Search NASA⌕ Search

SEARCH · Search NASA

Results for “Silicate Earth”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2

Liquidus Phases of the Richardson H5 Chondrite at High Pressures and Temperatures

Part of early mantle evolution may include a magma ocean, where core formation began before the proto-Earth reached half of its present radius. Temperatures were high and bombardment and accretion were still occurring, suggesting that the proto-Earth consisted of a core and an at least partially liquid mantle, the magma ocean. As the Earth accreted, pressure near the core increased and the magma ocean decreased in volume and became shallower as it began to cool and solidify. As crystals settled, or floated, the composition of the magma ocean could change significantly and begin to crystallize different minerals from the residual liquid. Therefore, the mantle may be stratified following the P-T phase diagram for the bulk silicate Earth. To understand mantle evolution, it is necessary to know liquidus phase relations at high pressures and temperatures. In order to model the evolution of the magma ocean, high pressure and temperature experiments have been conducted to simulate the crystallization process using a range of materials that most likely resemble the bulk composition of the early Earth.

Channon, M.↗

Thermodynamics and Kinetics of Silicate Vaporization

Silicates are a common class of materials that are often exposed to high temperatures. The behavior of these materials needs to be understood for applications as high temperature coatings in material science as well as the constituents of lava for geological considerations. The vaporization behavior of these materials is an important aspect of their high temperature behavior and it also provides fundamental thermodynamic data. The application of Knudsen effusion mass spectrometry (KEMS) to silicates is discussed. There are several special considerations for silicates. The first is selection of an appropriate cell material, which is either nearly inert or has well-understood interactions with the silicate. The second consideration is proper measurement of the low vapor pressures. This can be circumvented by using a reducing agent to boost the vapor pressure without changing the solid composition or by working at very high temperatures. The third consideration deals with kinetic barriers to vaporization. The measurement of these barriers, as encompassed in a vaporization coefficient, is discussed. Current measured data of rare earth silicates for high temperature coating applications are discussed. In addition, data on magnesium-iron-silicates (olivine) are presented and discussed.

thermodynamics↗

Rubidium and cesium in the earth and the moon

The purpose of the study is to provide an alternative perspective on both the mass balance issue and on the issue of secular change in the Rb-Cs ratio in the earth mantle. In particular, it is argued that the apparent secular change in the Rb/Cs ratio may be simply an artifact of alteration of older rocks through weathering and/or metamorphism subsequent to formation. It is also shown that there is not necessarily a need for a hidden, undepleted reservoir, and the consistency of this result with other mass calculations is explored. New methods for estimating the Rb/Cs ratio of the bulk silicate earth are suggested.

Jones, John H.↗

Development of Refractory Silicate-YSZ Dual Layer TBCs

Development of advanced thermal barrier coatings (TBCs) is the most promising approach for increasing the efficiency and performance of gas turbine engines by enhancing the temperature capability of hot section metallic components. Spallation of the yttria-stabilized zirconia (YSZ) top coat, induced by the oxidation of the bond coat coupled with the thermal expansion mismatch strain, is considered to be the ultimate failure mode for current state-of-the-art TBCS. Enhanced oxidation resistance of TBCs can be achieved by reducing the oxygen conductance of TBCs below that of thermally grown oxide (TGO) alumina scale. One approach is incorporating an oxygen barrier having an oxygen conductance lower than that of alumina scale. Mullite, rare earth silicates and glass ceramics have been selected as potential candidates for the oxygen barrier. This paper presents the results of cyclic oxidation studies of oxygen barrier/YSZ dual layer TBCs.

He, Yirong↗

Varying Processing Parameters in the Development of Slurry-Based Oxide Bond Coat for Environmental Barrier Coatings

Silicon carbide (SiC)-based ceramic matrix composites (CMCs) are replacing nickel-base superalloys in some hot-section aircraft engine materials due to their lower density and higher working temperature. CMCs require an environmental barrier coating (EBC) for protection from corrosive combustion species. Current-generation EBCs consist of a rare earth silicate topcoat and a silicon bond coat; however, the relatively low melting point of silicon (1414°C) limits the upper use temperature of these coatings. To extend the capability of next-generation EBCs, an oxide-based bond coat capable of withstanding temperatures of up to 1480°C has been developed at NASA Glenn Research Center. In this study, the oxide-based bond coat was applied to monolithic SiC via a slurry coating process. Parameters including slurry particle size and viscosity were varied, and coating performance was evaluated after steam cycling at 1480°C. The effect of including different rare earth constituents in the bond coat was also explored.

