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At least 181 records · Page 10

Ceramic Paste for Patching High-Temperature Insulation

A ceramic paste that can be applied relatively easily, either by itself or in combination with one or more layer(s) of high-temperature ceramic fabrics, such as silicon carbide or zirconia, has been invented as a means of patching cracks or holes in the reinforced carbon-carbon forward surfaces of a space shuttle in orbit before returning to Earth. The paste or the paste/fabric combination could also be used to repair rocket-motor combustion chambers, and could be used on Earth to patch similar high-temperature structures. The specified chemical composition of the paste admits of a number of variations, and the exact proportions of its constituents are proprietary. In general, the paste consists of (1) silicon carbide, possibly with addition of (2) hafnium carbide, zirconium carbide, zirconium boride, silicon tetraboride, silicon hexaboride, or other metal carbides or oxides blended with (3) a silazane-based polymer. Because the paste is viscous and sticky at normal terrestrial and outer-space ambient temperatures, high-temperature ceramic fabrics such as silicon carbide or zirconia fabric impregnated with the paste (or the paste alone) sticks to the damaged surface to which it is applied. Once the patch has been applied, it is smoothed to minimize edge steps as required [forward-facing edge steps must be < or equal to 0.030 in. (< or equal to 0.76 mm) in the original intended space-shuttle application]. The patch is then heated to a curing temperature thereby converting it from a flexible material to a hard, tough material. The curing temperature is 375 to 450 F (approx.190 to 230 C). In torch tests and arc-jet tests, the cured paste was found to be capable of withstanding a temperature of 3,500 F (approx. 1,900 C) for 15 minutes. As such, the material appears to satisfy the requirement, in the original space-shuttle application, to withstand re-entry temperatures of approx.3,000 F (approx. 1,600 C).

Adam, Steven J.↗

Ultrahigh-Temperature Ceramics

Ultrahigh temperature ceramics (UHTCs) are a class of materials that include the diborides of metals such as hafnium and zirconium. The materials are of interest to NASA for their potential utility as sharp leading edges for hypersonic vehicles. Such an application requires that the materials be capable of operating at temperatures, often in excess of 2,000 C. UHTCs are highly refractory and have high thermal conductivity, an advantage for this application. UHTCs are potentially applicable for other high-temperature processing applications, such as crucibles for molten-metal processing and high-temperature electrodes. UHTCs were first studied in the 1960 s by the U.S. Air Force. NASA s Ames Research Center concentrated on developing materials in the HfB2/SiC family for a leading-edge application. The work focused on developing a process to make uniform monolithic (2-phase) materials, and on the testing and design of these materials. Figure 1 shows arc-jet models made from UHTC materials fabricated at Ames. Figure 2 shows a cone being tested in the arc-jet. Other variations of these materials being investigated elsewhere include zirconium based materials and fiber-reinforced composites. Current UHTC work at Ames covers four broad topics: monoliths, coatings, composites, and processing. The goals include improving the fracture toughness, thermal conductivity and oxidation resistance of monolithic UHTCs and developing oxidation-resistant UHTC coatings for thermal-protection-system substrates through novel coating methods. As part of this effort, researchers are exploring compositions and processing changes that have yielded improvements in properties. Computational materials science and nanotechnology are being explored as approaches to reduce materials development time and improve and tailor properties.

