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105 records · Page 6

Burner rig hot corrosion of silicon carbide and silicon nitride

A number of commercially available SiC and Si3N4 materials were exposed to 1000 C for 40 h in a high-velocity, pressurized burner rig as a simulation of an aircraft turbine environment. Na impurities (2 ppm) added to the burner flame resulted in molten Na2SO4 deposition, attack of the SiC and Si3N4, and formation of substantial Na2O+x(SiO2) corrosion product. Room-temperature strength of the materials decreased as a result of the formation of corrosion pits in SiC and grain-boundary dissolution and pitting in Si3N4.

Fox, Dennis S.↗

Brine volcanism and the interior structures of asteroids and icy satellites

Brine vulcanism, in which MgSO4 and Na2SO4 are shown by carbonaceous chondrite mineralogies and elemental abundances to be the most important solutes, is presently suggested to account for the resurfacing observed on such icy satellites as Europa and Ganymede, and to have been a significant factor in the evolution of chondritic asteroids. Hypersaline brines have lower viscosities than familiar silicate lavas, although they remain more viscous than pure water; aqueous sulfate flows are seen as capable of constructing the vast, low-relief volcanic plains observed on Ganymede and Europa.

Kargel, Jeffrey S.↗

SO2-rock interaction on Io - Reaction under highly oxidizing conditions

Laboratory simulations are used here to test the possibility that interactions of SO2 and silicates can produce Na-S compounds which can account for the observed surface enrichment of Na relative to Si on Io. It is concluded that there are three viable hypotheses for the nature and origin of the Na compounds on the surface of Io: (1) Na2SO4 from SO2-silicate interactions, (2) Na-sulfides from elemental S, silicate interactions, and (3) directly erupted volcanic Na. The present studies indicate the elemental Si is not required to form Na compounds in crustal igneous interactions. Thus, the presence of Na compounds provides no constraint on elemental S but igneous formation of Na-S compounds is not tied to models of Io which contain elemental S.

Johnson, M. L.↗

NMR studies on Na+ transport in Synechococcus PCC 6311

The freshwater cyanobacterium Synechococcus PCC 6311 is able to adapt to grow after sudden exposure to salt (NaCl) stress. We have investigated the mechanism of Na+ transport in these cells during adaptation to high salinity. Na+ influx under dark aerobic conditions occurred independently of delta pH or delta psi across the cytoplasmic membrane, ATPase activity, and respiratory electron transport. These findings are consistent with the existence of Na+/monovalent anion cotransport or simultaneous Na+/H+ +anion/OH- exchange. Na+ influx was dependent on Cl-, Br-, NO3-, or NO2-. No Na+ uptake occurred after addition of NaI, NaHCO3, or Na2SO4. Na+ extrusion was absolutely dependent on delta pH and on an ATPase activity and/or on respiratory electron transport. This indicates that Na+ extrusion via Na+/H+ exchange is driven by primary H+ pumps in the cytoplasmic membrane. Cells grown for 4 days in 0.5 m NaCl medium, "salt-grown cells," differ from control cells by a lower maximum velocity of Na+ influx and by lower steady-state ratios of [Na+]in/[Na+]out. These results indicate that cells grown in high-salt medium increase their capacity to extrude Na+. During salt adaptation Na+ extrusion driven by respiratory electron transport increased from about 15 to 50%.

Non-NASA Center↗

Antarctic Mirabilite Mounds as Mars Analogs: The Lewis Cliffs Ice Tongue Revisited