R. I. Webster↗

Corrosion resistant thermal barrier coating

A thermal barrier coating system for protecting metal surfaces at high temperature in normally corrosive environments is described. The thermal barrier coating system includes a metal alloy bond coating, the alloy containing nickel, cobalt, iron, or a combination of these metals. The system further includes a corrosion resistant thermal barrier oxide coating containing at least one alkaline earth silicate. The preferred oxides are calcium silicate, barium silicate, magnesium silicate, or combinations of these silicates.

Levine, S. R.↗

Solidus and liquidus temperatures and mineralogies for anhydrous garnet-lherzolite to 15 GPa

Strong convergence is noted, in experimental data for systems pertaining to anhydrous fertile garnet-lherzolite in the 6.5-15 GPa range, either to a common temperature or to temperatures differing by only about 100 C. The major element composition of magmas generated by even minor degrees of partial melting may be similar to the composition of the primordial, bulk silicate earth in an upper mantle stratigraphic column more than 160 km deep. Whether or not the solidus and liquidus intersect, the liquidus mineralogy for undepleted garnet-lherzolite compositions is found to change from olivine, at low pressures, to pyroxene, garnet, or a solid solution of both, at pressures greater than 10-15 GPa.

Herzberg, C. T.↗

Environmental Barrier Coatings for Turbine Engines: A Design and Performance Perspective

Ceramic thermal and environmental barrier coatings (TEBC) for SiC-based ceramics will play an increasingly important role in future gas turbine engines because of their ability to effectively protect the engine components and further raise engine temperatures. However, the coating long-term durability remains a major concern with the ever-increasing temperature, strength and stability requirements in engine high heat-flux combustion environments, especially for highly-loaded rotating turbine components. Advanced TEBC systems, including nano-composite based HfO2-aluminosilicate and rare earth silicate coatings are being developed and tested for higher temperature capable SiC/SiC ceramic matrix composite (CMC) turbine blade applications. This paper will emphasize coating composite and multilayer design approach and the resulting performance and durability in simulated engine high heat-flux, high stress and high pressure combustion environments. The advances in the environmental barrier coating development showed promise for future rotating CMC blade applications.

Zhu, Dongming↗

Mass Spectrometric Studies of Oxides

Current studies at NASA Glenn on oxide thermodynamics are discussed. Previous studies on the vaporization of B2O3 in reducing atmospheres led to inconsistent studies when B was used as a reductant. It is shown that liquid B2O3 does not wet B and a clear phase separation was noted in the Knudsen cell. This problem was solved by using FeB and Fe2B to supply a different and constant activity of B. The thermodynamic data thus derived are compared to quantum chemical composite calculations. A major problem in high temperature mass spectrometry is the determination of accurate ionization cross sections, particularly for molecules. The method of Deutsch and Mark shows promise and some sample calculations are discussed. Finally current studies on the thermodynamics of rare earth silicates are discussed. Here the problems are obtaining a measurable signal from SiO2 vaporization and non-equilibrium vaporization. The use of a Ta reducing agent provides a stronger signal, which is related to silica activity. The Whitman-Motzfeld relation adapted to KEMS measurements is applied to obtain equilibrium pressures.

Jacobson, Nathan S.↗

Kinetic Monte Carlo Simulation of Oxygen Diffusion in Ytterbium Disilicate

Silicon-based ceramic components for next-generation jet turbine engines offer potential weight savings, as well as higher operating temperatures, both of which lead to increased efficiency and lower fuel costs. Silicon carbide (SiC), in particular, offers low density, good strength at high temperatures, and good oxidation resistance in dry air. However, reaction of SiC with high-temperature water vapor, as found in the hot section of jet turbine engines in operation, can cause rapid surface recession, which limits the lifetime of such components. Environmental Barrier Coatings (EBCs) are therefore needed if long component lifetime is to be achieved. Rare earth silicates such as Yb2Si2O7 and Yb2SiO5 have been proposed for such applications; in an effort to better understand diffusion in such materials, we have performed kinetic Monte Carlo (kMC) simulations of oxygen diffusion in Ytterbium disilicate, Yb2- Si2O7. The diffusive process is assumed to take place via the thermally activated hopping of oxygen atoms among oxygen vacancy sites or among interstitial sites. Migration barrier energies are computed using density functional theory (DFT).

