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Microstructure Evolution and Durability of Advanced Environmental Barrier Coating Systems for SiC/SiC Ceramic Matrix Composites

Environmental barrier coated SiC-SiC ceramic matrix composites (CMCs) systems will play a crucial role in next generation turbine engines for hot-section component applications because of their ability to significantly increase engine operating temperatures with improved efficiency, reduce engine weight and cooling requirements. Advanced HfO2 and rare earth silicate environmental barrier coatings (EBCs), along with multicomponent hafnium and rare earth silicide EBC bond coats have been developed. The coating degradation mechanisms in the laboratory simulated engine thermal cycling, and fatigue-creep operating environments are also being investigated. This paper will focus on the microstructural and compositional evolutions of an advanced environmental barrier coating system on a SiC-SiC CMC substrate during the high temperature simulated durability tests, by using a Field Emission Gun Scanning Electron Microscopy, Energy Dispersive Spectroscopy (EDS) and Wavelength Dispersive Spectroscopy (WDS). The effects of Calcium-Magnesium-Alumino-Silicate (CMAS) from road sand or volcano-ash deposits on the degradation mechanisms of the environmental barrier coating systems will also be discussed. The detailed analysis results help understand the EBC-CMC system performance, aiming at the durability improvements to achieve more robust, prime-reliant environmental barrier coatings.

ceramic matrix composites↗

Laboratory Investigation of the Effect of Venusian Weathering on Mineral Spectra

Introduction: The recent selection of two missions to Venus has renewed the importance of deter-mining weathering reactions between minerals and the Venusian atmosphere, and the spectral signatures of minerals before, during, and after these reactions. The rate at which weathering reactions progress also constrain show long unstable minerals will be present on the surface (e.g., [1]), and enables the use of mineralogy as a constraint on surface age(e.g., [2-3]).In order to gain an understanding of how mineral compositions and spectra change with weathering, we have begun conducting experiments in a 1 atm experimental setup at Wesleyan University. This setup exposes minerals to the temperature and most abundant gases of the Venus atmosphere (CO2, SO2, N2).We conducted initial experiments using biotite, calcite, and montmorillonite in order to test our methodology with minerals that may be relevant to recording the history of water on Venus. Methods: Experiments were conducted in Thermo Fisher Scientific Lindberg/Blue M Mini-Mite horizontal tube furnaces at Wesleyan University. Experiments used natural mineral chips and powders, and were conducted at 1 atmosphere and 460 °C under pre-mixed gases provided by Air Gas(Table 1). The furnaces are set up in a flow through configuration so that solid samples are exposed to a fixed gas composition, and quartz glass process tubes were used in all experiments (1/4” diameter for experiment V4, ½” diameter for all others). These conditions were maintained for the du-rations listed in Table 1, at which point the furnace was turned off with gas flowing until the sample was cool enough to extract under N2and be placed in a desiccator for storage. Run products were carbon coated and examined using a Hitachi SU5000 Field Emission Gun Scanning Electron Microscope (SEM) equipped with an EDAX Octane Pro EDS detector located at Wesley-an University. Visible-Near Infrared Spectroscopy (VNIR) analysis was performed on powdered samples under a nitrogen atmosphere using an ASD Fieldspec Proover the 350-2500 nm range. Powdered mineral samples were milled to a particle size of < 45μm and were spiked with an internal standard (Al2O3, corundum) to obtain quantitative mineralogy. Samples were analyzed using a Panalytical X’Pert pro X-ray Diffractometer (XRD), with an X’Celerator high speed detector and Co Kα radiation, with data collected at a step size of 0.02 ̊/minute step counting rate from 2 to 80 degrees 2θ at 45 mA/40kV in the X-ray Diffraction Laboratory located at NASA Johnson Space Center. Materials Data Inc (MDI) software suite, JadeTMv9 was used for Rietveld refinement to determine phase abundances and mineral identification by comparing XRD patterns to International Center for Diffraction Data (ICDD) database patterns. Table 1: Experimental matrix. Experiment Name Duration (Days)Gas Com-position (trace gas)MineralsV487SO2/N2(1.4%)Montmorillonite, biotiteV519SO2/N2(1.4%)CalciteV619CO2/SO2/N2(1.4% SO2, 2.1% N2)Montmorillonite, biotiteV828SO2/N2(1.4%)Biotite, calcite Results: Calcite. In both experiments, calcite was exposed to the SO2/N2gas mixture, and in both experimental run products, XRD analysis detected anhydrite, which is consistent with EDS measurements conducted in the SEM. The XRD analyses show greater amounts of anhydrite present after 28 days than 19, suggesting the calcite reaction progressed further given longer duration. Grain surface morphology as seen in the SEM also shows secondary mineral growth (Fig. 1). VNIR spectra show no change, as expected since anhydrite lacks spectral features in this wavelength range. Montmorillonite. Montmorillonite was exposed to two different gas mixtures, the SO2/N2mix and CO2/SO2/N2mix over different durations (87 and 19 days, respectively). VNIR analyses of both run products show a reduction in the 1441and1910 nm water features as well as a shift of the 1411 and 2011 nm features to shorter wavelengths that may indicate re-structuring in the crystal lattice and the production of amorphous phases [4]. XRD results are consistent with this, showing a shift of the 001 peak from 15Åto 10Åin both run products. The amount of X-ray amorphous material in the montmorillonite run products was greater than that present in the unreacted clay, being the greatest in the 87 day V4 experiment. No other secondary phases were detected in the run products, however sulfur was present in EDS analyses of powder samples.

