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At least 19 records

Factors influencing organic carbon preservation in marine sediments

The organic matter that escapes decomposition is buried and preserved in marine sediments, with much debate as to whether the amount depends on bottom-water O2 concentration. One group argues that decomposition is more efficient with O2, and hence, organic carbon will be preferentially oxidized in its presence, and preserved in its absence. Another group argues that the kinetics of organic matter decomposition are similar in the presence and absence of O2, and there should be no influence of O2 on preservation. A compilation of carbon preservation shows that both groups are right, depending on the circumstances of deposition. At high rates of deposition, such as near continental margins, little difference in preservation is found with varying bottom-water O2. It is important that most carbon in these sediments decomposes by anaerobic pathways regardless of bottom-water O2. Hence, little influence of bottom-water O2 on preservation would, in fact, be expected. As sedimentation rate drops, sediments deposited under oxygenated bottom water become progressively more aerobic, while euxinic sediments remain anaerobic. Under these circumstances, the relative efficiencies of aerobic and anaerobic decomposition could affect preservation. Indeed, enhanced preservation is observed in low-O2 and euxinic environments. To explore in detail the factors contributing to this enhanced carbon preservation, aspects of the biochemistries of the aerobic and anaerobic process are reviewed. Other potential influences on preservation are also explored. Finally, a new model for organic carbon decomposition, the "pseudo-G" model, is developed. This model couples the degradation of refractory organic matter to the overall metabolic activity of the sediment, and has consequences for carbon preservation due to the mixing together of labile and refractory organic matter by bioturbation.

Non-NASA Center↗

Thermochemical Interactions of Yttria-Stabilized Zirconia and Molten Lunar Regolith Simulants

Oxygen produced from lunar resources through in-situ resource utilization (ISRU) is critical to maintaining a permanent human presence on the lunar surface. Molten regolith electrolysis and carbothermal reduction are two promising ISRU techniques for generating oxygen directly from lunar regolith, which is primarily a mixture of oxide minerals; however, both processes require operating temperatures of 1600C to melt lunar regolith and dissociate the molten oxides. These conditions limit the use of many oxide refractory materials, such as Al2O3 and MgO, due to rapid degradation resulting from reactions between the refractory materials and molten lunar regolith. Yttria-stabilized zirconia (YSZ) is a promising refractory oxide to provide containment of molten regolith while demonstrating limited reactivity. This work focuses on corrosion studies of YSZ powders and dense YSZ crucibles in contact with molten lunar mare and highlands regolith simulants at 1600C. The interactions between YSZ and molten regolith are characterized using SEM/EDS, XRD, and EBSD with an emphasis on elemental and microstructural analysis to assess reactivity and degradation of YSZ. Due to lunar regolith’s similar composition to calcium-magnesium-aluminosilicates (CMAS) and YSZ’s usage as a thermal barrier coating, these interactions can serve to inform YSZ/CMAS behavior by simulating cases of elevated CMAS/YSZ ratios and for higher than intended gas turbine temperatures.

Kevin Yu↗

Thermochemical Interactions Between Yttria-Stabilized Zirconia and Molten Lunar Regolith Simulants

Oxygen produced through in-situ resource utilization (ISRU) is critical to maintaining a permanent human presence on the lunar surface. Molten regolith electrolysis and carbothermal reduction are two promising ISRU techniques for generating oxygen directly from lunar regolith, which is primarily a mixture of oxide minerals; however, both processes require operating temperatures of 1600 C to melt lunar regolith and dissociate the molten oxides. These conditions limit the use of many oxide refractory materials, such as Al2O3 and MgO, due to rapid degradation resulting from reactions between the refractory materials and molten lunar regolith. Yttria-stabilized zirconia (YSZ) is shown here to be a promising refractory oxide to provide containment of molten regolith while demonstrating limited reactivity. This work focuses on corrosion studies of YSZ powders and dense YSZ crucibles in contact with molten lunar maria and highlands regolith simulants at 1600 C. The interactions between YSZ and molten regolith are characterized using SEM/EDS, XRD, and EBSD. A FactSage thermochemical model is created to compare with the experimental results. These combined analyses suggest that lunar maria regolith will degrade YSZ faster than lunar highlands regolith due to the lower viscosity of the maria regolith. The feasibility of long-term molten regolith containment with YSZ is discussed based on the YSZ powder and crucible results.