Computer Simulation↗

A Synthesis of Experimental Data Describing the Partitioning of Moderately Volatile Elements in Major Rock Forming Minerals: Implications for the Moon

Highly volatile elements [condensation temperatures below about 700 K] and water are highly informative about lunar bulk composition (hence origin), differentiation and magmatic evolution, and the role of impacts in delivering volatiles to the Moon. Fractionation of volatile elements compared to moderately volatile and refractory elements are informative about high-temperature conditions that operated in the proto-lunar disk. Existing data show clearly that the Moon is depleted in volatile elements compared to the bulk silicate Earth. For example, K/Th is ~400-700 in the Moon compared to 2800-3000 in Earth. A complicating factor is that the abundances of the highly volatile elements in major lunar lithologies vary by approximately two orders of magnitude. Perhaps most interesting, H2O is not correlated with the concentration of volatile elements, indicating a decoupling of highly volatile elements from the even more volatile H2O. We contend that this decoupling could be a significant tracer of processes operating during lunar formation, differentiation, and bombardment, and the combination of analyzing both volatile elements and water is likely to provide significant insight into lunar geochemical history. This variation and lack of correlation raises the question: what were the relative contributions of crystallization in the magma ocean, subsequent mantle overturn, production of secondary magmas, and addition of volatiles by large impacts in producing this apparently large range in volatile abundances? This current study will produce new partitioning data relevant to the role and distribution of the volatile and non-volatile, yet geochemically significant elements (Co, Ni, Zn, Se, Rb, Sr, Mo, Ag, Cd, In, Sb, Ce, Yb, Tl, Pb, Bi) during the thermal and magmatic evolution of the Moon.

Vander Kaaden, Kathleen E.↗

Environmental Barrier Coatings for Ceramic Matrix Composites - An Overview

Ceramic Matrix Composites (CMCs) are increasingly being considered as structural materials for advanced power generation equipment. Broadly speaking the two classes of materials are oxide-based CMCs and non-oxide based CMCs. The non-oxide CMCs are primarily silicon-based. Under conditions prevalent in the gas turbine hot section the water vapor formed in the combustion of gaseous or liquid hydrocarbons reacts with the surface-SiO2 to form volatile products. Progressive surface recession of the SiC-SiC CMC component, strength loss as a result of wall thinning and chemical changes in the component occur, which leads to the loss of structural integrity and mechanical strength and becomes life limiting to the equipment in service. The solutions pursued to improve the life of SiC-SiC CMCs include the incorporation of an external barrier coating to provide surface protection to the CMC substrate. The coating system has become known as an Environmental Barrier Coating (EBC). The relevant early coatings work was focused on coatings for corrosion protection of silicon-based monolithic ceramics operating under severely corrosive conditions. The development of EBCs for gas turbine hot section components was built on the early work for silicon-based monolithics. The first generation EBC is a three-layer coating, which in its simplest configuration consists of a silicon (Si) base coat applied on top of the CMC, a barium-strontium-aluminosilicate (BSAS) surface coat resistant to water vapor attack, and a mullite-based intermediate coating layer between the Si base coat and BSAS top coat. This system can be represented as Si-Mullite-BSAS. While this baseline EBC presented a significant improvement over the uncoated SiC-SiC CMC, for the very long durations of 3-4 years or more expected for industrial operation further improvements in coating durability are desirable. Also, for very demanding applications with higher component temperatures but shorter service lives more rugged EBCs will be necessary. A second generation of EBCs incorporates rare earth silicates which have extremely favorable resistance against environmental attack and a higher temperature capability. Performance data for this class of EBCs is more limited and especially field data are not as extensive as for the first generation EBCs. Extensive laboratory, rig and engine testing, including testing of EBC coated SiC-SiC CMCs in actual field applications is in progress. The development of next generation EBCs with even higher temperature capability than the second generation EBC is also underway. This paper will discuss the current status of EBC technology and future direction based on literature survey.

