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All sourcesNASA NTRSDOE OSTI
NASA NTRS2014

The Development of HfO2-Rare Earth Based Oxide Materials and Barrier Coatings for Thermal Protection Systems

Advanced hafnia-rare earth oxides, rare earth aluminates and silicates have been developed for thermal environmental barrier systems for aerospace propulsion engine and thermal protection applications. The high temperature stability, low thermal conductivity, excellent oxidation resistance and mechanical properties of these oxide material systems make them attractive and potentially viable for thermal protection systems. This paper will focus on the development of the high performance and high temperature capable ZrO2HfO2-rare earth based alloy and compound oxide materials, processed as protective coating systems using state-or-the-art processing techniques. The emphasis has been in particular placed on assessing their temperature capability, stability and suitability for advanced space vehicle entry thermal protection systems. Fundamental thermophysical and thermomechanical properties of the material systems have been investigated at high temperatures. Laser high-heat-flux testing has also been developed to validate the material systems, and demonstrating durability under space entry high heat flux conditions.

Ceramic Matrix Composites↗
NASA NTRS2017

Development of Advanced Environmental Barrier Coatings for SiC/SiC Ceramic Matrix Composites: Path Toward 2700 F Temperature Capability and Beyond

Advanced environmental barrier coating systems for SiC-SiC Ceramic Matrix Composite (CMC) turbine and combustor hot section components are currently being developed to meet future turbine engine emission and performance goals. One of the significant coating development challenges is to achieve prime-reliant environmental barrier coating systems to meet the future 2700F EBC-CMC temperature stability and environmental durability requirements. This presentation will emphasize recent NASA environmental barrier coating system testing and down-selects, particularly the development path and properties towards 2700-3000F durability goals by using NASA hafnium-hafnia-rare earth-silicon-silicate composition EBC systems for the SiC-SiC CMC turbine component applications. Advanced hafnium-based compositions for enabling next generation EBC and CMCs capabilities towards ultra-high temperature ceramic coating systems will also be briefly mentioned.

Ceramic Matrix Composite↗
NASA NTRS1994

The evolution of enstatite and chondrules in unequilibrated enstatite chondrites: Evidence from iron-rich pyroxene

FeO-rich (Fs(sub 6)-34) pyroxene lacking cathodoluminescence (CL), hereafter black pyroxene, is a major constituent of some of the chondrules and fragments in unequilibrated (type 3) enstatite chondrites (UECs). It contains structurally oriented zones of Cr-, Mn-, V-rich, FeO-poor enstatite with red CL, associated with mm-sized blebs of low-Ni, Fe-metal and, in some cases, silica. These occurrences represent clear evidence of pyroxene reduction. The black pyroxene is nearly always rimmed by minor element (Cr, Mn, V)-poor enstatite having a blue CL. More commonly, red and blue enstatites, unassociated with black pyroxene, occur as larger grains in chondrules and fragments, and these constitute the major silicate phases in UECs. The rare earth element (REE) abundance patterns of the black pyroxene are LREE-depleted. The blue enstatite rims, however, have a near-flat to LREE-enriched pattern, approx. 0.5-4x chondritic. The petrologic and trace element data indicate that the black pyroxene is from an earlier generation of chondrules that formed in a nebular region that was more oxidizing than that of the enstatite chondrites. Following solidification, these chondrules experienced a more reducing nebular environment and underwent reduction. Some, perhaps most, of the red enstatite that is common throughout the UECs may be the product of solid-state reduction of black pyroxene. The blue enstatite rims grew onto the surfaces of the black pyroxene and red enstatite as a result of condensation from a nebular gas. The evolutionary history of some of the enstatite and chondrules in enstatite chondrites can be expressed in a four-stage model that includes: Stage 1. Formation of chondrules in an oxidizing nebular environment. Stage 2. Solid-state reduction of the more oxidized chondrules and fragments to red enstatite in a more reducing nebular environment. Stage 3. Formation of blue enstatite rims on the black pyroxene as well as on the red enstatite. Stage 4. Reprocessing, by various degrees of melting, of many of the earlier-formed materials.

Weisberg, Michael K.↗
NASA NTRS1998

Technologies for Non-Destructive Evaluation of Surfaces and Thin Coating

A study was made on two commercially available terbium-doped silicate glasses. There is an increased interest in silicate glasses doped with rare-earth ions for use in high-energy particle detection and radiographic applications. These glasses are of interest due to the fact that they can be formed into small fiber sensors; a property that can be used to increase the spatial resolution of a detection system. Following absorption of radiation, the terbium ions become excited and then emit photons via 4f-4f electronic transitions as they relax back to the ground state. The lifetime of these transitions is on the order of milliseconds. A longer decay component lasting on the order of minutes has also been observed. While radiative transitions in the 4f shell of rare-earth ions are generally well understood by the Judd-Olfelt theory, the presence of a longer luminescence decay component is not. Experimental evidence that the long decay component is due, in part, to the thermal release of trapped charge carriers will be presented. In addition, a theoretical model describing the time evolution of the radiation-induced luminescence will be presented.