Kevin Yu↗

High temperature barrier coatings for refractory metals

Improvements in high temperature oxidation resistant metal coating technology will allow NASA and commercial entities to develop competitive civil space transport and communication systems. The success of investigations completed in this program will have a positive impact on broadening the technology base for high temperature materials. The work reported herein describes processes and procedures for successfully depositing coherent oxidation barrier coatings on refractory metals to prevent degradation under very severe operating environments. Application of the new technology developed is now being utilized in numerous Phase 3 applications through several prominent aerospace firms. Major achievements have included: (1) development of means to deposit thick platinum and rhodium coatings with lower stress and fewer microcracks than could be previously achieved; (2) development of processes to deposit thick adherent coatings of platinum group metals on refractory substrates that remain bonded through high temperature excursions and without need for intermediate coatings (bonding processes unique to specific refractory metals and alloys have been defined; (3) demonstration that useful alloys of refractory and platinum coatings can be made through thermal diffusion means; (4) demonstration that selected barrier coatings on refractory substrates can withstand severe oxidizing environments in the range of 1260 deg and 1760 deg C for long time periods essential to the life requirements of the hardware; and (5) successful application of the processes and procedures to prototype hardware. The results of these studies have been instrumental in improved thermal oxidation barrier coatings for the NASP propulsion system. Other Phase 3 applications currently being exploited include small uncooled thrusters for spacecraft and microsatellite maneuvering systems.

Malone, G. A.↗

Biphase Metal Electrodes For AMTEC

New biphase metal electrodes for alkali metal thermoelectric converter (AMETEC) exhibit low electrical resistance, fast alkali metal transport, and good power densities and lifetime at operating temperatures from 1,100 to 1,160 K. Electrodes expected to last as long as 10,000 h in service without significant degradation. Made of two refractory metals, one forms strong bonds with sodium, other inert to sodium.

Williams, R.↗

Materials interactions between the thermoelectric converter and the 5kwe reactor system

The integration of a compact thermoelectric converter with a 5-kwe reactor system is described. Material interaction uncertainties study is also presented. This includes degradation of the required austenitic - refractory metal transition joint during operation at high temperatures; loss of corrosion resistance; embrittlement by the presence of hydrogen; and loss of design margin by transport of interstitial elements. Analysis and limited experimental evidence indicate that these potential materials interactions can be adequately controlled. Group 5-2 refractory metals can be utilized without unacceptable adverse effect on system reliability.

Ferry, P. B.↗

ALMA Mapping of Rapid Gas and Dust Variations in Comet C/2012 S1 (ISON): New Insights into the Origin of Cometary HNC

Observations of the sungrazing comet C/2012 S1 (ISON) were carried out using the Atacama Large Millimeter/submillimeter Array at a heliocentric distance of 0.58-0.54 AU (Astronomical Units) (pre-perihelion) on 2013 November 16-17. Temporally resolved measurements of the coma distributions of HNC, CH3OH, H2CO, and dust were obtained over the course of about an hour on each day. During the period UT 10:10-11:00 on November 16, the comet displayed a remarkable drop in activity, manifested as a greater than 42 percent decline in the molecular line and continuum fluxes. The H2CO observations are consistent with an abrupt, approximately 50 percent reduction in the cometary gas production rate soon after the start of our observations. On November 17, the total observed fluxes remained relatively constant during a similar period, but strong variations in the morphology of the HNC distribution were detected as a function of time, indicative of a clumpy, intermittent outflow for this species. Our observations suggest that at least part of the detected HNC originated from degradation of nitrogen-rich organic refractory material, released intermittently from confined regions of the nucleus. By contrast, the distributions of CH3OH and H2CO during the November 17 observations were relatively uniform, consistent with isotropic outflow and stable activity levels for these species. These results highlight a large degree of variability in the production of gas and dust from comet ISON during its pre-perihelion outburst, consistent with repeated disruption of the nucleus interspersed with periods of relative quiescence.

techniques: interferometric↗

Alkali metal-refractory metal biphase electrode for AMTEC

An electrode having increased output with slower degradation is formed of a film applied to a beta-alumina solid electrolyte (BASE). The film comprises a refractory first metal M.sup.1 such as a platinum group metal, suitably platinum or rhodium, capable of forming a liquid or a strong surface adsorption phase with sodium at the operating temperature of an alkali metal thermoelectric converter (AMTEC) and a second refractory metal insoluble in sodium or the NaM.sup.1 liquid phase such as a Group IVB, VB or VIB metal, suitably tungsten, molybdenum, tantalum or niobium. The liquid phase or surface film provides fast transport through the electrode while the insoluble refractory metal provides a structural matrix for the electrode during operation. A trilayer structure that is stable and not subject to deadhesion comprises a first, thin layer of tungsten, an intermediate co-deposited layer of tungsten-platinum and a thin surface layer of platinum.