Johnson, Sylvia M.↗

Lightweight, Ultra-High-Temperature, CMC-Lined Carbon/Carbon Structures

Carbon/carbon (C/C) is an established engineering material used extensively in aerospace. The beneficial properties of C/C include high strength, low density, and toughness. Its shortcoming is its limited usability at temperatures higher than the oxidation temperature of carbon . approximately 400 C. Ceramic matrix composites (CMCs) are used instead, but carry a weight penalty. Combining a thin laminate of CMC to a bulk structure of C/C retains all of the benefits of C/C with the high temperature oxidizing environment usability of CMCs. Ultramet demonstrated the feasibility of combining the light weight of C/C composites with the oxidation resistance of zirconium carbide (ZrC) and zirconium- silicon carbide (Zr-Si-C) CMCs in a unique system composed of a C/C primary structure with an integral CMC liner with temperature capability up to 4,200 F (.2,315 C). The system effectively bridged the gap in weight and performance between coated C/C and bulk CMCs. Fabrication was demonstrated through an innovative variant of Ultramet fs rapid, pressureless melt infiltration processing technology. The fully developed material system has strength that is comparable with that of C/C, lower density than Cf/SiC, and ultra-high-temperature oxidation stability. Application of the reinforced ceramic casing to a predominantly C/C structure creates a highly innovative material with the potential to achieve the long-sought goal of long-term, cyclic high-temperature use of C/C in an oxidizing environment. The C/C substructure provided most of the mechanical integrity, and the CMC strengths achieved appeared to be sufficient to allow the CMC to perform its primary function of protecting the C/C. Nozzle extension components were fabricated and successfully hot-fire tested. Test results showed good thermochemical and thermomechanical stability of the CMC, as well as excellent interfacial bonding between the CMC liner and the underlying C/C structure. In particular, hafnium-containing CMCs on C/C were shown to perform well at temperatures exceeding 3,500 F (.1,925 C). The melt-infiltrated CMC-lined C/C composites offered a lower density than Cf/SiC. The melt-infiltrated composites offer greater use temperature than Cf/SiC because of the more refractory ceramic matrices and the C/C substructure provides greater high-temperature strength. The progress made in this work will allow multiple high-temperature components used in oxidizing environments to take advantage of the low density and high strength of C/C combined with the high-temperature oxidation resistance of melt-infiltrated CMCs.

Wright, Matthew J.↗

Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Jordan, Jeffrey D.↗

Development of Matrix Microstructures in UHTC Composites

One of the major issues hindering the use of ultra high temperature ceramics for aerospace applications is low fracture toughness. There is considerable interest in developing fiber-reinforced composites to improve fracture toughness. Considerable knowledge has been gained in controlling and improving the microstructure of monolithic UHTCs, and this paper addresses the question of transferring that knowledge to composites. Some model composites have been made and the microstructures of the matrix developed has been explored and compared to the microstructure of monolithic materials in the hafnium diboride/silicon carbide family. Both 2D and 3D weaves have been impregnated and processed.

Johnson, Sylvia↗

Hardness and Microstructure of Binary and Ternary Nitinol Compounds

The hardness and microstructure of twenty-six binary and ternary Nitinol (nickel titanium, nickel titanium hafnium, nickel titanium zirconium and nickel titanium tantalum) compounds were studied. A small (50g) ingot of each compound was produced by vacuum arc remelting. Each ingot was homogenized in vacuum for 48 hr followed by furnace cooling. Specimens from the ingots were then heat treated at 800, 900, 1000 or 1100 degree C for 2 hr followed by water quenching. The hardness and microstructure of each specimen was compared to the baseline material (55-Nitinol, 55 at.% nickel - 45 at.% titanium, after heat treatment at 900 degC). The results show that eleven of the studied compounds had higher hardness values than the baseline material. Moreover, twelve of the studied compounds had measured hardness values greater 600HV at heat treatments from 800 to 900 degree C.

