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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.
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Rare-earth chalcogenides and boron-rich borides show promise. Report discusses search for materials performing more efficiently in high-temperature thermoelectric conversion. Begins with summary of developments during past three decades. Followed by brief introduction to theory of thermoelectric energy conversion, then by experimental findings and by some additional theory on specific materials.
The interest of NASA in the application of ceramics in heat engines is reviewed. This interest started in the early 1950s with attempts to apply oxides, borides, and cermets as gas turbine components. These attempts, as other similar efforts around the world at that time, generally met with failure due to the brittle nature of the materials and a lack of understanding of how to accommodate brittleness by appropriate design approaches. More recent efforts of the 1970s have concentrated on the silicon nitride and silicon carbide family of ceramics. This class of materials demonstrated thermal stability and thermal shock resistance in gas turbine environments. Subsequent programs funded by the DOE and managed by NASA have demonstrated great strides in material fabricability and the application of FEM design concepts. However, the materials remain brittle and lacking in reliability and reproducibility. This reliability/reproducibility problem is viewed as the major current impediment to the application of ceramics in heat engines; approaches to its solution are discussed.
Report reviews recent theoretical and experimental research on thermoelectric materials. Recent work with narrow-band semiconductors demonstrated possibility of relatively high thermoelectric energy-conversion efficiencies in materials withstanding high temperatures needed to attain such efficiencies. Among promising semiconductors are boron-rich borides, especially boron carbides.
Demanding tribological properties are required of the materials used for the sliding seal between the sidewalls and the lower wall of the variable area hypersonic engine. Temperatures range from room temperature and below to operating temperatures of 1000 C in an environment of air, hydrogen, and water vapor. Candidate sealing materials for this application are an alumina-boria-silicate, ceramic, fabric rope sliding against the engine walls which may be made from copper- or nickel-based alloys. Using a pin-on-disk tribometer, the friction and wear properties of some of these potential materials and possible lubrication methods are evaluated. The ceramic fabric rope displayed unacceptably high friction coefficients (0.6 to 1.3) and, thus, requires lubrication. Sputtered thin films of gold, silver, and CaF2 reduced the friction by a factor of two. Sprayed coatings of boride nitride did not effectively lubricate the fabric. Static heat treatment tests at 950 C indicate that the fabric is chemically attacked by large quantities of silver, CaF2, and boron nitride. Sputtered films or powder impregnation of the fabric with gold may provide adequate lubrication up to 1000 C without showing any chemical attack.
Thermoelectric energy conversion utilizing nuclear heat sources has been employed for several decades to generate power for deep space probes. In the past, lead telluride and, more recently, silicon-germanium alloys have been the prime choices as thermoelectric materials for this application. Currently, a number of refractory semiconductors are under investigation at the Jet Propulsion Laboratory in order to produce power sources of higher conversion efficiency and, thus, lower mass per unit of power output. Included among these materials are improved Si-Ge alloys, rare earth compounds and boron-rich borides. The criteria used to select thermoelectric materials, in general, and the above materials, in particular, will be discussed. The current state of the art and the accomplishments to date in thermoelectric materials research will be reviewed.
Chemical compatibility of several reinforcement materials with FeAl alloys within the concentration range 40 to 50 at pct Al have been analyzed from thermodynamic considerations at 1173 and 1273 K. The reinforcement materials considered in this study include carbides, borides, oxides, nitrides, and silicides. Although several chemically compatible reinforcement materials are identified, the coefficients of thermal expansion for none of these materials match closely with that of FeAl alloys and this might pose serious problems in the design of composite systems based on FeAl alloys.
Chemical compatibility of several reinforcement materials with beta phase NiAl alloys within the concentration range 40 to 50 at. percent Al have been analyzed from thermodynamic considerations at 1373 and 1573 K. The reinforcement materials considered in this study include carbides, borides, oxides, nitrides, beryllides, and silicides. Thermodynamic data for NiAl alloys have been reviewed and activity of Ni and Al in the beta phase have been derived at 1373 and 1573 K. Criteria for chemical compatibility between the reinforcement material and the matrix have been defined and several chemically compatible reinforcement materials have been defined.
