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Ceramic oxide compositions as high temperature thermal energy storage materials
In order to test their reactivity with Atomic Oxygen, twenty five materials were flown on the EOIM-3 (Evaluation of Oxygen Interactions with Materials) portion of the STS-46 Mission. These materials include refractory metals, candidate insulation materials, candidate radiator coatings, and a selection of miscellaneous materials. This report documents the results of the pre- and post-flight analysis of these materials.
Space power system material compatibility tests of selected refractory metal alloys with boiling potassium
Turbogenerator material compatibility tests of niobium and tantalum alloys with boiling potassium
NASA, DoD, and industry have a vision for reusable hypersonic vehicles (Mach > 5). The realization of this vision will require high-specific-strength, high-temperature, reusable structures. In the sub-sonic and super-sonic flight regimes, high-specific-strength structures can be obtained via the use of aluminum, titanium, and composite materials. In the high-temperature environments associated with hypersonic flight, high specific strength is obtained via refractory-composite materials. NASA Langley Research Center has multiple efforts focused on evaluating refractory-composites for use as airframe hot structures for reusable hypersonic vehicles. Current efforts span the entire building-block approach, including coupon, element, subcomponent, and component manufacturing and testing. The coupon level work includes progressive damage testing and analysis, restrained thermal growth testing, stressed oxidation testing, and evaluation of laminate properties for several layup architectures. Element testing includes evaluation of over-temperature capability and co-processed bonding, fastener development, and analysis and testing of beaded (corrugated) panels. Subcomponent level work includes a solid rocket motor booster fin and a portion of a control surface, and component level work includes a control surface static test article. The current presentation will provide an update of work being performed at NASA, which is expected to transition refractory-composite materials to reusable hypersonic vehicles.
We have examined the physical and chemical processes which accompany the propagation of a J-type shock through molecular astrophysical gas of density 10(exp 7.5) - 10(exp 12) H nuclei per cu cm. Our study is primarily relevant to the high-density accretion shocks which are associated with the supersonic infall of material during the collapse of a molecular cloud core to form a protostar. We have carried out a general parameter study to determine the characteristic infrared emission spectrum of dense molecular shocks and the extent of grain destruction within such shocks as a function of relevant shock parameters. Accretion shocks with mass accretion rates approximately greater than 10(exp -5) solar masses per y are plausible sources of the CO v = 2-0 vibrational band emission observed in many protostars, at least for sources of moderate CO v = 2-0 luminosity (approximately less than few x 10(exp 23) W). Rovibrational emissions from H2O and OH are also predicted to be luminous in dense molecular accretion shocks. Vaporization is the dominant mechanism of grain destruction within dense molecular shocks, leading to the efficient removal of those grains which are heated to their vaporization temperature by the combined effects of radiative heating, drag heating, and thermal heating by the hot postshock gas. The criteria for grain vaporization are obtained for grains composed of several different materials: metallic iron, silicate, troilite, refractory organic materials, volatile organic materials, and water ice.
In the event of a nuclear detonation, actinide and fission product-containing debris can be analyzed to provide information about the nature of the device. In-field sample dissolution prior to transport to a laboratory is critical for reducing the time between an event and delivery of information to decision makers. However, the best dissolution methods utilize liquid strong acid solutions, which are incompatible with field collection Standard Operating Procedure. What is required are solid materials that, when mixed with water in the field, can provide the strong digestion and dissolution properties of nitric and hydrofluoric acids. Fluorohydrogenate ionic liquids have shown a remarkable ability to dissolve a wide range of materials, from refractory actinide oxides to cementitious material such as calcium silicates. These strong dissolution properties are due to the neutral hydrofluoric acid that is bound to the anion component of the ionic liquid. Because these materials are liquids, they are also incompatible with Standard Operating Procedure. However, the physiochemical properties of ionic liquids, such as the melting point, can be readily tuned through minor modification of the molecular structure of the cations and anions. Thus, we hypothesize that by synthesizing modified cations, novel ionic compounds with melting points above ambient but with the same anion and bound hydrofluoric acid – and thus similar digestion and dissolution properties – as current fluorohydrogenate ionic liquids can be produced. These solid materials would be compatible with current Standard Operating Procedure, and would allow for rapid, in-field dissolution of samples, shortening the time to actionable information after an event.
