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Experimental investigation identifies materials suitable for use in potassium lubricated turbo-generator journal bearing and shaft applications at high temperatures. Attention is given to nonrefractory metals and alloys, refractory metals and alloys, Fe-Ni-Co bonded carbides, refractory compounds, and refractory metal bonded carbides.
Introduction. Alloys such as aluminum, nickel-base, and austenitic stainless steels are susceptible to solidification cracking during welding and 3D printing. Compositional optimization is one method used to effectively mitigate solidification cracking of those alloy systems. With the surge in hypersonic and in-space propulsion activities, refractory metals (Nb, Mo, Ta, W, and Re) and their alloy derivatives are increasing in importance due to their extreme high melting point and retention of high-temperature strength; however, their chemistry was most typically optimized to promote ductility during mechanical operations such as drawing and forming. Welding of such alloys has been a challenge due to a number of issues including solidification cracking, atmospheric contamination (O, C, and N), as well as a shift in ductile-to-brittle transition to higher temperature following grain growth induced by welding. Compositional optimization of refractory alloys for solidification cracking resistance in particular is desirable as their usage increases with the advent of advanced manufacturing methods such as 3D printing. This work evaluates the effect of compositional variation in refractory metal systems on the solidification cracking susceptibility with the goals of optimizing existing alloys and joining process techniques, and formulating new alloys with increased solidification cracking resistance. Experimental Procedures. A python code was developed in a Jupyter notebook environment (Michael and Sowards, 2023) to facilitate the calculation of crack susceptibility index proposed by Kou (2015). Composition is entered as a single point, or as a 1-D or 2-D array. The notebook calls pycalphad (Otis and Liu, 2017 and Bocklund et al, 2020) to calculate the evolution of fraction solid as a function of temperature (under either Scheil or equilibrium assumptions) and then evaluates steepness of the fraction solid curve near the terminal stage of solidification to predict solidification cracking resistance. Open source thermodynamic databases available at online repositories are used (van de Walle). The process is setup in an automated fashion to generate plots that show variation in solidification cracking susceptibility according to composition on 1-D line plots or 2-D contour plots. The Jupyter notebook and crack susceptibility algorithm was also integrated with a widely used commercial CALPHAD code for validation and alloy exploration. Results and Discussion. The crack susceptibility model was first validated against a series of refractory alloy compositions evaluated in past work which utilized a specialized Varestraint test built inside a vacuum chamber environment (Lessman and Gold, 1971). The alloys tested in the Varestraint apparatus included T-111 (Ta-8W-2Hf), ASTAR-811C (Ta-8W-1Re-0.7Hf-0.025C), FS-85 (Nb-27Ta-10W-1Zr), T-222 (Ta-9.6W-2.4Hf-0.01C), Ta-10W, B-66 (Nb-5Mo-5V-1Zr), and SCb-291 (Nb-10W-10Ta). The initial test of the model showed a strong correlation with empirical Varestraint data, i.e., a Spearman rank correlation between model predictions and hot cracking measurements was observed to be greater than 0.8. Following the validation, a set of refractory metal binary mixtures was investigated to evaluate sensitivity of Nb, Mo, W, and Ta to C, N, and O content. A series of plots were produced that suggest ppmw ranges of C, N, and O where solidification cracking increases significantly and reaches a maximum. Also comparative ranking of each primary refractory metal to each interstitial was produced. For example C produces greater cracking response in Mo whereas O produces greater cracking response in Ta and Nb. Such compositional values have utility in setting limits on pickup of these interstitial elements during welding and printing rather than using a one-size-fits-all approach. Furthermore, the results have use in determining additive powder recycling requirements, which is especially pertinent for refractory metal powders due to their high cost compared to conventional alloys. Another application created thousands of hypothetical alloys within the nominal specified composition range of two widely used refractory alloys C103 (Nb-10Hf-1Ti) and TZM (Mo-0.5Ti-0.1Zr). The cracking index was calculated for the alloys and results were fed into machine learning regression techniques including Multiple Linear Regression, Ridge Regression, and Lasso Regression to determine relative potency each alloying element had on computed solidification cracking index. A series of linear equations were produced that relate composition of C103 and TZM to solidification cracking index. The crack susceptibility of C103 for example is described by an equation of the form: cracking index ~ O + 0.667*C + 0.635*N + 0.00037*Ta – 0.0008*Hf (in wt.