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Ultra-High Temperature Ceramic (UHTC) Development

During the last decade, NASA Ames has been developing new, Ultra-High Temperature Ceramic (UHTC) materials for Thermal Protection Systems applications. The UHTC s are a family of materials including compositions of HfE32 and ZrB2 with a Sic second phase. A collaboration with Glenn was recently initiated to evaluate the viability of some UHTC materials that had been produced by an outside vendor for use in gas turbine en,@ne environments. Results from this collaboration have indicated that compositions based on HfB2 show the most promise, among the UHTC compositions evaluated, for use in these environments. Work at ARC has been initiated to fabricate these materials in-house and evaluate methods of improving their properties for use in engine environments.

Johnson, Sylvia↗

Perspectives and challenges of ultra-high temperature ceramics for fusion plasma-facing applications

Ultra-high temperature ceramics (UHTCs) offer several potential advantages as plasma-facing components (PFCs) in fusion reactors due to their extreme melting points, tailorable thermal conductivity, and attractive unirradiated mechanical properties including fracture toughness comparable or superior to tungsten. Here, recent developments and material properties of UHTCs are briefly reviewed, along with an overview of limited studies on their responses to neutron irradiation and an evaluation of plasma-surface interactions. Five key research pathways, primarily focused on irradiation effects, for advancing UHTCs in PFC applications are discussed: (1) assessing irradiation effects on the coupled thermal–mechanical performance (2) addressing the lack of studies on irradiation, plasma-surface interactions, and their synergistic effects; (3) investigating high-temperature (>1000 °C) neutron irradiation effects critical for PFC performance; (4) optimizing multi-component UHTC compositions or composites to improve thermal or mechanical properties; (5) enhancing radiation resistance to mitigate microcracking and void swelling through strategies such as increasing sink strength by reducing grain size, introducing fine particles, and leveraging complex concentrated alloy concepts.

36 MATERIALS SCIENCE↗

Development of Processing Techniques for Advanced Thermal Protection Materials

During the period June 1, 1996 through May 31, 1997, the main effort has been in the development of materials for high temperature applications. Thermal Protection Systems (TPS) are constantly being tested and evaluated for thermal shock resistance, high temperature dimensional stability, and tolerance to environmental effects. Materials development was carried out by using many different instruments and methods, ranging from intensive elemental analysis to testing the physical attributes of a material. The material development concentrated on two key areas: (1) development of coatings for carbon/carbon composites, and (2) development of ultra-high temperature ceramics (UHTC). This report describes the progress made in these two areas of research during this contract period.

Selvaduray, Guna↗

SHARP-B2: Flight Test Objectives, Project Implementation and Initial Results

On September 28, 2000 the SHARP-B2 flight experiment was launched from Vandenberg Air Force Base, California. SHARP-B2 is the 2nd Ballistic flight test in the SHARP (Slender Hypervelocity Aerothermodynamic Research Probes) program which develops and tests new thermal protection materials and sharp body concepts. The flight tested Ultra-High Temperature Ceramics (UHTCs), which may radically change the design and performance of future aerospace vehicles. The new designs may overturn an age-old tenet of aerodynamics: that blunt-body aerospace vehicles, but not those with sharp leading edges, can survive the searing temperatures created as the vehicles tear through the atmosphere. Sharp leading edges offer numerous advantages over the blunt-body design currently in use. They could allow a space shuttle or crew return vehicle to maneuver in space more like an airplane and potentially allow astronauts to return to Earth from anywhere on orbit. They may allow improved astronaut safety by decreasing the risk of aborting into the ocean. They may reduce the electromagnetic interference that causes the communications blackouts that plague reentering blunt-body space vehicles. Reducing the amount of drag could lead to a reduction in propulsion requirements. Planetary probes could make use of sharp-body technology for aerobraking and to maximize their maneuvering capability. SHARP-B2 was a joint effort among NASA Ames, Sandia National Laboratories, the U.S. Air Force and the U.S. Army. It was funded by the Pathfinder Program at NASA's Marshall Space Flight Center. The SHARP-B2 payload was carried aboard a U.S. Air Force Minuteman III missile carrying a modified Mk 12A reentry vehicle (RV), which blasted off from Vandenberg Air Force Base near Lompoc, CA, at 3:01 a.m. PDT on Sept. 28. The RV was equipped with four 5. 1 inch-long strakes, or sharp leading edges. Each strake contained three UHTCs: ZrB2/SiC/C; ZrB2/SiC; and HfB2/SiC. Once it reached an altitude of about 400 nautical miles, the RV was released, returning through Earth's atmosphere at speeds exceeding Mach 22. One pair of strakes was designed to retract just before reaching temperatures high enough to cause the material to begin ablating. The other pair was designed to retract shortly after ablation began, at an expected temperature of nearly 5,100 degrees Fahrenheit. Sensors in the strakes measured how closely performance matched pre-flight calculations, and data was successfully collected throughout the 23-minute flight. A parachute was deployed (but not fully inflated) and the RV splashed down in a lagoon at the Kwajalein missile range in the Pacific Ocean. Within 3 hours radar track analysis showed ocean entry to be precisely at the latitude/longitude coordinates estimated during pre-flight simulation. An hour later a ship was deployed by the Army to recover the reentry vehicle, which was recovered in 165 feet of water, just 500 feet from its planned splash-down point. This is the first RV recovery in over a decade.

