High temperature protective coatings for refractory metals Progress report
Microbend tester and heat-treating apparatus development for study of high temperature protective coatings for refractory metals
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Microbend tester and heat-treating apparatus development for study of high temperature protective coatings for refractory metals
High temperature research on creep rupture strength of refractory metal fiber and nickel alloy composites
Available creep data for the refractory-metal alloys C-103 (Nb/10 percent Hf/1 percent Ti/0.7 percent Zr), ASTAR-811C (Ta/8 percent W/1 percent Re/0.7 percent Hf/0.025 percent C), W-5Re (W/5 percent Re), and W-25Re (W/25 percent Re) were correlated by the Orr-Sherby-Dorn method and extrapolated to 1 percent creep over 10 years. Useful life was specified to be 2 standard estimates of error below the mean surface through the data. Over the temperature range of 1200 to 1800 K, ASTAR-811C was found to be the strongest of these alloys. In particular, ASTAR-811C was found to have at 1800 K the same creep strength as W-25Re at 1420 K. The difference between these results and those of Horak and Booker likely devolves from the comparative lack of long-time data on tungsten alloys.
Stress rupture and tensile properties of refractory metal wires at 2000 and 2200 deg F
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.
We report ground-state structures and phase transitions in Σ5[001] tilt grain boundaries (GBs) in body-centered-cubic (bcc) refractory metals Nb, Ta, Mo, and W. Σ5 tilt GBs have been extensively investigated over the past several decades, with their ground-state structure—composed of kite-shaped structural units—previously thought to be well understood. By performing a rigorous GB structure search that optimizes the number of atoms in the boundary core, we predict different quasiaperiodic “split kite” phases analogous to those previously found in GBs in face-centered-cubic metals. Furthermore, our results suggest that complex aperiodic phases of GBs appear to be a general phenomenon, as validated through density functional theory calculations. Moreover, the atoms in the split kite phase demonstrate distinct collective diffusion dynamics. Phase-contrast image simulations of split kites show better agreement with experimental observations, offering an alternative explanation for previous microscopy results and motivating future atomically resolved imaging of the GB structure.
Data on binary-metal eutectics and melting-point minimums have been assembled for use in selecting brazing filler compositions for refractory metals. Data are presented in four tables for ready reference. Brief discussion of problems and potentials of metallides is included in appendix.
A direct-current arc in argon at atmospheric pressure was used to determine effective work functions of refractory metals, including tantalum, tungsten, molybdenum, and niobium. The procedure is experimentally advantageous, because surface cleanliness of the specimen is not critical, high vacuum is not required, and the anode-cathode spacing is not critical. The experimental procedure involves striking an arc to a metal wire cathode to form a melted ball having an emitting area defined by its diameter. The literature melting point of the metal is taken as the emitting temperature. By using these parameters and the known arc current, effective work functions were calculated from the Richardson-Dushman equation. The calculated work functions agree with recommended handbook values to within about 0.1 V and have typical repeatabilities of 0.02 V.
The vacuum plasma spraying (VPS) technique was employed to produce dense and net shaped components of a new tungsten-rhenium (W-Re) refractory metal alloy. The fine grain size obtained using this technique enhanced the mechanical properties of the alloy at elevated temperatures. The alloy development also included incorporation of thermodynamically stable dispersion phases to pin down grain boundaries at elevated temperatures and thereby circumventing the inherent problem of recrystallization of refractory alloys at elevated temperatures. Requirements for such alloys as related to high temperature space propulsion components will be discussed. Grain size distribution as a function of cooling rate and dispersion phase loading will be presented. Mechanical testing and grain growth results as a function of temperature will also be discussed.
Uranium nitride has been under consideration at NASA and the Department of Energy for nuclear thermal propulsion applications intended for deep space exploration vehicles. It is critical to the success of the technology development that the behavior of the fuel system is properly characterized in operational environments. This body of work fabricated ceramic metal composites consisting of uranium ceramic fuel in a molybdenum and molybdenum–tungsten metal matrix, both with and without an exterior molybdenum barrier. Specimens were introduced to a high temperature hydrogen environment and characterized through x-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy to identify characteristic changes. A portion of the specimens was fabricated with a 1.27 mm thick molybdenum barrier in order to isolate the material from the hydrogen environment. Instability of the uranium nitride occurred as low as 2073 K, leading to aggressive instability approaching 2658 K. Carbon reactions with the metal matrix were observed as well as alloying between the uranium and metal matrix constituents. The liquid uranium resulting from the instability of the uranium nitride was observed to attack the grain boundaries of the refractory metal, resulting in the formation of a liquid uranium molybdenum eutectic melt. Specimens encased in a barrier experienced similar results. The authors conclude this is a significant challenge to applications of this cermet at these temperatures. Alternate configurations with resilient hermetic seals or lower temperature applications such as power reactors may have more success.