%) From that equation, it is clear that O has strong propensity to induce solidification cracking. Interestingly, Hf is shown to reduce calculated cracking response. Finally, realizing the potential of this method to discover new refractory alloy formulations across the period table that have low solidification cracking sensitivity, the code was applied to new untested alloy systems including W-Zr-C, W-Ta-C, and others. Conclusions. In summary, an open source numerical method has been developed using Python code to calculate Kou’s crack susceptibility index. The method was applied to refractory metals which are inherently difficult to study from a weldability testing standpoint since inert shielding gas is not sufficient and welding is typically done in vacuum, especially in light of findings presented here where oxygen has profound influence on solidification cracking. This work revealed the effect of compositional variations on a series of refractory metals and showed the framework defined here will be useful in 1) the development of new alloys that have improved weldability and 3D printability, 2) placing compositional limits on existing alloys, and 3) ensuring adequate controls of manufacturing processes such as 3D printing where powder reuse is critical. Keywords. pycalphad; Python; refractory metals; solidification cracking. References. B. Bocklund et. al. (2020) http://doi.org/10.5281/zenodo.3630657. S. Kou. (2015) https://doi.org/10.1016/j.actamat.2015.01.034. G.G. Lessmann and R.E. Gold. Welding Journal, issue 1, pp. 1-s – 8-s (1971). F.N. Michael and J.W. Sowards. NASA/TM-20230002218 (2023). R. Otis and Z.-K. Liu. (2017) http://doi.org/10.5334/jors.140. A. Van de Wallle et. al. (2018) https://doi.org/10.1016/j.calphad.2018.04.003.
A translucent crystal concentrates and transmits energy to a heat exchanger, which in turn heats a propellant gas, working gas of a dynamic power system, or a thermopile. Materials are the limiting issue in such a system. Central is the durability of the crystal, which must maintain the required chemical, physical/optical, and mechanical properties as it is heated and cooled. This report summarizes available data to date on the materials issues with this system. We focus on the current leading candidate materials, which are sapphire (Al2O3) for higher temperatures and silica (SiO2) for lower temperatures. We use data from thermochemical calculations; laboratory coupon tests with silica and sapphire; and system tests with sapphire. The required chemical properties include low-vapor pressure and interfacial stability with supporting structural materials. Optical properties such as transmittance and index of refraction must be maintained. Thermomechanical stability is a major challenge for a large, single-crystal ceramic and has been discussed in another report. In addition to the crystal, other materials in the proposed system include refractory metals (Nb, Ta, Mo, W, and Re), carbon (C), and high-temperature ceramic insulation. The major issue here is low levels of oxygen, which lead to volatile refractory metal oxides and rapid consumption of the refractory metal. Interfacial reactions between the ceramic crystal and refractory metal are also discussed. Finally, high-temperature ceramic insulating materials are also likely to be used in this system. Outgassing is a major issue for these materials. The products of outgassing are typically reactive with the refractory metals and must be minimized.
From man landing on the moon to a simple satellite being launched into orbit, many incredible space accomplishments have been witnessed by us all. However, what goes un-noticed to the common man is the extensive research and testing that lasts months, years, and even decades. Much of this required research just so happens to take place in the corridors of the Glen Research Center building number 49. In the Advanced Materials division of G.R.C., a number of researchers have the responsibility of discovering which metal, ceramic, or polymer is best for a specific application. Under the guidance of mentor extraordinaire Frank Ritzert, I am involved in many critical projects dealing with refractory metals, two of which I will mention in this report. The Jupiter Icy Moons Orbiter (JIMO) project actually was under full swing back in the 50's and early 60's. To enable the 14 year trek to the icy moons of Europa, Callisto, and Ganymede, nuclear propulsion methods were selected. Due to the extreme temperature of the reactor and the extended time period, a refractory metal would need to be implemented. After years of research and progress, the program was suddenly canceled. About a decade ago, the JIMO project was re-instated and now has a goal for departure around 2014. However, a few obstacles lie in our way concerning the use of refractory metals. In certain areas of the orbiter a joint is required between the refractories and other less dense metals. Two of these joints are with nickel based super alloys. Being an intern for Frank Ritzert, the refractory metals expert, I have the opportunity to develop the best method to braze refractory metals to Nickel 201. This involves the actual brazing, electron microscopy and reporting the results. My second project involves a certain part of the orbiter where Niobium 1Zirconium, a refractory metal, is joined with Hastelloy-X a Ni based metal. Small quantities of oxygen, helium and other impurities in the Ni alloy could diffuse into the Nb1Zr causing imbrittlement and possibly major failure. I will be testing the effects of Hast-X on Nb1Zr in a high temperature for 10, 50, 100, and 500 hours. After the samples are run through the heat treatment, strength and chemistry will be tested and reported. My appreciation for the research that goes behind every project has and will continue to grow. By digging through old documents written in the 50's and 60's, scouring through forgotten closets, and learning from those with experience in the refractory metals, I am bound to have an incredible learning experience here at NASA.