A R Santos↗

Olivine Compositional Variation of Asteroid Ryugu Samples: Possible Precursors of Ryugu’s Parent Asteroid

JAXA’s Hayabusa2 spacecraft successfully recovered samples from Cb-type asteroid Ryugu and returned samples are now under detailed scrutiny by the international community. The ongoing initial analysis has so far revealed that the Ryugu samples are pristine primitive asteroidal materials mostly composed of secondary minerals such asphyllosilicates, carbonates, Fe sulfides and magnetite associated with organic matter [e.g., 1]. However, some samples contain small amounts of anhydrous silicates and oxides such as olivine that are thought to be the precursors of the Ryugu parent asteroid. Their sizes are mostly <5 mm, and detailed mineralogical analysis is possible using an electron microprobe with field emission gun (FE-EPMA). Here we report results of our extensive FE-EPMA analysis of an hydrous minerals focusing on olivine to compare with literature chondritic data. We also performed synchrotron XRD of olivine crystals to evaluate the shock degree of Ryugu samples. These analyses allow us to discuss the formation of Ryugu in light of the solar system early evolution.

T Mikouchi↗

The Zircon-Reidite Shock Transformation: A Tem Study of Reidite Produced at A Newly Established 21.2 GPa Shock Pressure Threshold

The high-pressure polymorph of zircon (Zr2SiO4) is reidite, a phase with the scheelite structure that was first discovered to form at ca. 12 GPa in static high-pressure experiments [1]. Reidite was subsequently found to occur in naturally shocked zircons from several terrestrial impact localities [2,3], as well as in shock recovery-reverberation experiments performed above 20 GPa [4]. The nature and distribution of reidite occurrences in terrestrial impact localities has pointed to its potential use as a shock pressure indicator, as well as to the importance of understanding its age-reset effects in zircon geochronology [3]. In this study we have used coordinated SEM/Electron Backscatter Diffraction (EBSD) and Field-Emission Scanning Transmission Electron Microscopy (FE-STEM) to study the micro- and nanostructure of reidite and its shocked zircon host produced at 21.2 GPa under experimental shock recovery/reverberation conditions [5]. Our results document the TEM microstructure of reidite formed at a 21.2 GPa experimental shock pressure that is significantly lower than that observed in previous studies [4]. At these conditions the sample developed a diverse set of microstructures that have not been previously documented on the TEM scale.

shock metamorphism↗

Hypervelocity Dust Impact in Olivine: Fib/Tem Characterization and Comparison of Experimental and Natural Microcraters