Salute, Joan↗

Composites: Processing and Fabrication Methodologies of Nonoxide Ceramic Composites. Processing HfB2 Composites for Use in Extreme Environments

HfB2 and ZrB2 composites containing SiC are known to have good thermal shock and configurational stability at elevated temperatures. These are promising ultra-high temperature ceramics (UHTCs) for use on the sharp leading edges of next generation space vehicles. Sharp leading edges on these vehicles will need to: withstand repeated exposures to temperatures > 2200 C in oxidizing environments; have good thermal shock and ablation resistance; and withstand the mechanical stress of launch and reentry. The HfB2/SiC composite is currently undergoing processing improvements in an effort to better the performance of a material that has been studied for approx. 35 years. The potential for HfB2/SiC composites to meet the requirements of hypersonic flight depends on controlling processing techniques. This presentation will focus on understanding processing steps now being undertaken to optimize the material properties of HfB2/SiC composites at NASA Ames Research Center. Correlation between processing techniques and microstructure will be shown. Preliminary oxidation studies will also be discussed.

Gusman, Michael I.↗

Evaluation of Ultra-High Temperature Ceramics for Aeropropulsion Use

Among the ultra-high temperature ceramics (UHTC) are a group of materials consisting of zirconium diboride or hafnium diboride plus silicon carbide, and in some instances, carbon. These materials offer a good combination of properties that make them candidates for airframe leading edges on sharp-bodied reentry vehicles. These UHTC perform well in the environment for such applications, i.e., air at low pressure. The purpose of this study was to examine three of these materials under conditions more representative of a propulsion environment, i.e., higher oxygen partial pressure and total pressure. Results of strength and fracture toughness measurements, furnace oxidation and high velocity thermal shock exposures are presented for ZrB2 plus 20 volume % SiC, ZrB2 plus 14 volume % SiC plus 30 volume % C, and SCS-9a SiC fiber reinforced ZrB2 plus 20 volume % SiC. The poor oxidation resistance of UHTCs is the predominant factor limiting their applicability to propulsion applications.

Levine, Stanley R.↗

Sharp Hypervelocity Aerodynamic Research Probe

The objective of this flight demonstration is to deploy a slender-body hypervelocity aerodynamic research probe (SHARP) from an orbiting platform using a tether, deorbit and fly it along its aerothermal performance constraint, and recover it intact in mid-air. To accomplish this objective, two flight demonstrations are proposed. The first flight uses a blunt-body, tethered reentry experiment vehicle (TREV) to prove out tethered deployment technology for accurate entries, a complete SHARP electronics suite, and a new soft mid-air helicopter recovery technique. The second flight takes advantage of this launch and recovery capability to demonstrate revolutionary sharp body concepts for hypervelocity vehicles, enabled by new Ultra-High Temperature Ceramics (UHTCs) recently developed by Ames Research Center. Successful demonstration of sharp body hypersonic vehicle technologies could have radical impact on space flight capabilities, including: enabling global reentry cross range capability from Station, eliminating reentry communications blackout, and allowing new highly efficient launch systems incorporating air breathing propulsion and zeroth staging.