Williams, Roger M.↗

Degradation of Yttria-Stabilized Zirconia in Molten Regolith Electrolysis Applications

The generation of oxygen from lunar resources is an enabling technology to support a sustained human presence on the lunar surface. Molten regolith electrolysis is a promising process for directly electrolyzing lunar regolith, which is primarily a mixture of oxide minerals. During electrolysis, metallic products (Fe, Si) are formed at the cathode and oxygen is produced at the anode. In order to perform electrolysis, the regolith must be molten to enable ionic transport of metallic cations and oxygen anions, requiring an operating temperature of 1600C. Common refractory oxide materials, such as Al2O3 and MgO, undergo rapid degradation due to the high operating temperature and contact with the corrosive molten regolith. This work investigates yttria-stabilized zirconia (YSZ) for molten regolith electrolysis applications. Corrosion studies are presented to elucidate the degradation mechanism of YSZ powders and crucibles exposed to lunar regolith simulants at 1600C. Two regolith simulants are used to represent regolith from the lunar maria (JSC-1A) and the lunar highlands (LHS-1). Degradation of YSZ in contact with regolith simulants is evaluated using SEM/EDS, XRD, and EBSD. Furthermore, a modified molten regolith electrolysis reactor is presented utilizing YSZ at the anode to enable facile collection of oxygen produced during electrolysis.

Kevin Yu↗

Materials degradation in low earth orbit (LEO); Proceedings of the Symposium, 119th Annual Meeting of the Minerals, Metals, and Materials Society, Anaheim, CA, Feb. 17-22, 1990

The current understanding of the effect of space environment on materials and the development of protective coatings is examined in reviews and reports. Consideration is given to hyperthermal atomic oxygen reactions, the effect of atomic oxygen on altered and coated Kapton surfaces for spacecraft applications in LEO, silicon dioxide space coatings studied ellipsometrically, atomic oxygen effects on spacecraft materials, atomic oxygen beam source for erosion simulation, and atomic oxygen effects on refractory materials. Particular attention is given to ellipsometric analysis of materials degradation in space, studies of the interaction of 8 km/s oxygen atoms with selected materials, characterization and calibration of the EOIM-III flight mass spectrometer in a high velocity oxygen atom beam, the reaction efficiency of thermal energy oxygen atoms with polymeric materials, and effects of simulated space environments on the properties of selected materials.

Srinivasan, V.↗

Research on rechargeable oxygen electrodes.

A research program is described which consisted of studying the effects of electrode cycling in very pure KOH solutions, with and without controlled additions of impurities, on oxide formation, oxygen evolution kinetics, oxygen reduction kinetics (including hydrogen peroxide formation), and changes in electrode structure. Bright platinum, platinized platinum, and Teflon-bonded platinum black electrodes were studied. Three main problem areas are identified: the buildup of a refractory anodic layer on prolonged cycling, which leads to a degradation of performance; the dissolution and subsequent deposition of dendritic platinum in the separator, leading to short-circuit ing and loss of electrocatalyst; and the disruptive effect of bubbling during gas evolution on charge. Each of these problem areas is analyzed, and remedial solutions are proposed.

Giner, J.↗

Refractory Materials for Flame Deflector Protection

Fondu Fyre (FF) is currently the only refractory material qualified for use in the flame trench at KSC's Shuttle Launch Pads 39A and 3913. However, the material is not used as it was qualified and has undergone increasingly frequent and severe degradation due to the launch blasts. This degradation is costly as well as dangerous for launch infrastructure, crew and vehicle. The launch environment at KSC is unique. The refractory material is subject to the normal seacoast environment, is completely saturated with water before launch, and is subjected to vibrations and aggressive heat/blast conditions during launch. This report presents results comparing two alternate materials, Ultra-Tek FS gun mix and Kruzite GR Plus, with Fondu Fyre. The materials were subjected to bulk density, porosity, compression strength, modulus of rupture and thermal shock tests. In addition, test specimens were exposed to conditions meant to simulate the launch environment at KSC to help better understand how the materials will perform once installed.

Calle, Luz M.↗

Commercial off-the-Shelf (COTS) Refractory Material Evaluation

Fondu Fyre (FF) is currently the only refractory material qualified for use in the flame trench at KSC's Shuttle Launch Pads 39A and 39B. However, the material is not used as it was qualified and has undergone increasingly frequent and severe degradation due to the launch blasts. This degradation is costly as well as dangerous for launch infrastructure, crew and vehicle. FF is applied at the pad via the gunnite process, where wetted refractory material is sprayed onto a steel grid mounted on a support structure. The water content in this process can be manually adjusted by operators, causing distinct visual and physical discrepancies among repair areas. Since the application process is unlikely to change for new refractory materials, it is important to understand the effects of water content on commercial off-the-shelf (COTS) refractory materials. The purpose of this study was to evaluate the performance of the FF with respect to various water contents as well as heat treatments, to simulate aging and exposure to the blast. Initial results indicated that different water contents and heat treatments result in distinct differences in crushing strength, apparent porosity and bulk density. However, water content became an insignificant factor in both crush strength and porosity when FF was cured to at least 1500 deg. Additionally, inspection of the material's surface microstructure by scanning electron microscopy indicated distinguishable characteristics for different heat treatment levels. Results from this study will help guide future studies on the development and identification of new refractory materials.