The flux of objects impacting the surfaces of solar system airless bodies is dominated by micrometeoroids less than 1 mm diameter whose impact effects play a major role in the space weathering of airless body surfaces. To obtain better understanding of how small scale impact effects vary as a function of impact speed in an important lunar and asteroidal mineral, we produced artificial microcraters in San Carlos olivine using Fe metal dust particles 0.10 to 5 µm in diameter electrostatically accelerated to speeds between 0.35 to 25 km s-1. The crater morphologies, size distrrubiton and microstruc-tures were characterized by field-emission SEM (FE-SEM) and also by FIB cross sectioning of selected craters for field-emission scanning transmission electron microscopy (FE-STEM). These same techniques were also applied to study a natural 20 µm-diameter microcrater in a olivine grain on the surface of lunar rock 12075. Measured microcrater diameters in the experimental sample range between 0.20 to 5 µm with larger craters having more irregular outlines dominated by spallation fractures. FE-SEM and FE-STEM imaging docu-ment the formation of shock melt in the size population of experimental craters below approximately 1 µm in diameter, corresponding to particle impact speeds in the 10-25 km s-1 range. The natural olivine crater exhibits similar shock melt features along the perimeter of its cavity, but the shock melt also contains nanophase Fe metal particles, something not observed in the experimental samples. FE-STEM imaging of the experimental craters reveals complex shock-generated dislocation and nanofracture microstructures in zones extend-ing 1-2 µm into the olivine from the crater cavity. The natural microcrater shows a lower density of shock-generated disloca-tions that extends a factor of 2 deeper into the the olivine than in the experimental samples.

Roy Gray Christoffersen↗

Testing the DC-electric field model in a solar flare observed by Yohkoh and the Compton Gamma-Ray Observatory

We apply a DC-electric field model to the analysis of soft and hard X-ray observations of a solar flare observed by Yohkoh and the Compton Gamma Ray Observatory (CGRO) on 6 September 1992. The flare was observed simultaneously in the soft X-ray Ca XIX line by the Yohkoh Bragg Crystal Spectrometer (BCS) and in hard X-rays (greater than 50 keV) by the CGRO Burst and Transient Spectrometer Experiment (BATSE). A strong stationary component of Ca XIX emission was present at the start of impulsive hard X-ray emission indicating an extended phase of heating prior to the production of energetic nonthermal electrons. We interpret the preflare Ca XIX emission as a signature of Joule heating by field-aligned currents. We relate the temporal variation of impulsive hard X-ray emission to the rate of runaway electron acceleration by the DC-electric field associated with the current. We find that the initial rise in hard X-ray emission is consistent with electron acceleration by a DC-electric field that increased from a preflare value of less than approximately 10(exp -5) V/cm to approximately (9 +/- 1) x 10(exp -5) V/cm at the time of the first hard X-ray peak and then remained constant during the rest of the impulsive phase. We attribute the increase in electric field strength to the formation of a current sheet at the reconnection point of two loop structures. The decrease in hard X-ray emission after flare maximum is consistent with a reduction in the number of runaway electrons due to an increase in coronal density produced by chromospheric evaporation. The increased density quenches the runaway process by enhancing collisional thermalization of electrons. To avoid the generation of an unrealistically large magnetic field, the flaring region must be highly filamented into greater than approximately 10(exp 6) oppositely directed current channels of approximately 30 cm width with an initial preflare current of approximately 3 x 10(exp 10) A per channel.

Zarro, D. M.↗

Plasma waves associated with diffuse auroral electrons at mid-altitudes

Using simultaneous observations from the DE-1 High-Altitude Plasma Instrument and the Plasma Wave Instrument, a study is made of 28 auroral-zone crossings, equally divided among dayside and nightside cases covering a range of Kp values from 1- to 8. In the diffuse auroral region, electrostatic emissions of frequencies up to a few kHz are associated with low-energy field-aligned electron beams. Of 18 cases (11 nightside; 7 dayside) examined at high resolution in the particle data, 15 (9 nightside; 6 dayside) exhibited field-aligned beams with electrostatic waves. In most cases, the beams were upward-directed, but occasionally they traveled both up and down the field line. The electrostatic emissions are interpreted as electron-acoustic waves excited by the field-aligned beams.