Manos, Dennis M.↗
NASA NTRS1996

Time Evolution of Radiation-Induced Luminescence in Terbium-Doped Silicate Glass

A study was made on two commercially available terbium-doped silicate glasses. There is an increased interest in silicate glasses doped with rare-earth ions for use in high-energy particle detection and radiographic applications. These glasses are of interest due to the fact that they can be formed into small fiber sensors; a property that can be used to increase the spatial resolution of a detection system. Following absorption of radiation, the terbium ions become excited and then emit photons via 4f-4f electronic transitions as they relax back to the ground state. The lifetime of these transitions is on the order of milliseconds. A longer decay component lasting on the order of minutes has also been observed. While radiative transitions in the 4f shell of rare-earth ions are generally well understood by the Judd-Olfelt theory, the pr'esence of a longer luminescence decay component is not. Experimental evidence that the long decay component is due, in part, to the thermal release of trapped charge carriers will be presented. In addition, a theoretical model describing the time evolution of the radiation-induced luminescence will be presented.

West, Michael S.↗
NASA NTRS2019

Molten Silicate Reactivity with Environmental Barrier Coating Materials for Gas Turbine Engine Applications

Rare earth (RE) disilicates are utilized in environmental barrier coatings (EBCs) to protect SiC-based ceramic matrix composites (CMCs) from destructive reactions with water vapor and other combustion species. These coating materials, however, degrade when exposed to molten silicate deposits primarily composed of calcium-magnesium aluminosilicates (CMAS). Coating materials are exposed to CMAS by engine ingestion of dust particulates from terrestrial sources during operation. Due to continual increases in engine operating temperature, it is important to understand the high temperature thermochemical mechanisms that drive corrosion of these materials. This work focuses on characterizing reaction products between disilicates and CMAS and optimizing coating chemistries to mitigate damage.

Stokes, Jamesa L.↗
NASA NTRS2016

Thermochemistry of CaO-MgO-Al2O3-SiO2 (CMAS) and Advanced Thermal and Environmental Barrier Coating Systems

CaO-MgO-Al2O3-SiO2 (CMAS) oxides are constituents in a broad number of materials and minerals which have recently inferred to discussions in materials science, planetary science, geochemistry and cosmochemistry communities. In materials science, there is increasing interest in the degradation studies of thermal (TBC) and environmental (EBC) barrier coatings of gas turbines by molten CMAS. These coatings have been explored to be applied on silicon-based ceramics and composites which are lighter and more temperature capable hot-section materials of gas turbines than the current Ni-based superalloys. The degradation of the coatings occurs when CMAS minerals carried by the intake air into gas turbines, e.g. in aircraft engines, reacts at high temperatures (1000C) with the coating materials. This causes premature failure of the static and rotating components of the turbine engines. We discuss some preliminary results of the reactions between CMAS and Rare-Earth (RE Y, Yb and Gd) oxide stabilized ZrO2 systems, and stability of the resulting oxides and silicates.

CaO-MgO-Al2O3-SiO2 (CMAS)↗
NASA NTRS1988

Decoupled Rb-Sr and Sm-Nd isotopic evolution of the continental crust

Evidence was presented that the Rb-Sr and Sm-Nd isotopic systems are decoupled in crust-mantle evolution. Rare earth element (including Sm and Nd) residue principally in silicates, and are resistant to mobilization by weathering and metamorphism. In contrast, Rb and Sr are easily fractionated by crustal processes and residue in carbonates as well as in silicates. As a result, continental Sr, but not Nd, can be recycled into the mantle by exchange of seawater with basalt at spreading ridges and by subduction of carbonates associated with ridge processes. These effects result in mean Rb-Sr ages of the continental crust and of the upper mantle that are too young. Crustal growth curves based largely on Rb-Sr data, such that of Hurley and Rand, are therefore incorrect.

Goldstein, S. L.↗
NASA NTRS1988

Partitioning of rare earth elements between hibonite and melt and implications for nebular condensation of the rare earth elements

The effect of oxygen fugacity on the partitioning of REEs between hibonite and silicate melt is investigated in hibonite-growth experiments at 1470 C. The experimental procedures and apparatus are described, and the results are presented in extensive tables and graphs and characterized in detail. The absolute activity coefficients in hibonite are estimated as 330 for La, 1200 for Eu(3+), and 24,000 for Yb. It is inferred that ideal solution behavior cannot be assumed when calculating REE condensation temperatures for (Ca, Al)-rich inclusions in carbonaceous chondrites.