Seeding air flows with particles to enable measurements of gas velocities via laser anemometry and/or particle image velocimetry techniques can be quite exasperating. The seeding requirements are compounded when high temperature environments are encountered and special care must be used in selecting a refractory seed material. The pH stabilization techniques commonly employed in ceramic processing are used to obtain stable dispersions for generating aerosols of refractory seed material. By adding submicron alumina particles to a preadjusted pH solution of ethanol, a stable dispersion is obtained which when atomized produces a high quality aerosol. Commercial grade alumina powder is used with a moderate size distribution. The technique is not limited to alumina/ethanol and is also demonstrated with an alumina/H2O system. Other ceramic powders in various polar solvents could also be used once the point of zero charge (pH(sub pzc)) of the powder in the solvent has been determined.
Carbide-based fuel assembly includes outer structural member of ceramic matrix composite material (e.g., SiC—SiC composite), insulation layer of porous refractory ceramic material (e.g., zirconium carbide with open-cell foam structure or fibrous zirconium carbide), and interior structural member of refractory ceramic-graphite composite material (e.g., zirconium carbide-graphite or niobium carbide-graphite). Spacer structures between various layers provide a defined and controlled spacing relationship. A fuel element bundle positioned between support meshes includes a plurality of distributively arranged fuel elements or a solid, unitary fuel element with coolant channels, each having a fuel composition including high assay, low enriched uranium (HALEU). Fuel assemblies are distributively arranged in a moderator block and the upper end of the outer structural member is attached to a metallic inlet tube for hydrogen propellant and the lower end of the outer structural member is interfaced with a support plate, forming a nuclear thermal propulsion reactor.
Description of arc jet engines, with some of the operational parameters pertinent to the selection of materials
Laser anemometry enables the measurement of complex flow fields via the light scattered from small particles entrained in the flow. In the study of turbomachinery, refractory seed materials are required for seeding the flow due to the high temperatures encountered. In this work we present a pH stabilization technique commonly employed in ceramic processing to obtain stable dispersions for generating aerosols of refractory seed material. By adding submicron alumina particles to a preadjusted pH solution of ethanol, a stable dispersion is obtained which when atomized, produces a high quality aerosol. Commercial grade alumina powder is used with a moderate size distribution. Other metal oxide powders in various polar solvents could also be used once the point of zero charge (pH(pzc)) of the powder in the solvent has been determined. Laser anemometry measurements obtained using the new seeding technique are compared to measurements obtained using Polystyrene Latex (PSL) spheres as the seed material.
The key objective of this project was to develop a new and more efficient methodology for engineering and economically producing optimized robust catalysts for the reduction or elimination of tars in biomass gasification. Whereas current catalyst technology typically disposes thin layers of catalytically-active material onto rigid supports via wet chemistry-based methods, this project investigated novel thermal methods for directly incorporating catalytically active materials onto robust supports as well as novel approaches for incorporating catalytically active materials on and/or within an otherwise inert refractory support material which is then subsequently formed and processed to create a catalytically-active material on all exposed surfaces. Specifically, the focus of this engineered catalyst development was on materials which were derived from, or otherwise related to, olivine-like minerals, due to the inherent attrition resistance and moderate catalytic properties exhibited by natural olivine when used in a fluidized bed biomass gasifier. Task 1 of this project successfully demonstrated the direct thermal impregnation of catalytically-active materials onto an olivine substrate, with the production of a Ni-olivine catalyst. Nickel and nickel oxide were thermally impregnated onto an olivine substrate and when reduced were shown to demonstrate improved catalytic activity over the baseline olivine material and equal the tar-decomposing performance of Ni-olivine catalysts prepared by conventional wet impregnation. Task 2 involved coordination with our subcontracted project partners to further develop and characterize catalyst formulations and to optimize activity and production methods. Within this task, several significant new materials were developed. NexTech Materials developed a sintered ceramic nickel-magnesium-silicate catalyst that demonstrated superb catalytic activity and high resistance to deactivation by H2S. Alfred University developed both supported and integrated (bulk) catalysts via a glass-ceramic processing route which were shown to exhibit excellent catalytic activity and superior resistance to attrition deactivation. With the discovery of these active, robust, glass-based catalysts, and with the permission of the project officer, the investigation of waste-based materials as originally proposed for Task 3 and pilot-scale testing proposed in Task 5 were deferred indefinitely in favor of further investigation of the glass-ceramic based catalyst materials. This choice was justified in part because during FY 2006 and through FY 2007, funding restrictions imposed by congressional budget choices significantly reduced funding for DOE biomass-related projects. Funding for this project was limited to what had been authorized which slowed the pace of project work at GTI so that our project partners could continue in their work. Thereafter, project work was allowed to resume and with restored funding, the project continued and concentrated on the development and testing of glass-ceramic catalysts in bulk or supported formats. Work concluded with a final development devoted to increasing the surface area of glass-ceramic catalysts in the form of microspheres. Following that development, project reporting was completed and the project was concluded.