Application of isotropic pressure or uniaxial strain alters the elastic properties of materials; sufficiently large strains can drive structural transformations. Linear elasticity describes stability against infinitesimal strains, while nonlinear elasticity describes the response to finite deformations. Here, it was previously shown that uniaxial strain along [100] drives refractory metals and alloys towards mechanical instabilities. These include an extensional instability, and a symmetry-breaking orthorhombic distortion caused by a Jahn-Teller-Peierls instability that splays the cubic lattice vectors. Here we analyze these transitions in depth. Eigenvalues and eigenvectors of the Wallace tensor identify and classify linear instabilities in the presence of strain. We show that both instabilities are discontinuous, leading to discrete jumps in the lattice parameters. We provide physical intuition for the instabilities by analyzing the changes in first-principles energy, stress, bond lengths, and angles upon application of strain. Electronic band structure calculations show differential occupation of bonding and antibonding orbitals, driven by the changing bond lengths and leading to the structural transformations. Strain thresholds for these instabilities depend on the valence electron count.
The Thermal Spray Laboratory at NASA's Marshall Space Flight Center has developed and demonstrated a fabrication technique using Vacuum Plasma Spray (VPS) to form structural components from a tungsten/rhenium alloy. The components were assembled into an absorption cavity for a fully-functioning, ground test unit of a solar thermal propulsion engine. The VPS process deposits refractory metal onto a graphite mandrel of the desired shape. The mandrel acts as a male mold, forming the required contour and dimensions of the inside surface of the deposit. Tungsten and tungsten/25% rhenium were used in the development and production of several absorber cavity components. These materials were selected for their high temperature (less than 2500 C) strength. Each absorber cavity comprises 3 coaxial shells with two, double-helical flow passages through which the propellant gas flows. This paper describes the processing techniques, design considerations, and process development associated with forming these engine components.
The Thermal Spray Laboratory at NASA's Marshall Space Flight Center has developed and demonstrated a fabrication technique using Vacuum Plasma Spray (VPS) to form structural components from a tungsten/rhenium alloy. The components were assembled into an absorber cavity for a fully-functioning, ground test unit of a solar then-nal propulsion engine. The VPS process deposits refractory metal onto a graphite mandrel of the desired shape. The mandrel acts as a male mold, forming the required contour and dimensions of the inside surface of the deposit. Tungsten and tungsten/25% rhenium were used in the development and production of several absorber cavity components. These materials were selected for their high temperature (greater than 25000 C [greater than 4530 F]) strength. Each absorber cavity comprises 3 coaxial shells with two, double-helical flow passages through which the propellant gas flows. This paper describes the processing techniques, design considerations, and process development associated with forming these engine components.
Concepts for future space power systems include nuclear and focused solar heat sources coupled to static and dynamic power-conversion devices; such systems must be designed for service lives as long as 30 years, despite service temperatures of the order of 1600 K. Materials are a critical technology-development factor in such aspects of these systems as reactor fuel containment, environmental protection, power management, and thermal management. Attention is given to the prospective performance of such refractory metals as Nb, W, and Mo alloys, W fiber-reinforced Nb-matrix composites, and HfC precipitate-strengthened W-Re alloys.
Because of the import status and essential nature of their use, cobalt, chromium, tantalum, and niobium were identified as strategic and critical in the aerospace industry. NASA's Conservation of Strategic Aerospace Materials (COSAM) program aims to reduce the need for strategic materials used in gas turbine engines. Technological thrusts in two major areas are under way to meet the primary objective of conserving the use of strategic materials in nickelbase superalloys. These thrusts consist of strategic element substitution and alternative material identification. The program emphasizes cooperative research teams involving NASA Lewis Research Center, universities, and industry. The adoption of refractory metals in nickel-base superalloys is summarized including their roles in mechanical strengthening and environmental resistance; current research activities under way in the COSAM Program are presented as well as research findings to date.
Tendency toward gas porosity exploited. Falling through drop tube, fine drops of molten metal lose heat to surroundings, forming hard shells around precipitated gas. Second heating/cooling cycle in drop tube of lower pressure lets gas expand. Process produces smaller shells in greater variety of materials than possible with such current processes as based on hollow-jet instability, dry-chemical blowing or fluid-droplet drying. Shell aspect ratio (ratio of radius to wall thickness) controllable. New process makes shells having diameters smaller than 100 micrometer. There are several candidate shell materials including refractory metals.
Space power requirements for future NASA and other U.S. missions will range from a few kilowatts to megawatts of electricity. Maximum efficiency is a key goal of any power system in order to minimize weight and size so that the space shuttle may be used a minimum number of times to put the power supply into orbit. Nuclear power has been identified as the primary source to meet these high levels of electrical demand. One way to achieve maximum efficiency is to operate the power supply, energy conversion system, and related components at relatively high temperatures. NASA Lewis Research Center has undertaken a research program on advanced technology of refractory metal alloys and composites that will provide baseline information for space power systems in the 1900's and the 21st century. Basic research on the tensile and creep properties of fibers, matrices, and composites is discussed.
Refractory alloys applications to space electric power conversion systems, discussing alkali metal Rankine cycle systems and corrosion and erosion tests