Drake, Michael J.↗
NASA NTRS1995

Second Annual Research Center for Optical Physics (RCOP) Forum

The Research Center for Optical Physics (RCOP) held its Second Annual Forum on September 23-24, 1994. The forum consisted of two days of technical sessions with invited talks, submitted talks, and a student poster session. Participants in the technical sessions included students and researchers from CCNY/CUNY, Fisk University, Georgia Institute of Technology, Hampton University, University of Maryland, the Univeristy of Michigan, NASA Langley Research Center, North Caroline A and T University, Steven's Institute of Technology, and NAWC-Warminster. Topics included chaotic lasers, pumped optical filters, nonlinear responses in polythiophene and thiophene based thin films, crystal growth and spectroscopy, laser-induced photochromic centers, raman scattering in phorphyrin, superradiance, doped fluoride crystals, luminescence of terbium in silicate glass, and radiative and nonradiative transitions in rare-earth ions.

Allario, Frank↗
NASA NTRS2017

Thermochemistry of Calcium-Magnesium-Aluminum-Silicate (CMAS) and Components of Advanced Thermal and Environmental Barrier Coating Systems

There is increasing interest in the degradation mechanism studies of thermal and environmental barrier coatings (TEBCs) of gas turbines by molten CaO-MgO-Al(exp. 2)O(exp. 3)-SiO(exp. 2) CMAS). CMAS minerals are usually referred as silicon-containing sand dust and volcano ash materials that are carried by the intake air into gas turbines, e.g. in aircraft engines, and their deposits often react at high temperatures (greater than 1200 degrees C) with the engine turbine coating systems and components. The high temperature reactions causes degradation and accelerated failure of the static and rotating components of the turbine engines. We discuss some results of the reactions between the CMAS and Rare-Earth (RE = Y, Yb, Dy, Gd, Nd and Sm) - oxide stabilized ZrO(exp. 2) or HfO(exp. 2) systems, and the stability of the resulting oxides and silicates. Plasma sprayed hollow tube samples (outside diameter = 4.7 mm, wall thickness = 0.76 mm and = 26 mm height) were half filled with CMAS powder, wrapped and sealed with platinum foil, and heat treated at 1310 degrees C for 5h. Samples were characterized by differential scanning calorimetry (DSC), X-ray diffraction, and cross-section electron microscopy analysis and energy dispersive X-ray spectroscopy. It was found that CMAS penetrated the samples at the grain boundaries and dissolved the TEBC materials to form silicate phases containing the rare-earth elements. Furthermore, it was found that apatite crystalline phases were formed in the samples with total rare-earth content higher than 12 mol% in the reaction zone for the ZrO(exp. 2) system. In general, samples with the nominal compositions (30YSZ), HfO(exp. 2)-7Dy(exp. 2)O(exp. 2) and ZrO(exp. 2)-9.5Y(exp. 2)O(exp. 3)-2.25Gd(exp. 2)O(exp. 3)-2.25Yb(exp. 2)O(exp. 3) exhibited lower reactivity or more resistance to CMAS than the other coating compositions of this work.

degradation↗
NASA NTRS2021

Thermal Expansion Coefficients of Ca2Y8(SiO4)6O2 and Ca2Yb8(SiO4)6O2 Apatite-type Silicates

High temperature X-ray diffraction (XRD) scans of Y2Si2O7 and Yb2Si2O7 reactions with calcium-magnesium-aluminosilicates (CMAS) were utilized to determine thermal expansion coefficients (CTEs) of Ca2Y8(SiO4)6O2 and Ca2Yb8(SiO4)6O2 apatite materials. In order to validate these measurements, the CTEs of Y2Si2O7, Yb2Si2O7 and SiO2 were also determined from the same scans. The directional CTEs for γ-Y2Si2O7 were determined to be αa=5.84×10-6/K, αb=6.81×10-6/K and αc=0.81×10-6/K, and β-Yb2Si2O7 was determined to have values of αa=6.89×10-6/K, αb=4.81×10-6/K and αc=2.78×10-6/K. The average CTEs of γ-Y2Si2O7 and β-Yb2Si2O7 were determined to be 4.5×10-6/K and 4.7×10-6/K, respectively, which agreed with previous analyses. Ca2Y8(SiO4)6O2 exhibited directional CTEs of αa=9.36×10-6/K and αc=7.95×10-6/K (averaged between two sets of data), whereas Ca2Yb8(SiO4)6O2 had values that were very similar (αa=9.63×10-6/K, αc=7.45×10-6/K). Both results for the Ca2RE8(SiO4)6O2 apatites correlated well with the limited data on apatite-type silicates available in literature.

rare earth↗
NASA NTRS1974

The distribution of Sr and REE between diopside and silicate liquid

Experimental determination of the distribution coefficients in diopside-liquid pairs for strontium and nine rare-earth elements in the system CaMgSi2O6-NaAlSi3O8-CaAl2Si2O8. In experiments in air at 1265 C it is found that most of the Sr(2+), Eu(2+), and RE(3+) ions substitute for Ca(2+) and, in addition, a coupled substitution of Al(3+) for Si(4+) occurs. All of the trace ions considered are found to be excluded from the diopside lattice relative to the liquid. In the case of the trivalent ions the exclusion is much more pronounced for La and Ce, which have ionic radii larger than that of Ca(2+) in 8-fold oxygen coordination. Divalent Sr and Eu with even larger radii are also strongly excluded.