Sharber, J. R.↗

Diamond-Coated Carbon Nanotubes for Efficient Field Emission

Field-emission cathodes containing arrays of carbon nanotubes coated with diamond or diamondlike carbon (DLC) are undergoing development. Multiwalled carbon nanotubes have been shown to perform well as electron field emitters. The idea underlying the present development is that by coating carbon nanotubes with wideband- gap materials like diamond or DLC, one could reduce effective work functions, thereby reducing threshold electric-field levels for field emission of electrons and, hence, improving cathode performance. To demonstrate feasibility, experimental cathodes were fabricated by (1) covering metal bases with carbon nanotubes bound to the bases by an electrically conductive binder and (2) coating the nanotubes, variously, with diamond or DLC by plasma-assisted chemical vapor deposition. In tests, the threshold electric-field levels for emission of electrons were reduced by as much as 40 percent, relative to those of uncoated- nanotube cathodes. Coating with diamond or DLC could also make field emission-cathodes operate more stably by helping to prevent evaporation of carbon from nanotubes in the event of overheating of the cathodes. Cathodes of this type are expected to be useful principally as electron sources for cathode-ray tubes and flat-panel displays.

Dimitrijevic, Stevan↗

Some recent observations and interpretation of the Jupiter decimeter emission

The decimetric emission consists partly of thermal radiation from the planetary disk and partly of nonthermal radiation from a region of larger angular extent and is thought to result from synchrotron emission by relativistic electrons in the magnetic field. Four topics relating to the decimetric emission are discussed. (1) A comparison is made of maps giving detailed brightness contours. One was obtained for epoch 1963.8 and was at a wavelength of 10.4 cm. The second was for epoch 1967.2 at 21.3 cm. (2) Interferometric data at 21.1 cm taken in April 1968 and May 1979 indicate that the emission centroid is fixed in Jupiter and rotates with it. (3) Circular polarization observations are described and are used to obtain a surface magnetic field strength at the equator between 3.2 and 15.2 gauss. (4) An upper limit on the Faraday rotation is used to set an upper limit on the density of thermal electrons surrounding Jupiter, and uncertainties in the results are discussed.

Berge, G. L.↗

Laboratory Instruments Available to Support Space Station Researchers at Marshall Space Flight Center

A number of research instruments are available at NASA's Marshall Space Flight Center (MSFC) to support ISS researchers and their investigations. These modern analytical tools yield valuable and sometimes new informative resulting from sample characterization. Instruments include modern scanning electron microscopes equipped with field emission guns providing analytical capabilities that include angstron-level image resolution of dry, wet and biological samples. These microscopes are also equipped with silicon drift X-ray detectors (SDD) for fast yet precise analytical mapping of phases, as well as electron back-scattered diffraction (EBSD) units to map grain orientations in crystalline alloys. Sample chambers admit large samples, provide variable pressures for wet samples, and quantitative analysis software to determine phase relations. Advances in solid-state electronics have also facilitated improvements for surface chemical analysis that are successfully employed to analyze metallic materials and alloys, ceramics, slags, and organic polymers. Another analytical capability at MSFC is a mganetic sector Secondary Ion Mass Spectroscopy (SIMS) that quantitatively determines and maps light elements such as hydrogen, lithium, and boron along with their isotopes, identifies and quantifies very low level impurities even at parts per billion (ppb) levels. Still other methods available at MSFC include X-ray photo-electron spectroscopy (XPS) that can determine oxidation states of elements as well as identify polymers and measure film thicknesses on coated materials, Scanning Auger electron spectroscopy (SAM) which combines surface sensitivity, spatial lateral resolution (approximately 20 nm), and depth profiling capabilities to describe elemental compositions in near surface regions and even the chemical state of analyzed atoms. Conventional Transmission Electron Microscope (TEM) for observing internal microstructures at very high magnifications and the Electron Probe Micro-analyzer (EPMA) for very precise microanalysis are available as needed by the researcher. Space Station researchers are invited to work with MSFC in analyzing their samples using these techniques.

Panda, Binayak↗

Study of the Effects of the Electric Field on Charging Measurements on Individual Micron-size Dust Grains by Secondary Electron Emissions

The dust charging by electron impact is an important dust charging process in Astrophysical, Planetary, and the Lunar environments. Low energy electrons are reflected or stick to the grains charging the dust grains negatively. At sufficiently high energies electrons penetrate the grain leading to excitation and emission of electrons referred to as secondary electron emission (SEE). Available theoretical models for the calculation of SEE yield applicable for neutral, planar or bulk surfaces are generally based on Sternglass Equation. However, viable models for charging of individual dust grains do not exist at the present time. Therefore, the SEE yields have to be obtained by some experimental methods at the present time. We have conducted experimental studies on charging of individual micron size dust grains in simulated space environments using an electrodynamic balance (EDB) facility at NASA-MSFC. The results of our extensive laboratory study of charging of individual micron-size dust grains by low energy electron impact indicate that the SEE by electron impact is a very complex process expected to be substantially different from the bulk materials. It was found that the incident electrons may lead to positive or negative charging of dust grains depending upon the grain size, surface potential, electron energy, electron flux, grain composition, and configuration. In this paper we give a more elaborate discussion about the possible effects of the AC field in the EDB on dust charging measurements by comparing the secondary electron emission time-period (tau (sub em) (s/e)) with the time-period (tau (sub ac) (ms)) of the AC field cycle in the EDB that we have briefly addressed in our previous publication.