intermetallics↗

High-Melt Carbon-Carbon Coating for Nozzle Extensions

Carbon-Carbon Advanced Technologies, Inc. (C-CAT), has developed a high-melt coating for use in nozzle extensions in next-generation spacecraft. The coating is composed primarily of carbon-carbon, a carbon-fiber and carbon-matrix composite material that has gained a spaceworthy reputation due to its ability to withstand ultrahigh temperatures. C-CAT's high-melt coating embeds hafnium carbide (HfC) and zirconium diboride (ZrB2) within the outer layers of a carbon-carbon structure. The coating demonstrated enhanced high-temperature durability and suffered no erosion during a test in NASA's Arc Jet Complex. (Test parameters: stagnation heat flux=198 BTD/sq ft-sec; pressure=.265 atm; temperature=3,100 F; four cycles totaling 28 minutes) In Phase I of the project, C-CAT successfully demonstrated large-scale manufacturability with a 40-inch cylinder representing the end of a nozzle extension and a 16-inch flanged cylinder representing the attach flange of a nozzle extension. These demonstrators were manufactured without spalling or delaminations. In Phase II, C-CAT worked with engine designers to develop a nozzle extension stub skirt interfaced with an Aerojet Rocketdyne RL10 engine. All objectives for Phase II were successfully met. Additional nonengine applications for the coating include thermal protection systems (TPS) for next-generation spacecraft and hypersonic aircraft.

Thompson, James↗

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

humic acid↗

Processing and Characterization of Thousand-Hour 500 C Durable 4H-SiC JFET Integrated Circuits

This work reports fabrication and testing of integrated circuits (ICs) with two levels of interconnect that consistently achieve greater than 1000 hours of stable electrical operation at 500 C in air ambient. These ICs are based on 4H-SiC junction field effect transistor (JFET) technology that integrates hafnium ohmic contacts with TaSi2 interconnects and SiO2 and Si3N4 dielectric layers over approximately 1-micrometer scale vertical topology. Following initial burn-in, important circuit parameters remain stable for more than 1000 hours of 500 C operational testing. These results advance the technology foundation for realizing long-term durable 500 C ICs with increased functional capability for sensing and control combustion engine, planetary, deep-well drilling, and other harsh-environment applications.

Microelectronics↗

Processing and Characterization of Thousand-Hour 500 C Durable 4H-SiC JFET Integrated Circuits

This work reports fabrication and testing of integrated circuits (ICs) with two levels of interconnect that consistently achieve greater than 1000 hours of stable electrical operation at 500 C in air ambient. These ICs are based on 4H-SiC junction field effect transistor (JFET) technology that integrates hafnium ohmic contacts with TaSi2 interconnects and SiO2 and Si3N4 dielectric layers over 1-m scale vertical topology. Following initial burn-in, important circuit parameters remain stable for more than 1000 hours of 500 C operational testing. These results advance the technology foundation for realizing long-term durable 500 C ICs with increased functional capability for sensing and control combustion engine, planetary, deep-well drilling, and other harsh-environment applications.

JFET↗

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

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

ceramic matrix composites↗

Advanced Environmental Barrier Coating and SA Tyrannohex SiC Composites Integration for Improved Thermomechanical and Environmental Durability

The development of 2700 degF capable environmental barrier coating (EBC) systems, particularly, the Rare Earth "Hafnium" Silicon bond coat systems, have significantly improved the temperature capability and environmental stability of SiC/SiC Ceramic Matrix Composite Systems. We have specifically developed the advanced 2700 degF EBC systems, integrating the EBC to the high temperature SA Tyrannohex SiC fiber composites, for comprehensive performance and durability evaluations for potential turbine engine airfoil component applications. The fundamental mechanical properties, environmental stability and thermal gradient cyclic durability performance of the EBC - SA Tyrannohex composites were investigated. The paper will particularly emphasize the high pressure combustion rig recession, cyclic thermal stress resistance and thermomechanical low cycle fatigue testing of uncoated and environmental barrier coated Tyrannohex SiC SA composites in these simulated turbine engine combustion water vapor, thermal gradients, and mechanical loading conditions. We have also investigated high heat flux and flexural fatigue degradation mechanisms, determined the upper limits of operating temperature conditions for the coated SA composite material systems in thermomechanical fatigue conditions. Recent progress has also been made by using the self-healing rare earth-silicon based EBCs, thus enhancing the SA composite hexagonal fiber columns bonding for improved thermomechanical and environmental durability in turbine engine operation environments. More advanced EBC- composite systems based on the new EBC-Fiber Interphases will also be discussed.

