARTA, implicit surfaces are generated from the grid corner point values via a marching cubes algorithm, therefore creating a new set of surface elements every time ablation is performed. The finite-rate oxidation model developed by Gopalan et. al, was adapted to tally surface reactions and other surface data on a per-grid cell basis. The ablation functionality was also adjusted so once the reactions have occurred, the number of reactions leading to CO formation can be converted to corner point reduction values; therefore, carbon removal is directly proportional to surface recession. We also develop robust algorithms which handle the evolution of the flow cells and solid material regions, including split cells (flow cell divided in two by a solid surface). Finally, we demonstrate our implicit chemistry model for 2D and 3D geometries by producing reaction statistics and detailed visualization of oxidation-induced material recession at the microscale.

V Arias↗

Redistribution of Ti and Al in deuterium charged TiAl

The redistribution of titanium and aluminum in a single-phase TiAl alloy that has been exposed to a high pressure of deuterium gas at high temperature is studied. The microstructure in the as-received, uncharged condition consisted of single-phase gamma TiAl grains and a random distribution of precipitates. Precipitates were distributed throughout the matrix and along the grain boundaries. The chemistry of the precipitates varied considerably; some were rich in Al, while other were mostly Ti with some Si and Al. The dislocation density in most grains was low, although in a few grains a high dislocation density was observed. FCC deuterides with a lattice parameter of 0.45 nm form in a Ti-52.1Al-2.1Ta (at. pct) alloy after exposure to 1.38 MPa of deuterium gas at 650 C for 213 hr. The structure and lattice parameter are consistent with the formation of Ti(l)D2. The deuterides that form in this alloy are enriched in Ti and deficient in Al and Ta compared to the deuteride-free matrix. Regions of the matrix contiguous with the deuterides have a correspondingly enhanced aluminum and tantalum concentration.

Legzdina, D.↗

FIB-NanoSIMS-TEM Coordinated Study of a Wark-Lovering Rim in a Vigarano Type A CAI

Wark-Lovering (WL) rims are thin multi layered mineral sequences that surround most Ca, Al-rich inclusions (CAIs). Unaltered WL rims are composed of the same primary high temperature minerals as CAIs, such as melilite, spinel, pyroxene, hibonite, perovskite, anorthite and olivine. It is still unclear whether the rim minerals represent a different generation formed by a separate event from their associated CAIs or are a byproduct of CAI formation. Several models have been proposed for the origins of WL rims including condensation, flashheating, reaction of a CAI with a Mg-Si-rich reservoir (nebular gas or solid); on the basis of mineralogy, abundances of trace elements, O and Mg isotopic studies. Detailed mineralogical characterizations of WL rims at micrometer to nanometer scales have been obtained by TEM observations, but so far no coordinated isotopic - mineralogical studies have been performed. Thus, we have applied an O isotopic imaging technique by NanoSIMS 50L to investigate heterogeneous distributions of O isotopic ratios in minerals within a cross section of a WL rim prepared using a focused ion beam (FIB) instrument. After the isotopic measurements, we determine the detailed mineralogy and microstructure of the same WL FIB section to gain insight into its petrogenesis. Here we present preliminary results from O isotopic and elemental maps by NanoSIMS and mineralogical analysis by FE-SEM of a FIB section of a WL rim in the Vigarano reduced CV3 chondrite.

Cai, A.↗