Bull, Jeffrey↗

The NASA Sharp Flight Experiment

The Slender Hypersonic Aerothermodynamic Research Program (SHARP) was initiated by NASA Ames, and executed in partnership with Sandia National Laboratory and the US Air Force, to demonstrate sharp, passive leading edge designs for hypersonic vehicles, incorporating new ultra-high temperature ceramics (UHTC's). These new ceramic composites have been undergoing development, characterization and ground testing at NASA Ames for the last nine years. This paper will describe the background, flight objectives, design and pertinent flight results of SHARP, and some of the potential implications for future hypersonic vehicle designs.

Rasky, Daniel J.↗

Ultra-high Temperature Ceramic Composites for Leading Edges

Ultra-high temperature ceramics (UHTC) have performed unreliably due to material flaws and attachment design. These deficiencies are brought to the fore by the low fracture toughness and thermal shock resistance of UHTC. If these deficiencies are overcome, we are still faced with poor oxidation resistance as a limitation on UHT applicability to reusable launch vehicles. We have been addressing the deficiencies of UHTC for the past two years via a small task at GRC that is in the Airframe part of the Next Generation Launch Technology Program. Our focus is on composite constructions and functional grading to address the mechanical issues and on composition modification to address the oxidation issue. The progress on approaches to improving oxidation resistance by alloying and functional grading will be reported. In particular, initial tests of tantalum additions have shown potential for major improvement. Less promising results of additional tests at higher temperatures will be presented. Two fabrication approaches are being pursued to produce carbon fiber reinforced UHTC composites: prepregging and rigid perform infiltration. Fabrication procedures and microstructures for composites will be reported.

Levine, Stanley R.↗

Ultra-High Temperature Ceramic Composites for Leading Edges

Ultra-high temperature ceramics (UHTC) have performed unreliably due to material flaws and attachment design. These deficiencies are brought to the fore by the low fracture toughness and thermal shock resistance of UHTC. If these deficiencies are overcome, we are still faced with poor oxidation resistance as a limitation on UHTC applicability to reusable launch vehicles. We have been addressing the deficiencies of UHTC for the past two years via a small task at GRC that is in the Airframe part of the Next Generation Launch Technology Program. Our focus is on composite constructions and functional grading to address the mechanical issues and on composition modification to address the oxidation issue. The progress on approaches to improving oxidation resistance by alloying and functional grading will be reported. In particular, initial tests of tantalum additions have shown potential for major improvement. Results for additional tests at higher temperatures will be presented. These oxidation improvements are being incorporated in the composites approaches. Two fabrication approaches are being persued to produce carbon fiber reinforced UHTC composites: prepregging and rigid perform infiltration. Fabrication procedures, microstructures, and initial mechanical property and oxidation results for composites will be reported.

Levine, Stanley R.↗

Characterization of an Ultra-High Temperature Ceramic Composite

Ultra-high temperature ceramics (UHTC) are of interest for hypersonic vehicle leading edge applications. Monolithic UHTCs are of concern because of their low fracture toughness and brittle behavior. UHTC composites (UHTCC) are being investigated as a possible approach to overcome these deficiencies. In this study a small sample of a UHTCC was evaluated by limited mechanical property tests, furnace oxidation exposures, and oxidation exposures in a flowing environment generated by an oxy-acetylene torch. The composite was prepared from a carbon fiber perform using ceramic particulates and a pre-cerns about microcracking due to thermal expansion mismatch between the matrix and the carbon fiber reinforcements, and about the oxidation resistance of the HfB2-SiC coating layer and the composite constituents. However, positive performance in the torch test warrants further study of this concept.

Levine, Stanley R.↗

Oxidation of ZrB2-and HfB2-Based Ultra-High Temperature Ceramics: Effects of Ta Additions

Several compositions of ZrB2- and HfB2-based Ultra-High Temperature Ceramics (UHTC) were oxidized in stagnant air at 1627 C in ten minute cycles for times up to 100 minutes. These compositions include: ZrB2 - 20v% SiC, HfB2 - 20v% SiC, ZrB2 - 20v% SiC - 20v% TaSi2, ZrB2 - 33v% SiC, HfB2 - 20v% SiC - 20v% TaSi2, and ZrB2 - 20v% SiC - 20v% TaC. The weight change due to oxidation was recorded. The ZrB2 - 20v% SiC - 20v% TaSi2 composition was also oxidized in stagnant air at 1927 C and in an arc jet atmosphere. Samples were analyzed after oxidation by x-ray diffraction, field emission scanning electron microscopy, and energy dispersive spectroscopy to determine the reaction products and to observe the microstructure. The ZrB2 - 20v% SiC - 20v% TaSi2 showed the lowest oxidation rate at 1627 C, but performed poorly under the more extreme tests due to liquid phase formation. Effects of Ta-additions on the oxidation of the diboride-based UHTC are discussed.