Tyrannohex SiC Ceramics↗

Fabrication of Phononic-Isolated Kinetic Inductance Detectors

Kinetic inductance detectors (KID) have received increased interest due to their relative ease of fabrication, low noise, and scalability to large format arrays required by next generation of astronomical telescopes. The development of KIDs has progressed rapidly, with very low noise equivalent power demonstrated by several groups and KIDs arrays implemented in several ground-based and air-borne instruments. In this paper, we describe a new fabrication process which consists of a membrane isolated KID incorporating a phononic bandgap structure tuned to block recombination phonons from escaping to the thermal bath. This architecture is designed to increase the quasi-particle lifetime and results in increased responsivity to signal photons and lower noise. These devices have been fabricated as lumped-element resonators with hafnium inductors and Nb capacitors on low stress silicon nitride and silicon-on-insulator membranes. We discuss the fabrication process, which uses a combination of sub-micron laser based direct write lithography and nanoscale electron beam lithography.

Denis, Kevin L.↗

Ag isotopic and chalcophile element evolution of the terrestrial and martian mantles during accretion: new constraints from Bi, Pd, and Ag metal-silicate partitioning.

The Earth’s timing of accretion and acquisition of moderately volatile compounds is uncertain. Hafnium-W and Mn-Cr isotopic data can bracket the timing of early planetary differentiation and core formation. The Ag-Pd system has also been utilized but its application has been limited by a lack of high pressure and temperature metal-silicate partitioning for Pd and Ag. Be-cause Ag (and Bi) are volatile chalcophile siderophile elements, understanding their early distribution can constrain the origin of volatile elements in differentiated bodies and planets. Unfortunately, neither Ag or Bi have been studied across the wide range of pressure and temperature conditions that are relevant to accretion and core-mantle differentiation. Here, new high-pressure and temperature multi-anvil metal-silicate equilibrium experiments for Bi and Ag have been carried out at conditions relevant to planetary accretion and metal silicate differentiation that allow a more refined and complete understanding of element partitioning during core formation. The new metal-silicate partitioning data utilized to predict the distributions of Bi, Pd, and Ag at conditions of accretion for Earth and Mars and show that the Pd/Ag ratio is significantly fractionated during accretion, allowing for the production of detectable 107Ag anomalies produced while 107Pd (half life = 6.5 M.y.) was still extant. Application of the new partitioning results to Earth shows that D(Bi) and D(Ag) (D = metal/silicate concentration ratio) are lowered due to the effect of pressure and Si alloyed in the metallic liquid, resulting in higher predicted mantle Bi and Ag abundances than in the bulk silicate Earth (BSE), as well as high and variable Pd/Ag. The unradiogenic Ag isotopic composition of the BSE could have been generated by early accretion of volatile-poor (high Pd/Ag) precursors, followed by later accretion of volatile–rich (low Pd/Ag) material, in agreement with earlier studies of Pd-Ag and Mn-Cr (Schönbächler et al., 2010). However, these main accretion phases would have to be followed by segregation of a sulfide liquid (at least 1.5% of magma ocean) at high pressures (>30 GPa), to explain the PUM Bi, Pd, and Ag, as well as Au, Pt, Cu and Ni concentrations as proposed previously. If the early accreted bulk Earth was volatile depleted with high Pd/Ag ratios, portions of the mantle may contain ancient domains that developed positive 107Ag isotopic anomalies (as also argued by noble gases, Nd, W, and Os isotopes). In comparison, Bi, Pd, and Ag concentrations in the martian mantle could have been set by simple metal-silicate equilibrium. Mars accreted and differentiated relatively rapidly, while also developing a deep magma ocean with a high Pd/Ag ratio that could have evolved positive 107Ag anomalies, in contrast to Earth. Measurements on shergottites may reveal these predicted Ag isotopic anomalies.