It has been proposed, based on geomorphic and geochemical arguments, that subsurface water has played an important role in the history of water on the planet Mars [1]. Subsurface water, if present, could provide a protected and long lived environment for potential life. Discovery of gullies [2] and recurring slopes [3] on Mars suggest the potential for subsurface liquid water or brines. Recent attention has also focused on small (< approx. 1km dia.) mound-like geomorphic features discovered within the mid to high latitudes on the surface of Mars which may be caused by eruptions of subsurface fluids [4, 5]. We have identified massive but highly localized Na-sulfate deposits (mirabilite mounds, Na2SO4 .10H2O) that may be derived from subsurface fluids and may provide insight into the processes associated with subsurface fluids on Mars. The mounds are found on the end moraine of the Lewis Cliffs Ice Tongue (LCIT) [6] in the Transantarctic Mountains, Antarctica, and are potential terrestrial analogs for mounds observed on the martian surface. The following characteristics distinguish LCIT evaporite mounds from other evaporite mounds found in Antarctic coastal environments and/or the McMurdo Dry Valleys: (1) much greater distance from the open ocean (approx.500 km); (2) higher elevation (approx.2200 meters); and (3) colder average annual temperature (average annual temperature = -30 C for LCIT [7] vs. 20 C at sea level in the McMurdo region [8]. Furthermore, the recent detection of subsurface water ice (inferred as debris-covered glacial ice) by the Mars Reconnaissance Orbiter [9] supports the use of an Antarctic glacial environment, particularly with respect to the mirabilite deposits described in this work, as an ideal terrestrial analog for understanding the geochemistry associated with near-surface martian processes. S and O isotopic compositions.

Socki, Richard A.↗

Supercritical Water Mixture (SCWM) Experiment

The subject presentation, entitled, Supercritical Water Mixture (SCWM) Experiment, was presented at the International Space Station (ISS) Increment 33/34 Science Symposium. This presentation provides an overview of an international collaboration between NASA and CNES to study the behavior of a dilute aqueous solution of Na2SO4 (5% w) at near-critical conditions. The Supercritical Water Mixture (SCWM) investigation, serves as important precursor work for subsequent Supercritical Water Oxidation (SCWO) experiments. The SCWM investigation will be performed in DECLICs High Temperature Insert (HTI) for the purpose of studying critical fluid phenomena at high temperatures and pressures. The HTI includes a completely sealed and integrated test cell (i.e., Sample Cell Unit SCU) that will contain approximately 0.3 ml of the aqueous test solution. During the sequence of tests, scheduled to be performed in FY13, temperatures and pressures will be elevated to critical conditions (i.e., Tc = 374C and Pc = 22 MPa) in order to observe salt precipitation, precipitate agglomeration and precipitate transport in the presence of a temperature gradient without the influences of gravitational forces. This presentation provides an overview of the motivation for this work, a description of the DECLIC HTI hardware, the proposed test sequences, and a brief discussion of the scientific research objectives.

Hicks, Michael C.↗

The DECLIC Research Facility - a Fertile Platform for NASA/CNES Scientific Collaboration

The DECLIC (Device for the Study of Critical Liquids and Crystalization) Facility was launched to the International Space Station (ISS) on Shuttle flight 17-A (August 2009) and has been in service for a little over three years. Activity from the three originally planned investigations, the HTI (High Temperature Insert) investigation, the ALI (Alice Like Insert) investigation and the DSI (Directional Solidication Insert) investigation has led to fruitful collaborations among a team of scientists, sponsored by NASA and CNES, to extend the utility of the inserts and the breadth of science beyond its initial scope. These follow-on investigations plan to use inserts that have been returned to earth for refurbishment, two of which (i.e., HTI-R and DSI-R) simply entail changing the test sample and the third (i.e., ALI-R) entails a slight hardware modication to allow for precise changes in sample volume. The first investigation, the Supercritical Water Mixture (SCWM) experiment, uses the refurbished HTI-R, which will accommodate a dilute aqueous mixture of Na2SO4 -0.5% w. This investigation will extend earlier observations of pure water at near-critical conditions. The second experiment uses a modified insert, the DSI-R, with a different concentration of succinonitrile-camphor than the original flight sample. This will allow, among other objectives, a detailed study of dendritic sidebranch formation in extended three-dimensional arrays, with the goal of elucidating whether noise amplication and/or a deterministic limit cycle is the main cause of sidebranch formation. The final experiment, the ALI-R, uses a sample cell with variable density to allow for additional observations of thermo-physical properties on SF6 at near critical conditions. The presentation will provide a discussion of the DECLIC facility's hardware, its modied inserts, and an overview of the extended science that will be achieved through these collaborative activities.