Laboratory↗

Ag Isotopic Evolution of the Mantle During Accretion: New Constraints from Pd and Ag Metal-Silicate Partitioning

Decay of (sup 107) Pd to (sup 107) Ag has a half-life of 6.5 times 10 (sup 6) mega-annums. Because these elements are siderophile but also volatile, they offer potential constraints on the timing of core formation as well as volatile addition. Initial modelling has shown that the Ag isotopic composition of the bulk silicate Earth (BSE) can be explained if accretion occurs with late volatile addition. These arguments were tested for sensitivity for pre-cursor Pd/Ag contents, and for a fixed Pd/Ag ratio of the BSE of 0.1. New Ag and Pd partitioning data has allowed a better understanding of the partitioning behavior of Pd and Ag during core formation. The effects of S, C and Si, and the effect of high temperature and pressure has been evaluated. We can now calculate D(Ag) and D(Pd) over the wide range of PT conditions and variable metallic liquid compositions that are known during accretion. We then use this new partitioning information to revisit the Ag isotopic composition of the BSE during accretion.

Righter, K.↗

Performance and Durability of Advanced Environmental Barrier Coating Systems

This paper summarizes recent NASA environmental barrier coating (EBC) material advances for protecting the SiC/SiC Ceramic Matrix Composites (CMCs) for meeting next generation turbine engine performance requirements. We particularly present an advanced multicomponent rare earth silicate EBCs with HfO2-Si bond coat system, the temperature capability, environmental stability, and thermomechanical durability, advanced laboratory testing toward subelement demonstrations. Fundamental coating properties of the coating system will also be discussed, with the emphasis on the coating diffusion barrier performance and Calcium Magnesium Alumino-Silicate (CMAS) resistance.