Opila, Elizabeth↗

Issues for Ultra-High Temperature Composites

Ultra-high temperature ceramics (UHTC) have performed unreliably due to material flaws and attachment design. These deficiencies are brought to the fore by the low fracture toughness and thermal shock resistance of UHTC. In addition, poor oxidation resistance is a limitation on UHTC applicability to reu'sable launch vehicles. We have been addressing these deficiencies by investigating methods for improving the oxidation resistance of UHTC and by evaluating the performance of an early polymer precursor derived UHTC composite. Processing, mechanical property, and furnace oxidation and oxyacetylene torch exposure results are reported. From these results guidelines for UHTC composite architecture, constituents, and processing are developed.

Levine, Stanley R.↗

Characterization of a Ultra-high Temperature Ceramic Composite

Ultra-high temperature ceramics (UHTC) are of interest for hypersonic vehicle leading edge applications. Monolithic UHTCs are of concern because of their low fracture toughness and brittle behavior. UHTC composites (UHTCC) are being investigated as a possible approach to overcome these deficiencies. In this study a small sample of a UHTCC was evaluated by limited mechanical property tests, furnace oxidation exposures, and oxidation exposures in a flowing environment. The composite was prepared from a carbon fiber perform using ceramic particulates and a preceramic polymer. The as-received composite plate was non-uniform from front to back surface. Plate dimensions were 150 x 150 x 6 mm. The back surface had a fibrous, uniform appearance; XRD analysis revealed the presence of Sic and C. The front surface was smooth and non-uniform in appearance with evidence of a coarse grain structure produced by a liquid phase; XRD analysis revealed the presence of HfB2. Microcracks were present throughout the thickness as one might expect from a carbon fiber reinforced composite with attendant large thermal expansion mismatch between the matrix phases and the fibers. The HfB2 phase on the front surface was comparable in thickness to a fiber ply or about 0.6 mm, and surface microcracks were evident. Limited four point flexural tests were carried out at span to depth ratios of approximately 14 and 16 with markedly different results. Tests were run with the front or the back surface in tension. At the shorter span to depth failures occurred under a loading pin for both orientations. At a span to depth of 16 failures occurred in the center of the span with fracture clearly initiating from a tensile failure. Ultimate flexural strength, strain at ultimate stress, stress and strain at deviation from linear elastic behavior are reported. Strains at ultimate stress ranged from about 0.6 to 0.7 % for the back surface in tension, and 0.4 to 0.6 for the front surface in tension. At constant span to depth the strain at ultimate stress was about 0.2% greater for the back surface in tension and the ultimate strength was also higher. Strengths were in line with predictions from theory. Furnace oxidation studies were carried out at 1627 and 1927OC in a static furnace environment using ten minute cycles and one, five, and ten cycles. Limited oxidation studies were also carried out in a flowing oxyacetylene torch environment. Specimens were photographed, and weight and dimensional changes were determined. XRD and SEM characterizations were performed. Weight losses were attributed primarily to carbon fiber oxidation. The composite survived the torch test with little visible distress. Further details will be determined once metallographic studies are completed.

Levine, Stanley R.↗

Evaluation of Ultra-High Temperature Ceramics for Propulsion Application

Ultra-high temperature ceramic (UHTC) materials consisting of zirconium diboride or hafnium diboride plus silicon carbide offer a combination of properties that make them candidates for airframe leading edges on sharp-bodied reentry vehicles. These UHTC perform well in the environment for such applications, i.e. low pressure air. The purpose of this study was to examine three of these materials under conditions more representative of a propulsion environment, i.e. higher oxygen and total pressure. Results of stren$h and fracture toughness measurements, furnace oxidation, and thermal shock exposures are presented. The poor oxidation resistance of UHTCs is the predominant factor limiting their applicability to propulsion.