Tankosic, D.↗

Stable dielectric charge distributions from field enhancement of secondary mission

The emission of secondary electrons from dielectrics subject to numerous effects of electric field which are experimentally difficult to control is discussed. Measurements are reported using pulse techniques such that local fields do not build to significant levels, but measurements with fields present are also of interest. A specific series of measurements under controlled conditions are described and their implications in terms of fields, magnitude and angle, near the dielectric surface were examined. The measurements were made for a charged fluorinated-ethylene-propylene surface near a grounded aluminum half-round resting on the surface. The geometry produced a stable surface-charge gradient being controlled by a strongly enhanced secondary emission for which a model is constructed. Observations of surface flashovers under various conditions confirm the predictions of some scaling exercises.

Robinson, J. W.↗

Coordinated Mineralogical and Isotopic Analysis of a Cosmic Symplectite Identified in a Stardust Terminal Particle

Comet Wild-2 samples returned by the Stardust spacecraft contain a chemically diverse mixture of material, underscoring the complex nature of comets. Studies of entire Stardust aerogel tracks afford the opportunity to examine the fine-grained particle fragments distributed along the length of the track as well as the terminal particles. Previous TEM characterization of a terminal particle (TP) in track #147 revealed a symplectically intergrown iron sulfide and oxide assemblage. Mineralogically similar assemblages, known as cosmic symplectites (COS, formerly termed "new-PCP"), have only been identified in the primitive carbonaceous chondrite Acfer 094. Meteoritic COS have isotopically heavy O compositions (delta (sup 17), O-18 = 180per mille) that point to interactions with early solar system primordial water. In this study we report mineralogical and O isotopic measurements of the Wild-2 COS assemblage. Experimental: Track #147 is a "bulbous"-type track (4600 microns long) containing 7 terminal particles. The TPs were removed from the track, embedded in epoxy, and ultramicrotomed. A JEOL 2500SE 200 keV field-emission scanning-transmission electron microscope was used to obtain quantitative elemental maps and detailed mineralogical characterization. Following TEM analysis, two thin sections of TP4 (12 microns) were analyzed for O isotopes by raster ion imaging with the JSC NanoSIMS 50L. All three O isotopes were measured simultaneously using electron multipliers. San Carlos olivine grains were used as isotopic standards. Results and Discussion: The COS in the Wild-2 track #147 TP4 sample consists of symplectically intergrown pentlandite and nanocrystalline maghemite which coexists with high-Ca pyroxene with Na and Cr (kosmochlor component). This kosmochlor component could have a nebular origin and be precursors to type II chondrules in ordinary chondrites. Yet pentlandite is not a stable phase in the nebula. The COS in Acfer 094 also consists of pentlandite, but contains magnetite [4] rather than the more oxidized maghemite observed in the Wild-2 COS. The Acfer 094 COS display heavy O isotopic compositions that are the result of sulfidization and oxidation of Fe, Ni-metal grains and sulfides by O-17- and O-18-rich water in the solar nebula or possibly on the parent body. The O isotopic composition of the Wild-2 COS, however, is indistinguishable from terrestrial, indicating it was not altered by the same primordial aqueous reservoir as the Acfer 094 COS. The alteration could have occurred on the parent body by isotopically equilibrated ice. The mineralogy and petrography of Wild-2 samples suggests an incomplete or nascent hydration process. In future work we will analyze S isotopes in the track #147 TP4 COS and search for additional COS in Stardust samples.