accretion↗

Optical and Electrical Properties of Reactively Sputtered TiN, ZrN, and HfN Thin Films

Thin films of titanium, zirconium, and hafnium nitride are prepared by DC magnetron reactive sputtering at room temperature on fused silica, optical glass, and silicon substrates. Deposition parameters are investigated in order to obtain stoichiometric films. The optical and electrical properties of the films as a function of nitrogen partial pressure are determined. The results show that an inverse correlation exists between the optical reflectance and the electrical resistivity of the films. Ellipsometer data for all three films show that their refractive index in the visible spectrum is decreased by increasing the film thickness while the extinction coefficient is unchanged. Thin films of TiN have the lowest room temperature resistivity relative to ZrN and HfN thin films.

Reactive↗

Unified Material-Environment Interaction Model for Binary UHTC Composites

A new model for the surface chemistry of zirconium and hafnium diborides containing silicon-carbide when exposed to high temperature conditions in air is formulated. Oxidation dynamics are simplified by considering the diffusion-limited equilibrium regime within the material at elevated temperatures. This model is first assessed against experimental mass-gain data taken from UHTC samples heated to high temperature in an oxygen environment. Then, further evaluations of the new model are conducted using hypersonic CFD simulations to analyze conditions experienced by HfB2-SiC in arc jet experiments conducted at NASA Ames Research Center. Measurements of stagnation point heat transfer and pressure are then used to calibrate the simulations. Results of coupled CFD-material response simulations are then compared to the surface temperatures measured during the Ames arc jet test. Results support the use of the proposed model while highlighting the need for improved gas-phase data on the additional constituents considered.

ultra high temperature ceramic↗

Thermochemical Degradation of HfSiO4 by Molten CMAS

The thermochemical degradation of hafnium silicate (HfSiO4) was investigated with a molten calcium-magnesium-aluminosilicate (CMAS) glass relevant to gas turbine engine applications. Sintered HfSiO4 coupons were fabricated, within which wells were drilled and filled with CMAS glass powder at a loading of ~35 mg/cm2. Samples were heat treated at1200°C, 1300°C, 1400°C, and 1500°C for 1 hour, 10 hours, and 50 hours. At 1200°C and1300°C, slow formation of a Ca2HfSi4O12 cyclosilicate phase was observed at the HfSiO4-CMASinterface. At 1300°C and higher, rapid infiltration of CMAS into the material along the grain boundaries was observed. Initial conjecture into CMAS degradation mechanisms of HfSiO4 are presented herein.

CMAS↗

Shock- and Corrosion-Resistant Bearings for Space Mechanisms

Nickel-titanium (NiTi) alloys are an emerging class of materials for rolling element bearing applications that require superior corrosion resistance and/or high load capability. Certain space mechanisms fall into one or both of those categories. Often, due to size and mass considerations, space mechanism systems are limited in torque margin and necessarily require small, precision-instrument bearings with very little frictional drag (i.e., low torque). In addition, space mechanism bearings must survive launch conditions without suffering raceway dents known as brinnelling, which would increase operating torque and reduce overall smoothness. Consequently, a bearing material or design that reduces or eliminates brinnelling under high contact stress conditions would represent a beneficial technology advancement. One specific alloy, nickel-titanium-hafnium (NiTi-Hf), under development for several years at the NASA Glenn Research Center as a bearing material, has the potential to mitigate concerns about brinnelling under extreme load conditions due to its unusually high elastic strain capability. In the present work, a sample of small precision bearings produced with three different ball materials (steel, ceramic, and NiTi-Hf) is subjected to a range of load conditions sufficient to dent the races. The dent depth as a function of load is compared and demonstrates that NiTi-Hf has the potential to increase bearing load capacity from the perspective of brinnelling under severe load conditions; additional testing of full NiTi-Hf bearings demonstrates corrosion resistance superior to that of 440C bearings.

Bearings↗