Hicks, Michael C.↗

Supercritical Water Mixture (SCWM) Experiment in the High Temperature Insert-Reflight (HTI-R)

Current research on supercritical water processes on board the International Space Station (ISS) focuses on salt precipitation and transport in a test cell designed for supercritical water. This study, known as the Supercritical Water Mixture Experiment (SCWM) serves as a precursor experiment for developing a better understanding of inorganic salt precipitation and transport during supercritical water oxidation (SCWO) processes for the eventual application of this technology for waste management and resource reclamation in microgravity conditions. During typical SCWO reactions any inorganic salts present in the reactant stream will precipitate and begin to coat reactor surfaces and control mechanisms (e.g., valves) often severely impacting the systems performance. The SCWM experiment employs a Sample Cell Unit (SCU) filled with an aqueous solution of Na2SO4 0.5-w at the critical density and uses a refurbished High Temperature Insert, which was used in an earlier ISS experiment designed to study pure water at near-critical conditions. The insert, designated as the HTI-Reflight (HTI-R) will be deployed in the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on the International Space Station (ISS). Objectives of the study include measurement of the shift in critical temperature due to the presence of the inorganic salt, assessment of the predominant mode of precipitation (i.e., heterogeneously on SCU surfaces or homogeneously in the bulk fluid), determination of the salt morphology including size and shapes of particulate clusters, and the determination of the dominant mode of transport of salt particles in the presence of an imposed temperature gradient. Initial results from the ISS experiments will be presented and compared to findings from laboratory experiments on the ground.

salts↗

Alumina-Forming MAX Phases in Turbine Material Systems

Coatings for high temperature turbine components are based on low conductivity YSZ thermal barriers and protective NiAl, NiCoCrAlY bond coats. Good oxidation hot corrosion resistance, intermediate CTE, and strain tolerance of Ti2AlC and Cr2AlC MAX phases are thus of special interest. Their alumina scale growth follows a cubic law in accord with FeCrAlY alloys, with oxygen grain boundary diffusivity: Dgb 1.8 x 10-10 exp(-375 kJmole) m3s. Protective cubic kinetics are also found in high pressure burner rig (6 atm., 25 ms) and TGA tests of MAXthal 211Ti2AlC. The initial portion (0.1 hr) is dominated by fast TiO2 growth (with little evidence of scale volatility in high pressure water vapor, as found for SiO2 scales). Bulk Ti2AlC and Cr2AlC substrates show promise as potential bond coats for YSZ TBCs in 1000-1200 C furnace life (500 h) tests. Cr2AlC is proving to be very resistant to 700-900 C Na2SO4 hot corrosion and is of interest for disk alloys. Preliminary diffusion bonded Cr2AlC-superalloy hybrid couples have survived 1000 hr interrupted furnace tests at 800C with no indication of cracking or debonding. Diffusion zones of -NiAl+Cr7C3 were produced in these above 1000 C, but did not grow to any great extent after 1000 hr at 800 C. Processing as coatings presents challenges, however the basic properties of MAX phases provide novel opportunities for high temperature turbine components.

MAX phase↗

Oxidation of Alumina-Forming MAX Phases in Turbine Environments

Protective coatings for high temperature turbine components are based on YSZ thermal barriers and oxidation resistant, alumina-forming NiAl or NiCoCrAlY bond coats. Ti2AlC and Cr2AlC MAX phases are thus of special interest because of good oxidation resistance and CTE that can match Al2O3 and YSZ. Their alumina scales grow according to cubic kinetics due to grain growth in the scale, with initial heating dominated by fast TiO2 growth. Protective cubic kinetics are also found in high pressure burner rig tests of MAXthal 211 Ti2AlC, but with reduced rates due to volatile TiO(OH)2 formation in water vapor. YSZ-coatings on bulk Ti2AlC exhibit remarkable durability up to 1300C in furnace tests and at least a 25x life advantage compared to superalloys. At another extreme, Cr2AlC is resistant to low temperature Na2SO4 hot corrosion and exhibits thermal cycling stability bonded to a superalloy disk material. Accordingly, sputtered Cr2AlC coatings on disk specimens prevented hot corrosion detriments on LCF. Breakaway oxidation (Ti2AlC), scale spallation (Cr2AlC), interdiffusion, and processing as coatings still present serious challenges. However the basic properties of MAX phases provide some unusual opportunities for use in high temperature turbines.