Levine, Stanley R.↗

NASA Glenn Research Center UEET (Ultra-Efficient Engine Technology) Program: Agenda and Abstracts

Topics discussed include: UEET Overview; Technology Benefits; Emissions Overview; P&W Low Emissions Combustor Development; GE Low Emissions Combustor Development; Rolls-Royce Low Emissions Combustor Development; Honeywell Low Emissions Combustor Development; NASA Multipoint LDI Development; Stanford Activities In Concepts for Advanced Gas Turbine Combustors; Large Eddy Simulation (LES) of Gas Turbine Combustion; NASA National Combustion Code Simulations; Materials Overview; Thermal Barrier Coatings for Airfoil Applications; Disk Alloy Development; Turbine Blade Alloy; Ceramic Matrix Composite (CMC) Materials Development; Ceramic Matrix Composite (CMC) Materials Characterization; Environmental Barrier Coatings (EBC) for Ceramic Matrix Composite (CMC) Materials; Ceramic Matrix Composite Vane Rig Testing and Design; Ultra-High Temperature Ceramic (UHTC) Development; Lightweight Structures; NPARC Alliance; Technology Transfer and Commercialization; and Turbomachinery Overview; etc.

Manthey, Lri↗

Comparative neutron-irradiation effects on thermal conductivity degradation and dimensional stability of TiC, TiB 2 , and ZrB 2 at 200–1000 °C

Ultra-high-temperature ceramics (UHTCs), including TiC, Ti 11 B₂, and Zr 11 B₂, show great potential for plasma-facing components due to their excellent high-temperature properties prior to irradiation. However, their response to neutron irradiation remains insufficiently understood, limiting robust assessment of their viability for fusion energy applications. Here, this study examines the thermal conductivity, dimensional stability and microstructure of TiC, TiB₂, and ZrB₂ following neutron irradiation at temperatures of 200–1000 °C and fast neutron fluences of 2.0 × 10 25 to 1.1 × 10 26 n/m 2 (E > 0.1 MeV). Lattice swelling measured by synchrotron X-ray diffraction in all three UHTCs was maximized at 200 °C and decreased with increasing irradiation temperature, with no evidence of amorphization observed at 200 °C. Above 600 °C, significant macroscopic volume swelling was observed in irradiated Ti 11 B₂ and Zr 11 B₂, but not in TiC, likely due to cavity formation in the diborides. The post-irradiation thermal conductivity, measured at the irradiation temperature, ranged from 28 to 45 W/m·K, representing a 34–45% reduction relative to the unirradiated material. Notably, neutron-irradiated UHTCs exhibit recoverable thermal conductivity at elevated temperatures, comparable to ferritic–martensitic steels and potentially superior to W when transmutation effects are considered, highlighting promise for shielding or armor plasma-facing components. At 600 °C, both thermal conductivity degradation and lattice swelling saturated at doses exceeding 2–4 dpa.

fusion materials↗

Oxidation of Ultra-High Temperature Ceramics in Water Vapor

Ultra high temperature ceramics (UHTCs) including HfB2 + SiC (20% by volume), ZrB2 + SiC (20% by volume) and ZrB2 + SiC (14% by volume) + C (30% by volume) have historically been evaluated as reusable thermal protection systems for hypersonic vehicles. This study investigates UHTCs for use as potential combustion and aeropropulsion engine materials. These materials were oxidized in water vapor (90%) using a cyclic vertical furnace at 1 atm. The total exposure time was 10 hours at temperatures of 1200, 1300, and 1400 C. CVD SiC was also evaluated as a baseline comparison. Weight change measurements, X-ray diffraction analyses, surface and cross-sectional SEM and EDS were performed. These results will be compared with tests ran in static air at temperatures of 1327, 1627, and 1927 C. Oxidation comparisons will also be made to the study by Tripp. A small number of high pressure burner rig (HPBR) results at 1100 and 1300 C will also be discussed. Specific weight changes at all three temperatures along with the SIC results are shown. SiC weight change is negligible at such short duration times. HB2 + SiC (HS) performed the best out of all the tested UHTCS for all exposure temperatures. ZrB2 + Sic (ZS) results indicate a slightly lower oxidation rate than that of ZrBl + SiC + C (ZCS) at 1200 and 1400 C, but a clear distinction can not be made based on the limited number of tested samples. Scanning electron micrographs of the cross-sections of all the UHTCs were evaluated. A representative area for HS is presented at 1400 C for 26 hours which was the composition with the least amount of oxidation. A continuous SiO2 scale is present in the outer most edge of the surface. An image of ZCS is presented at 1400 C for 10 hours, which shows the most degradation of all the compositions studied. Here, the oxide surface is a mixture of ZrSiO4, ZrO2 and SO2.

Nguyen, QuynhGiao N.↗