Zhu, Dongming↗

Durability of YSZ Coated Ti2AlC in 1300 °C Mach 0.3 Burner Rig Tests

A thermal barrier coating system survived burner rig testing at 1300 °C for 500 h. A 160 µm thick yttria stabilized zirconia (YSZ) coating was applied to a Ti2AlC MAX phase bar sample by plasma spray physical vapor deposition (PS-PVD) and tested face-on in an atmospheric Mach 0.3 jet fuel burner, using 5-h thermal cycles. No thermal barrier coating (TBC) spallation or recession was observed, only a 2.4 mg/cm2 mass gain. The modest weight gain precluded severe volatility losses under high velocity burner conditions. The coating surface exhibited colonies of (111)flourite fiber-textured columns separated by craze patterns, with no visible moisture attack. The metastable tetragonal t' YSZ phase was obtained initially, transitioning to equilibrium teq and cubic YSZ, but with little detrimental monoclinic. The thickness of the alumina TGO was ~21 to 23 μm under the heated YSZ face and ~13 to 15 μm on the uncoated, cooler backside. The backside exhibited removal of initial transient TiO2 nodules and partial etching of the underlying Al2O3 scale by volatile hydroxides formed in high temperature, high velocity water vapor. Aerodynamic forces produced some bending of the cantilevered sample via creep. The test indicated exceptional stability of YSZ coatings on Ti2AlC under turbine conditions, with thermal expansion matching playing a key role. The purpose of this study was to demonstrate long term durability of YSZ/MAX phase system in aggressive high temperature burner rig testing. MAX phases have been keenly studied because of their unique crystal structure and intriguing properties (Refs. 1 and 2). Having Mn+1(Al,Si)(C,N)n general composition, they are defined as ceramics, but possess unusual desirable attributes such as high conductivity, thermal shock resistance, easy machinability, and deformation tolerance. The mechanical properties derive from weak M-(Al,Si) bonding in the basal plane that leads to sliding and kinking in preference to catastrophic crack growth. Like most ceramics they are phase stable at high temperatures, generally up to 1500 °C. High temperature oxidation resistance is excellent for alumina-forming Ti3AlC2, Ti2AlC, and Cr2AlC, as reviewed by Tallman, et al. (Ref. 3). Compatibility with α-Al2O3 scales is further enhanced in cyclic exposures by a close matching of thermal expansion coefficients, (Ref. 4) i.e., (~9.3, 10.2, 11.3×10–6/K for Al2O3, Ti2AlC, and YSZ, to be discussed). Turbine environments generally contain 10 percent water vapor in the combustion gases, therefore moisture effects can be a concern for some materials (Ref. 5). Furnace tests of MAX phases in high temperature steam generally showed little effect on Al2O3 scale growth (Ref. 6). However, high velocity and high pressure gas can influence scale losses by the formation of volatile reaction products, such as TiO(OH)2 and Al(OH)3 (Refs. 7 to 10). This phenomenon had been discussed for 1100 to 1300 °C high pressure burner rig tests of Ti2AlC (Ref. 11). A single cubic growth rate parameter kcubic was measurably lower than comparable furnace TGA data, but it could be matched reasonably well if corrected for a slight volatility term. In general, a two-parameter cubic-linear growth-volatility law was believed to apply. Corresponding scale volatility loss rates, directly measured at 1300 °C on a pre-oxidized sample, were moderate (0.012 mg/cm2/h) and largely attributed to removal of the initial TiO2 transient scale. A related CH4 burner study of high purity Cr2AlC MAX phase demonstrated 1200 °C durability after 500 rapid (5 min. heat and 2 min. cool) thermal shock cycling (29 h hot time) (Ref. 12). Heating and cooling rates were ~1000 and 500 °C per minute, with a gas velocity of 5 m/s, producing a 75 °C/mm gradient. A 7 μm Al2O3 surface scale and a 13 μm Cr7C3 depletion zone formed with no signs of failure. No evidence of scale volatility was evident, although weight change was not provided, the velocity was moderate, and the total hot time was not extensive. The same high gradient BRT was used to produce 1400 °C surface temperatures for a YSZ/Cr2AlC/IN738 system in the first study of MAX phases used as bond coats for thermal barrier coatings (TBC) (Ref. 25). Here TBC failure was reported after 745 cycles, with only a 1.5 μm Al2O3 scale entrained within a porous, Cr7C3 bondcoat depletion phase. YSZ thermal barrier coatings have been considered to be a compatible complement to Al-MAX phases because of thermal expansion matching and extremely low volatility in water vapor. Initial studies showed superior oxidative stability up to 1300 °C, for long times (at least 500 h) for Ti2AlC substrates and less (268 h) for Cr2AlC, while withstanding large alumina TGO scale thickness (~35 to 40 μm) (Refs. 13 and 14). By comparison, typical superalloy systems can only survive 1150 °C maximum interface temperatures for extended periods, with a maximum sustained TGO below 10 μm (Ref. 15). High temperature SiC based systems are known to form slow-growing SiO2 scales. But these are subject to rate enhancement and volatile Si(OH)4 products in the presence of water vapor, as described comprehensively by Opila, et al. (Refs. 5, 16 to 19). Net weight losses are generally observed in high velocity, high pressure burner rig studies (e.g., 0.084 mg/cm2/h at 1300 °C) (Ref. 20). Furthermore, the loss rates have been shown from chemical physics to scale with v1/2 and pH2O 2 (Ref. 16). Low activity, moisture-resistant environmental barrier coatings (EBC), such as rare earth silicates, are needed to prevent substrate recession under turbine conditions (Refs. 21 to 23).

Smialek, James L.↗

Calcium Isotope Constraints on Recycled Carbonates in Subduction-related Magmas

Calcium isotope ratios are readily mass-fractionated by low-temperature depositional processes that can be recorded in sedimentary rocks and, therefore, have the potential to track distinct geochemical signatures of recycled materials in mantle-derived igneous rocks. In this study, I report calcium isotopic compositions for well-characterized lavas from the Central American volcanic arc that exhibit a range of trace element and radiogenic isotope signatures that have been used to indicate variable amounts of subducted marine carbonate and hemipelagic sedimentary rocks, fresh carbonatite lavas from Oldoinyo Lengai Volcano, Tanzania, and an intrusive carbonatite clast erupted 12.8 ka from the Laacher See Volcano, Germany. I observed no calcium isotope evidence for recycled sedimentary rocks in the Central American arc magmas or in the Oldoinyo Lengai carbonatite volcanic rocks. They all exhibit isotopic compositions similar to rocks dominated by a primitive, mantle-like, bulk silicate Earth (BSE) composition. The exception in this work is the calcium isotope composition measured in the intrusive Laacher See carbonatite that is resolvable from BSE (δ^44 Ca = 0.0). Although this calcium isotopic signature might be related to ancient carbonate recycling, the magnitude and relatively light calcium isotopic composition (δ^44 Ca = –0.4) of this carbonatite could also reflect an origin that involved partial melting of altered lithospheric mantle, from which isotopically heavy Ca-bearing fluids have been lost. The decoupled signatures between trace elements and their radiogenic isotopes and those recorded by calcium isotope data are important because they likely reflect different sources and processes, and demonstrate that sediment subduction is not a bulk mixing process.