Chemical compatibility of several reinforcement materials with three niobium aluminides, Nb3Al, Nb2Al, and NbAl3, were examined from thermodynamic considerations. The reinforcement materials considered in this study include carbides, borides, nitrides, oxides, silicides, and Engel-Brewer compounds. Thermodynamics of the Nb-Al system were reviewed and activities of Nb and Al were derived at desired calculation temperatures. Criteria for chemical compatibility between the reinforcement material and Nb-Al compounds have been defined and several chemically compatible reinforcement materials have been identified.
Electrocatalysts and supports for the positive electrode of moderate temperature single-unit rechargeable alkaline fuel cells are being investigated and developed. Candidate support materials were drawn from transition metal carbides, borides, nitrides and oxides which have high conductivity (greater than 1 ohm/cm). Candidate catalyst materials were selected largely from metal oxides of the form ABO sub x (where A = Pb, Cd, Mn, Ti, Zr, La, Sr, Na, and B = Pt, Pd, Ir, Ru, Ni (Co) which were investigated and/or developed for one function only, O2 reduction or O2 evolution. The electrical conductivity requirement for catalysts may be lower, especially if integrated with a higher conductivity support. All candidate materials of acceptable conductivity are subjected to corrosion testing. Materials that survive chemical testing are examined for electrochemical corrosion activity. For more stringent corrosion testing, and for further evaluation of electrocatalysts (which generally show significant O2 evolution at at 1.4 V), samples are held at 1.6 V or 0.6 V for about 100 hours. The surviving materials are then physically and chemically analyzed for signs of degradation. To evaluate the bifunctional oxygen activity of candidate catalysts, Teflon-bonded electrodes are fabricated and tested in a floating electrode configuration. Many of the experimental materials being studied have required development of a customized electrode fabrication procedure. In advanced development, the goal is to reduce the polarization to about 300 to 350 mV. Approximately six support materials and five catalyst materials were identified to date for further development. The test results will be described.
Rapid solidification processing has been successfully used to create a uniform distribution of 30-nm TiB2 and HfC precipitates in a B2-ordered NiAl matrix, in order to enhance the matrix material's high-temperature strength and creep behavior. Attention is drawn to the question of the stability of carbide and boride dispersoids in an NiAl matrix during high-temperature exposures. The present alloys were consolidated at temperatures above 1422 K; the small size of precipitates in materials processed at such high temperatures gives an indication of their thermal stability, and further coarsening of the precipitates at elevated service temperatures is rendered unlikely by their low solubility in the matrix.
Demanding tribological properties are required of the materials used for the sliding seal between the sidewalls and the lower wall of the variable area hypersonic engine. Temperatures range from room temperature and below to operating temperatures of 1000 C in an environment of air, hydrogen, and water vapor. Candidate sealing materials for this application are an alumina-boria-silicate, ceramic, fabric rope sliding against the engine walls which may be made from copper- or nickel-based alloys. Using a pin-on-disk tribometer, the friction and wear properties of some of these potential materials and possible lubrication methods are evaluated. The ceramic fabric rope displayed unacceptably high friction coefficients (0.6 to 1.3) and, thus, requires lubrication. Sputtered thin films of gold, silver, and CaF2 reduced the friction by a factor of two. Sprayed coatings of boride nitride did not effectively lubricate the fabric. Static heat treatment tests at 950 C indicate that the fabric is chemically attacked by large quantities of silver, CaF2, and boron nitride. Sputtered films or powder impregnation of the fabric with gold may provide adequate lubrication up to 1000 C without showing any chemical attack.