ceramics↗

Effect of Pre- and Post-Coat Processing on the Fatigue Life of Coated Disk Alloys

Increasing temperatures in aero gas turbines is resulting in oxidation and hot corrosion attack of turbine disks. Since disks are sensitive to low cycle fatigue (LCF), any environmental attack, and especially hot corrosion pitting, can seriously degrade the life of the disk. Application of metallic coatings is one means of protecting disk alloys from this environmental attack. However, since LCF is sensitive to surface conditions, pre- and post-coat processing can have a significant effect on the LCF life of coated bars. Various pre-and post-coating conditions were examined with a Ni-45wt. Cr coating applied by High-power impulse magnetron sputtering (HiPiMS) to a Ni-based disk alloy. Initial pre-coat surface conditions examined a grit blasted surface. Later pre-coat surface treatments involved wet blasting, two shot peening levels (8N-200 and 16N-200) and a highly polished surface. Post-coat treatments involved two shot peening levels (4N-100 and 16N-200) and a post-coat diffusion anneal in high purity Ar or a low PO2 environment to encourage chromia scale formation. Half of the coated and uncoated bars were LCF tested at 760C without further environmental exposure to evaluate the pre- and post-coat treatments. The second half of samples were either oxidized for 500 hours at 760C in air, hot corroded for 50 hours at 760C in air using a Na2SO4-MgSO4 salt, or subjected to both exposures. Results of the LCF testing and post-test characterization of the various coatings will be presented and future research directions discussed.

LCF Life↗

Behavior of a Salt Water Solution Near the Critical Point Under Microgravity Conditions

The Supercritical Water Mixture (SCWM) experiment conducted on the International Space Station (ISS) is designed to study a salt-water solution in the vicinity of the critical transition with a test cell filled with Na2SO4 (aq) 0.5-w. This salt is a Type II salt which undergoes a dramatic decrease in solubility past waters critical point. The paper discusses the liquid-vapor-salt distribution in the test cell for subcritical, trans-critical, and supercritical regimes. In 0-g, the vapor-liquid interface manifests itself by the presence of a large single vapor bubble that is flattened between the two windows. In contrast with pure water, the vapor bubble remains centered in the test cell and is stable for temperatures up to Tc - 50 mK. The processes leading to critical transition during heat-up, as marked by the break-up of the vapor bubble, depends on the applied heating rate. For temperature ramps 1 mKmin, the bubble interface begins to breakup with the formation of a large number of smaller bubbles. For larger temperature ramps (10mKmin), temperature gradients arise in the cell pushing the bubble toward a window surface. As the critical threshold is crossed small variations in cell temperature ( 1 mK) cause an observable spatial variation in density. However, this spatial variation is not discernible as the temperature is increased further into the supercritical regime. The salt precipitation in the vicinity of the critical crossing appears to be heterogeneous in nature with precipitates observable on the cell windows. Direct imaging as well as light scattering indicate a hexagonal structure of the precipitated salt crystals in the near critical regime. The salt deposition is not fully reversible as the temperature is reduced due to window corrosion effects which traps some of the precipitated salt. Critical temperatures as high as 1.9 K above the value for pure water (647.25 K) have been measured. Finally, results on the critical transition phenomena in the presence of an imposed temperature gradient, demonstrating the remarkable stability of the central bubble, are also presented.

near-critical↗

The Effect of Europa and Enceladus Analog Seawater Composition on Isotopic Measurements of Volatile CO2