Ca isotopes↗

The Zn, S, and Cl Isotope Compositions of Mare Basalts: Implications for the Effects of Eruption Style and Pressure on Volatile Element Stable Isotope Fractionation on the Moon

We compare the stable isotope compositions of Zn, S, and Cl for Apollo mare basalts to better constrain the sources and timescales of lunar volatile loss. Mare basalts have broadly elevated yet limited ranges in δ(66)Zn, δ(34)S, and δ(37)Cl_(SBC+WSC) values of 1.27 ± 0.71, 0.55 ± 0.18, and 4.1 ± 4.0‰, respectively, compared to the silicate Earth at 0.15, –1.28, and 0‰, respectively. We find that the Zn, S, and Cl isotope compositions are similar between the low- and high-Ti mare basalts, providing evidence of a geochemical signature in the mare basalt source region that is inherited from lunar formation and magma ocean crystallization. The uniformity of these compositions implies mixing following mantle overturn, as well as minimal changes associated with subsequent mare magmatism. Degassing of mare magmas and lavas did not contribute to the large variations in Zn, S, and Cl isotope compositions found in some lunar materials (i.e., 15‰ in δ(66)Zn, 60‰ in δ(34)S, and 30‰ in δ(37)Cl). This reflects magma sources that experienced minimal volatile loss due to high confining pressures that generally exceeded their equilibrium saturation pressures. Alternatively, these data indicate effective isotopic fractionation factors were near unity. Our observations of S isotope compositions in mare basalts contrast to those for picritic glasses (Saal and Hauri 2021), which vary widely in S isotope compositions from –14.0 to 1.3‰, explained by extensive degassing of picritic magmas under high-P/P_(Sat) values (>0.9) during pyroclastic eruptions. The difference in the isotope compositions of picritic glass beads and mare basalts may result from differences in effusive (mare) and explosive (picritic) eruption styles, wherein the high-gas contents necessary for magma fragmentation would result in large effective isotopic fractionation factors during degassing of picritic magmas. Additionally, in highly vesiculated basalts, the δ(34)S and δ(37)Cl values of apatite grains are higher and more variable than the corresponding bulk-rock values. The large isotopic range in the vesiculated samples is explained by late-stage low-pressure “vacuum” degassing (P/P-(Sat) ~ 0) of mare lavas wherein vesicle formation and apatite crystallization took place post-eruption. Bulk-rock mare basalts were seemingly unaffected by vacuum degassing. Degassing of mare lavas only became important in the final stages of crystallization recorded in apatite—potentially facilitated by cracks/fractures in the crystallizing flow. We conclude that samples with wide-ranging volatile element isotope compositions are likely explained by localized processes, which do not represent the bulk Moon.

Halogens↗

Knudsen Effusion Mass Spectrometry: Principles and Applications

Knudsen Effusion Mass Spectrometry (KEMS) is a well-established technique in physical chemistry. First, we discuss the basic principles of the technique. It is based on a small enclosure which sets up a condensed/vapor near equilibria. A small, well-defined orifice allows the vapor to be sampled a mass spectrometer. Although the number of groups utilizing this method has decrease significantly from its height in 1960s, we will show that it is still useful for many problems in physical chemistry, materials science, geology, and nuclear science. Specific examples illustrate its versatility: Measurement of the enthalpy of formation of HfO(g); measurement of activities in the Ti-Al-O and Ni-Al systems; measurement of activities in several rare earth silicate systems; measurement of vapor pressures above olivine; dating of minerals with K/Ar method; and determination of adsorption/desorption behavior on nuclear fission products on graphite. These are only a small sampling of the many applications of this versatile technique.

Mass spectrometry, thermodynamics, high temperatur↗