The behavior of refractory hafnium and zirconium based materials are being investigated at NASA Ames as part of ongoing research aimed at developing superior heat resistant materials for aerospace applications. Hafnium and zirconium diboride based materials have shown high temperature capabilities in simulated reentry environments indicating that these materials may successfully operate as reusable oxidation resistant components for leading edge applications. Due to the refractory nature of these materials, processing of fine-grained uniform microstructures poses a number of challenges. To better understand the process-property-microstructure relationship, processing of these materials has been carried out with conventional hot pressing in addition to the novel approach of Spark Plasma Sintering (SPS). The two processing methods are compared and contrasted in an evaluation of the sintering behavior of high temperature diboride based materials and preliminary physical and mechanical properties are presented.
Research work concerning the metallic portion of the shuttle-orbiter heat shield (expected to experience temperatures up to 2500 F) is described. The five metals being evaluated are TD-Ni-Cr, Cb-C129Y, Cb752, Hayes 188, and Inconel 625. Brazing techniques whereby pairs of these materials are joined into thin-membered assemblies for heat shield applications are described. Results obtained with the vacuum-furnace brazing process are examined. In addition, the use of brazed aluminum-boron metal-matrix-contoured composite structures for heat shield applications is evaluated.
Advanced Rankine and other proposed space power systems utilize refractory metals in contact with both single-phase and two-phase alkali metals at elevated temperatures. A number of recent compatibility experiments are described which emphasize the excellent compatibility of refractory metals with the alkali metals, lithium, sodium, and potassium, under a variety of environmental conditions. The alkali metal compatibilities of tantalum-, columbium-, molybdenum-, and tungsten-base alloys are discussed.
The refractory inclusions embedded in the matrix of many carbonaceous and some ordinary or enstatite chondrites exhibit mineralogical and bulk composition characteristics which correlate with the first, or highest-temperature, condensation products that have been predicted to form from a hot, but cooling, solar nebula. These inclusions' isotopic compositions indicate presolar nucleosynthetic processes that have contributed to the production of the elements from which the solar system was formed; subsequently, the inclusions experienced melting, recrystallization, and alteration histories that have obscured the formation processes.
Optical techniques for high temperature emittance and reflectance studies of ablation material char
Optical metasurfaces are judicously engineered electromagnetic interfaces that can control and manipulate many of light’s quintessential properties, such as amplitude, phase, and polarization. These artificial surfaces are composed of subwavelength arrays of optical antennas that experience resonant light-matter interaction with incoming electromagnetic radiation. Their ability to arbitrarily engineer optical interactions has generated considerable excitement and interest in recent years and is a promising methodology for miniaturizing optical components for applications in optical communication systems, imaging, sensing, and optical manipulation. However, development of optical metasurfaces requires progress and solutions to inherent challenges, namely large losses often associated with the resonant structures; large-scale, complementary metal-oxide-semiconductor-compatible nanofabrication techniques; and incorporation of active control elements. Furthermore, practical metasurface devices require robust operation in high-temperature environments, caustic chemicals, and intense electromagnetic fields. Although these challenges are substantial, optical metasurfaces remain in their infancy, and novel material platforms that offer resilient, low-loss, and tunable metasurface designs are driving new and promising routes for overcoming these hurdles. In this review, we discuss the different material platforms in the literature for various applications of metasurfaces, including refractory plasmonic materials, epitaxial noble metal, silicon, graphene, phase change materials, and metal oxides. We identify the key advantages of each material platform and review the breakthrough devices that were made possible with each material. Finally, we provide an outlook for emerging metasurface devices and the new material platforms that are enabling such devices.