Science goals for icy ocean worlds missions include characterizing the chemical compositionof the surface and interior using remote sensing and in situ techniques. The next class of flightmass spectrometers for these missions will obtain compositional identifications and isotope ratiomeasurements of volatiles evolved from the ice surface (exosphere) and plumes. These massspectra will be combined with data from other flight instruments to infer the composition of theinterior from volatiles. To ensure accurate interpretation of these measurements, it is critical toverify whether the fundamental assumption that volatiles observed in icy ocean world exospheresor plumes will be a direct reflection of the sub-ice ocean. The present study evaluates whether isotopologues from an initial CO2 gas fractionate by interacting with seawater (brine) of varyingsalt composition and concentration. δ13CCO2 are affected by the pH of the brine and subsequentspeciation of {CO2}, where {CO2} represents the combination of CO2, H2CO3, HCO3-, and CO32-.{CO2} for low pH brines hypothesized for Europa will preferentially speciate as CO2. Analyzedδ13CCO2 for low pH brines are within error of the original δ13CCO2, demonstrating that volatile CO2in a low pH system will be a direct reflection of the original CO2. However, Europa’s radiativeenvironment and rapid depressurization due to plume ejection may impose fractionation effects.In contrast, high pH systems relevant to Enceladus or a more alkaline Europa are expected toform all carbonate species, while favoring speciation as HCO3-. High pH brines in theseexperiments include both an original CO2 gas and an isotopically distinct HCO3- (from NaHCO3salt). These alkaline experiments demonstrate that δ13CCO2 values are highly variable, and dependon the concentration of the dominant carbonate species, (Na)HCO3-. Mass balance estimatesindicate that measured δ13CCO2 is a thermodynamically predictable mixture of both carbonsources, suggesting that measurements of δ13C at Enceladus would directly reflect of the sourcesof CO2 and carbonate buffering in the ocean. δ18O measurements for CO2 interacting with KCland MgCl2 follow established models for δ18O-ionic strength. CO2 interacting with MgSO4,Na2SO4, and NaCl demonstrate an offset from established δ18O-ionic strength models dependingon the concentration of initial CO2. These results suggest that current predictive models for δ18Oin brines need to be resolved for changing concentrations of CO2

Ocean Worlds↗

Predicting the Seawater Chemistry of an Ocean World Using Machine Learning on Isotopic Measurements of Volatile CO2

Introduction: Given the long time intervals required for data transmission to and from ocean worlds targets, low bandwidth for data transmission, time required for data processing and analysis, and potentially extreme radiation environments (e.g., Europa), it is clear that ocean worlds missions will need more autonomous flight instruments and software in order to achieve established science goals. Protracted time intervals for data analysis (e.g., Europa Lander) strongly motivates the development of rapid, consistent and streamlined methods for interpreting data from flight mass spectrometers to e.g., determine how mass spectra from a plume or surface liquid/ice relates to the surface/subsurface. Since mass spectrometry also has the potential to correctly identify biosignatures[1], it is imperative that such methods for interpreting data are consistent and accurate. We used 848 isotope ratio mass spectra from laboratory analyses of CO2 that interacted with ocean worlds-relevant seawaters as a ‘training’ dataset for ‘unsupervised’ machine learning. In unsupervised learning, characteristics of the data are not labeled or linked, and any similarities found only result from the neural network. CO2 isotopologues analyzed for this dataset mimic the remote measurements of CO2 by a flight mass spectrometer, and are detailed in Theiling [2]. From this dataset, we used measured features of the spectra, such as retention time, intensity, and (isotopologue) mass ratios as inputs for our autoencoder neural network. Our neural network was trained to find similarities in these and other spectral features for seawaters of a particular composition and amount of initial CO2. Successful training then created an output of these similarities for various seawaters, which included MgSO4, Na2SO4, NaCl, MgCl2, KCl, and NaHCO3, and combinations of these salts. We then applied dimensionality reduction techniques such as Principal Component Analysis (PCA), T-Distributed Stochastic Neighbor Embedding (TSNE), and Uniform Manifold Approximation and Projection (UMAP) to demonstrate latent data features as a two-dimensional projection in a unitless, high-dimensional space. In this projection, a data point represents the combined effect of spectral features such as intensity, retention time, and isotope ratio. Our initial UMAP demonstrates data clustering (organization of the data by the neural network) based on the amount of CO2 that had initially interacted with each seawater. Further training using more ‘supervised’ learning techniques demonstrate strong clustering of preliminary data based on initial CO2 concentration, seawater chemical composition, and ionic strength (salinity). Our preliminary work therefore suggests that machine learning has the potential to identify compositional variants of an ocean world seawater based on mass spectra from volatile CO2 measurements. Acknowledgments: This work was funded through a Strategic Task Group at NASA Goddard Space Flight Center. The training dataset was collected through funding from the Oklahoma Space Grant Consortium. References: [1] Pappalardo, R. et al. (2013) Astrobiology, 13, 740–773. [2] Theiling (2020) Icarus, 114216.