Calle, Luz Marina↗

Influence of molybdenum on the creep properties of nickel-base superalloy single crystals

The Mo content of an alloy series based on Ni-6 wt pct Al-6 wt pct Ta was systematically varied from 9.8 to 14.6 wt pct, in order to ascertain the influence of Mo on the creep properties of single crystals. The optimum initial gamma-gamma prime microstructure for raft development and creep strength was established in each alloy before testing. It was found that, as the Mo content increased from 9.8 to 14.0 percent, the magnitude of the lattice mismatch increased; upon reaching 14.6 percent, a degradation of mechanical properties occurred due to the precipitation of a third phase. These results suggest that small refractory metal content and initial gamma-prime variations can profoundly affect mechanical properties.

Mackay, R. A.↗

Improved method of producing oxide-dispersion-strengthened alloys

Dispersion strengthened alloys having the required properties are produced by a process in which the refractory particles are less than 100 to 500 A thick. These are fine enough to ensure the strength characteristics without appreciable degradation of other characteristics. The alloy consists of a matrix metal and a dispersoid metal.

Grant, N. J.↗

Inorganic composites for space applications

The development of inorganic composite materials for space applications is reviewed. The composites do not contain any organic materials, and therefore, are not subject to degradation by ultraviolet radiation, volatilization of constituents, or embrittlement at low temperatures. The composites consist of glass, glass/ceramics or ceramic matrices, reinforced by refractory whiskers or fibers. Such composites have the low thermal expansion, refractories, chemical stability and other desirable properties usually associated with the matrix materials. The composites also have a degree of toughness which is extraordinary for refractory inorganic materials.

Malmendier, J. W.↗

Plasma-Sprayed Refractory Oxide Coatings on Silicon-Base Ceramics

Silicon-base ceramics are promising candidate materials for high temperature structural applications such as heat exchangers, gas turbines and advanced internal combustion engines. Composites based on these materials are leading candidates for combustor materials for HSCT gas turbine engines. These materials possess a combination of excellent physical and mechanical properties at high temperatures, for example, high strength, high toughness, high thermal shock resistance, high thermal conductivity, light weight and excellent oxidation resistance. However, environmental durability can be significantly reduced in certain conditions such as when molten salts, H2 or water vapor are present. The oxidation resistance of silicon-base materials is provided by SiO2 protective layer. Molten salt reacts with SiO2 and forms a mixture of SiO2 and liquid silicate at temperatures above 800C. Oxygen diffuses more easily through the chemically altered layer, resulting in a catastrophic degradation of the substrate. SiC and Si3N4 are not stable in pure H2 and decompose to silicon and gaseous species such as CH4, SiH, SiH4, N2, and NH3. Water vapor is known to slightly increase the oxidation rate of SiC and Si3N4. Refractory oxides such as alumina, yttria-stabilized zirconia, yttria and mullite (3Al2O3.2SiO2) possess excellent environmental durability in harsh conditions mentioned above. Therefore, refractory oxide coatings on silicon-base ceramics can substantially improve the environmental durability of these materials by acting as a chemical reaction barrier. These oxide coatings can also serve as a thermal barrier. The purpose of this research program has been to develop refractory oxide chemical/thermal barrier coatings on silicon-base ceramics to provide extended temperature range and lifetime to these materials in harsh environments.

Tewari, Surendra↗

Hot Hydrogen Testing of Refractory Metals and Ceramics

The objective of this investigation is to develop a technique with which refractory metal carbide samples can be exposed to hydrogen containing gases at high temperatures, and to use various microstructural and analytical techniques to determine the chemical and rate processes involved in hydrogen degradation in these materials. Five types of carbides were examined including WC, NbC, HfC, ZrC, and TaC. The ceramics were purchased and were all monolithic in nature. The temperature range investigated was from 850 to 1600 C with a hydrogen pressure of one atmosphere. Control experiments, in vacuum, were also conducted for comparison so that the net effects due to hydrogen could be isolated. The samples were analyzed prior to and after exposure. Gas samples were collected in selected experiments and analyzed using gas chromography. Characterization of the resulting microstructure after exposure to hydrogen was conducted using optical microscopy, x-ray diffraction, scanning electron microscopy, and weight change. The ceramics were purchased and were all monolithic in nature. It was found that all samples lost weight after exposure, both in hydrogen and vacuum. Results from the microstructure analyses show that the degradation processes are different among the five types of ceramics involved. In addition, the apparent activation energy for the degradation process is a function of temperature even within the same material. This indicates that there are more than one mechanism involved in each material, and that the mechanisms are temperature dependent.

Zee, Ralph↗