Nguyen, A. N.↗

Space Weathering of Olivine in Lunar Soils: A Comparison to Itokawa Regolith Samples

Regolith particles from airless bodies preserve a record of the space weathering processes that occurred during their surface exposure history. These processes have major implications for interpreting remote-sensing data from airless bodies. Solar wind irradiation effects occur in the rims of exposed grains, and impact processes result in the accumulation of vapordeposited elements and other surface-adhering materials. The grains returned from the surface of Itokawa by the Hayabusa mission allow the space weathering "style" of a chondritic, asteroidal "soil" to be compared to the lunar case. Here, we present new studies of space-weathered olivine grains from lunar soils, and compare these results to olivine grains from Itokawa. Samples and Methods: We analyzed microtome thin sections of olivine grains from the 20-45 micron fractions of three lunar soils: 71061, 71501 and 10084 (immature, submature and mature, respectively). Imaging and analytical data were obtained using a JEOL 2500SE 200kV field-emission scanning-transmission electron microscope equipped with a thin-window energy-dispersive x-ray spectrometer. Similar analyses were obtained from three Hayabusa olivine grains. Results and Discussion: We observed lunar grains showing a range of solar flare track densities (from <10(exp 9) to approx.10(exp 12)/sq cm). The lunar olivines all show disordered, highly strained, nanocrystalline rims up to 150-nm thick. The disordered rim thickness is positively correlated with solar flare track density. All of the disordered rims are overlain by a Si-rich amorphous layer, ranging up to 50-nm thick, enriched in elements that are not derived from the host olivine (e.g., Ca, Al, and Ti). The outmost layer represents impact-generated vapor deposits typically observed on other lunar soil grains. The Hayabusa olivine grains show track densities <10(exp 10)/sq cm and display disordered rims 50- to 100-nm thick. The track densities are intermediate to those observed in olivines in immature and submature lunar soils and indicate surface exposures of approx. 10(exp 5) years. The outermost few nanometers of the disordered rims on Hayabusa olivines are more Si-rich and Mg- and Fe-depleted relative to the cores of the grains and likely represent a minor accumulation of impact-generated vapors or sputter deposits. Nanophase Fe metal particles are less abundant in the Hayabusa rims compared to the rims on lunar grains. Conclusions: The Hayabusa and lunar olivine grain rims have widths and microstructures consistent with formation from atomic displacement damage from solar wind ions. The space weathering features in the Hayabusa grains are similar to those observed in olivines from immature to submature lunar soils. A major difference, however, is that the Hayabusa grains appear to lack the hypervelocity impact products (melt spherules, thick vapor deposits, and abundant nanophase Fe metal particles) that are common in lunar soil grains with a similar exposure history.

Keller, L. P.↗

A phenomenological model describing orificed, hollow cathode operation

A phenomenological model is presented which describes the emission processes occurring within the orificed, hollow cathode. The model defines a region of ion production inside the cathode and assumes that the cathode emission current can be accounted for by considering the ion and electron currents which cross the boundary of this region. Most of the current (approximately 72%) comes from electrons produced by field-enhanced, thermionic emission from a well-defined emission surface at the downstream end of the insert which circumscribes the ion product region. The electrons produced at the emission surface feed the ionization process in the region of ion production; the rest of the current (approximately 28%) is carried by the ions produced in the process. Moving at the Bohm velocity, these ions leave the production volume; they then complete the current path by being collected at various cathode potential surfaces, including the emission surface. The model establishes the ratio of ion to electron currents at the emission surface on the basis of the energy balance at that surface. Experimental results corroborating the principal assumptions of the model are presented and discussed.

Siegfried, D. E.↗

Microwave emission from the coronae of late-type dwarf stars

VLA microwave observations of 14 late-type dwarf and subgiant stars and binary systems are examined. In this extensive set of observations, four sources at 6 cm (Chi-1 Ori, UV Cet, YY Gem, and Wolf 630AB) were detected and low upper limits for the remaining stars were found. The microwave luminosities of the nondetected F-K dwarfs are as small as 0.01 those of the dMe stars. The detected emission is slowly variable in all cases and is consistent with gyroresonant emission from thermal electrons spiraling in magnetic fields of about 300 gauss if the source sizes are as large as R/R(asterisk) = 3-4. This would correspond to magnetic fields that are probably in the range 0.001-0.0001 gauss at the photospheric level. An alternative mechanism is gyrosynchrotron emission from a relatively small number of electrons with effective temperature.

Linsky, J. L.↗