Tensile tests on splat-quenched Ni3Al-Cr alloys showed a sharp decrease in ductility with long-time annealing. The growth of the initially very-fine-size anti-phase domains showed a tenuous correlation with ductility up to a critical size, where ductility was lost. The grain size was relatively unaffected by these annealing treatments, but the grain-boundary curvature decreased, implying less toughness. An important observation was that, for the longest annealing time, a chromium-rich precipitate formed, which the data indicate could be a boride. Miniaturized tensile tests were performed on samples which were all obtained from the same splat-quenched foil, and the various domain sizes were controlled by subsequent annealing treatments.
Aluminide-base intermetallic matrix composites are currently being considered as potential high-temperature materials. One of the key factors in the selection of a reinforcement material is its chemical stability in the matrix. In this study, chemical interactions between iron aluminides and several potential reinforcement materials, which include carbides, oxides, borides, and nitrides, are analyzed from thermodynamic considerations. Several chemically compatible reinforcement materials are identified for the iron aluminides with Al concentrations ranging from 40 to 50 at. pct.
Chemical compatibility of several reinforcement materials with three niobium aluminides, Nb3Al, Nb2Al, and NbAl3, were examined from thermodynamic considerations. The reinforcement materials considered in this study include carbides, borides, nitrides, oxides, silicides, and Engel-Brewer compounds. Thermodynamics of the Nb-Al system were reviewed and activities of Nb and Al were derived at desired calculation temperatures. Criteria for chemical compatibility between the reinforcement material and Nb-Al compounds have been defined and several chemically compatible reinforcement materials have been identified.
The absence of gravity allows containerless processing of materials which could not otherwise be processed. High melting point, hard materials such as borides, nitrides, and refractory metals are usually brittle in their crystalline form. The absence of dislocations in amorphous materials frequently endows them with flexibility and toughness. Systematic studies of the properties of many amorphous materials have not been carried out. The requirements for their production is that they can be processed in a controlled way without container interaction. Containerless processing in microgravity could permit the control necessary to produce amorphous forms of hard materials.
An advanced rapid solidification technology for processing reactive and refractory alloys, utilized to produce large quantities of melt-spun filaments of NiAl, is presented. The melt-spun filaments are pulverized to fine particle sizes, and subsequently consolidated by hot extrusion or hot isostatic pressing. Rapid solidification process gives rise to very fine-grained microstructures. However, exposure to elevated temperature during hot consolidation leads to grain growth. Alloying agents such as borides, carbides, and tungsten can pin the grain boundaries and retard the grain growth. Various alloy compositions are investigated. The eventual goal is to utilize the hot-extruded and forged stock to grow single-crystal NiAl blades for advanced gas-turbine engine applications. Single-crystal NiAl, containing a uniform dispersion of carbide strengthening precipitates, is expected to lead to highly creep-resistant turbine blades, and is of considerable interest to the aerospace propulsion industry.
The microstructural development following heat treatments of several rapidly-solidified Ni3Al-Cr and Ni3Al-Cr-B alloys is presented. Depending on composition, the as-solidified samples were either 100 percent gamma-prime phase - in the form of fine antiphase domains (APD) - or a mixture of gamma-prime (APDs) and beta phases. Upon annealing, the as-solidified microstructures transform to either APD-free gamma-prime or mixtures of gamma and gamma-prime phases. For those compositions where the quenched microstructures were 100 percent gamma-prime it was observed that APD coarsening followed conventional grain-growth kinetics, but when gamma phase precipitated on the APD boundaries the rate constant changed abruptly while the time exponent remained unaffected. It was also found that alloys containing critical amounts of chromium and boron are susceptible to precipitation of the boride Cr5B3.
Chemical compatibility between Fe-19.8Cr-4.8Al (weight percent), which is the base composition for the commercial superalloy MA956, and several carbides, borides, nitrides, oxides, and silicides was analyzed from thermodynamic considerations. The effect of addition of minor alloying elements, such as Ti, Y, and Y2O3, to the Fe-Cr-Al alloy on chemical compatibility between the alloy and various compounds was also analyzed. Several chemically compatible compounds that can be potential reinforcement materials and/or interface coating materials for Fe-Cr-Al based composites were identified.