Europa↗

Liquid Interfacial Electron Microscopy Identifies Nanogalvanic Corrosion in Pearlitic Steel

The nanoscale mechanisms of localized corrosion in low carbon steels have remained elusive due to the complexity of studying the degradative material behavior at nanoscale solid-liquid interfaces. We identified various steps in the nanogalvanic corrosion processes using in-situ liquid-cell scanning transmission electron microscopy (STEM) using a microfluidic holder by Hummingbird Scientific. Initial work, performed at low magnification, identified the initiation point on a 1018 low-carbon steel surface. This initiation point was determined to be a triple junction of two ferrite grains bridging a cementite grain in contact with a baseline electrolyte of 6 uM CO2 dissolved in a buffered (2.78 uM Na2SO4) aqueous solution, pH 6.1. The pre-etched low-carbon steel surface was prepared using focused ion beam lift-out procedures to extract a cross-section of the low-carbon steel surface, which then was thinned to about 150 nm and transferred to a SiN membrane microfluidic window. The transfer was made using a lift-out needle to attach the low-carbon steel lamella to the corner of the SiN window, and then Pt/C deposition held the lamella in contact with the window while it was released from the lift out needle. To identify the triple point on the low carbon steel lamella, prior to attachment on the SiN window, the sample was characterized for compositional variations with energy dispersive x-ray spectroscopy mapping, grain orientation and phase mapping with precession electron diffraction, and thickness mapping with energy filtered transmission electron microscopy. This pre-characterization prior to the in-situ experiment provided a map of the multiphase and multigrain structure, where the in-situ liquid cell imaging provided a clear understanding of the initiation point on the sample. These data were cross-correlated to paint a holistic picture of the triple junction site, enabling low electron-fluence in-situ snapshot imaging to avoid dominating the native corrosion reactions with effects from the incident electron beam. This initial result identified that localized, nanogalvanic corrosion at the phase interface was the dominant corrosion process in the low-carbon steel, so we next targeted the observation of an array of these nanogalvanic features phase boundaries in a pearlite grain. Near-surface ferrite/cementite phase interfaces that typify pearlitic low-carbon steel were extracted, pre-characterized, and imaged for the in-situ corrosion processes. The sample was a cross-section from a pearlite grain, with alternating ferrite and cementite grains that extended microns down from the pre-etched low-carbon steel pipe surface. After contact with a buffered aqueous solution, the phase boundaries between the ferrite and cementite began to dissolve, with observable material loss and thickness changes in the dark-field and bright-field STEM images. Within minutes, the corrosion front proceeded deeper into the material, claiming a thin layer of ferrite around all exposed phase boundaries before progressing laterally into the ferrite matrix, converting the ferrite to corrosion product normal to each buried cementite grain. Formation of the corrosion product causes a volumetric expansion, creating a lateral wedging force that mechanically ejects the cementite grains from their grooves and leaves behind percolation channels into the steel substructure. Rapid and deleterious, this nanogalvanic corrosion pathway represents an important target for understanding and preventing run-away degradation in this common building material. Observation of this corrosion mechanism was enabled by the combination of pre-characterization using standard structural, grain, and compositional analysis in the TEM, which provides maps for understanding the reaction propagation captured in low-dose, in-situ, liquid-cell STEM.

corrosion↗