Grutzeck, M.↗
NASA NTRS2017

Thermochemistry of CaO-MgO-Al2O3-SiO2 (CMAS) and Advanced Thermal and Environmental Barrier Coating Systems

CaO-MgO-Al2O3-SiO2 (CMAS) oxides are constituents in a broad number of materials and minerals which have recently inferred to discussions in materials science, planetary science, geochemistry and cosmochemistry communities. In materials science, there is increasing interest in the degradation studies of thermal (TBC) and environmental (EBC) barrier coatings of gas turbines by molten CMAS. CMAS minerals usually are carried by the intake air into gas turbines, e.g. in aircraft engines, and their deposits react at high temperatures (1000C) with the coating materials. This causes degradation and accelerated failure of the static and rotating components of the turbine engines. We discuss some preliminary results of the reactions between CMAS and Rare-Earth (RE Y, Yb, Dy, Gd, Nd and Sm) oxide stabilized ZrO2 or HfO2 systems, and the stability of the resulting oxides and silicates. Plasma sprayed hollow tube samples ( 2.2 mm and 26 mm height) were half filled with CMAS powder, wrapped and sealed with platinum foil, and heat treated at 1310 C for 5h. Samples were characterized by differential scanning calorimetry, X-ray diffraction and cross section electron microscopy analysis.

degradation↗
NASA NTRS1982

Primary igneous carbon in ureilites - Petrological implications

The ureilite meteorites are carbonaceous olivine-pyroxene achondrites. They typically contain up to 4 wt.% carbon (carbonaceous matrix) as graphite, diamond, and lonsdaleite. Shock degradation has effectively obliterated primary textures in the carbonaceous matrix of previously described ureilites, a factor that has hampered efforts to explain the origin of this material. In contrast, the Antarctic ureilite ALHA78019 displays perfectly preserved primary textures in the carbonaceous matrix characterized by euhedral graphite blades intergrown with Fe-Ni metal and sulfide (diamonds are absent). This petrographic feature suggests that most graphite in ureilites originated by crystallization from a C-rich metallic phase. Assuming that fO2 is controlled by C-CO-CO2 reactions, the compositions of silicates and metals in ureilites imply a two-stage redox history. The noble gases and rare earths of ureilites are discussed in light of this model.

Berkely, J. L.↗
NASA NTRSDate not supplied

Compositional Clues to the Origin of Refractory Metal Nuggets, Perovskite, and Zr-Rich Oxides in Hibonite from the Paris Cm Chondrite

Rare Ca-Al-rich inclusions (CAIs) in carbonaceous chondrites are dominated by Zr-, Sc-, Ti-,and/or Y-rich oxides and silicates, and often contain refractory metal nuggets (RMNs)[1-3]. These phases have ultra refractory (UR) rare earth element (REE)patterns that are complementary to Group II patterns[4]. Therefore, studies of such UR CAIs likely decipher a record of nebular conditions and processes at higher temperatures than other CAIs consisting mainly of spinel and melilite. Our previous TEM analyses reported a discovery of the assemblages of RMNs, perovskite, and Zr-rich oxides in hibonite from the Paris CM chondrite[5]. Here we present TEM results of a detailed chemical study of these UR phases to provide clues to their formation conditions in the early solar nebula.

J Han↗
NASA NTRS1985

The coming revolution in planetology

Current ideas about the moon appear to be mistaken on two fundamental points. First, at least within certain large classes of lunar craters, internal origin (i.e., some form of volcanism) predominates over impact; this result raises questions about the reality of the 'era of violent bombardment'. Second, the origin of tektites by meteoritic impact on the earth cannot be reconciled with physical principles and is to be abandoned. The only viable alternative is origin by lunar volcanism, which implies the following: continuance of (rare) explosive lunar volcanism to the present time; existence of silicic lunar volcanism and of small patches of silicic rock at the lunar surface; a body of rock in the lunar interior, probably at great depth, which is closely similar to the earth's mantle and which contains billions of tons of volatiles, probably including hydrogen; and origin of the moon from the earth after the formation of the earth's core.

Okeefe, J. A.↗