An improvement has been made to the design of the hollow cathode geometry that was created for the rare-earth electron emitter described in Compact Rare Earth Emitter Hollow Cathode (NPO-44923), NASA Tech Briefs, Vol. 34, No. 3 (March 2010), p. 52. The original interior assembly was made entirely of graphite in order to be compatible with the LaB6 material, which cannot be touched by metals during operation due to boron diffusion causing embrittlement issues in high-temperature refractory materials. Also, the graphite tube was difficult to machine and was subject to vibration-induced fracturing. This innovation replaces the graphite tube with one made out of refractory metal that is relatively easy to manufacture. The cathode support tube is made of molybdenum or molybdenum-rhenium. This material is easily gun-bored to near the tolerances required, and finish machined with steps at each end that capture the orifice plate and the mounting flange. This provides the manufacturability and robustness needed for flight applications, and eliminates the need for expensive e-beam welding used in prior cathodes. The LaB6 insert is protected from direct contact with the refractory metal tube by thin, graphite sleeves in a cup-arrangement around the ends of the insert. The sleeves, insert, and orifice plate are held in place by a ceramic spacer and tungsten spring inserted inside the tube. To heat the cathode, an insulating tube is slipped around the refractory metal hollow tube, which can be made of high-temperature materials like boron nitride or aluminum nitride. A screw-shaped slot, or series of slots, is machined in the outside of the ceramic tube to constrain a refractory metal wire wound inside the slot that is used as the heater. The screw slot can hold a single heater wire that is then connected to the front of the cathode tube by tack-welding to complete the electrical circuit, or it can be a double slot that takes a bifilar wound heater with both leads coming out the back. This configuration replaces the previous sheathed heater design that limited the cycling-life of the cathode.
A predictive analytical model is presented for the electrical conductivity of multi-principal-element alloys (MPEAs), including those containing aluminum, transition metals, and refractory metals. Given that the lattice parameter of the Wigner-Seitz cell of an MPEA is similarly variable to a bulk metallic glass, it is postulated that electron scattering can be approximated by a series of two-level systems. Here, the resulting reduced-order model enabled an accurate determination of electrical resistivity and electron thermal conductivity based on the scattering of electrons in a two-level system across a Bloch-potential-based virtual crystal approximation. Model results are compared to experimental four-point probe electrical resistivity measurements between 300 K and 700 K for Al 0.3 CoCrCuFeNi, CoCrFeMnNi, (CoCrFeMnNi) 0.98 W 0.02 , (CoCrFeMnNi) 0.95 W 0.05 , and Nb 4 Ta 4 V 3 Ti, for model validation.
The present paper reports on the fabrication, detailed structural characterizations, and theoretical modeling of titanium nitride (TiN) and its isostructural oxide derivative, titanium oxynitride (TiNO) thin films that have excellent plasmonic properties and that also have the potential to overcome the limitation of noble metal and refractory metals. The TiNO films deposited at 700 °C in high vacuum conditions have the highest reflectance (R = ~ 95%), largest negative dielectric constant (ε 1 = –161), and maximal plasmonic figure of merit (FoM = –ε 1 /ε 2 ) of 1.2, followed by the 600 °C samples deposited in a vacuum (R = ~ 85%, ε 1 = –145, FoM = 0.8) and 700 °C–5 mTorr sample (R = ~ 82%, ε 1 = –8, FoM = 0.3). To corroborate our experimental observations, we calculated the phonon dispersions and Raman active modes of TiNO by using the virtual crystal approximation. From the experimental and theoretical studies, a multilayer optical model has been proposed for the TiN/TiNO epitaxial thin films for obtaining individual complex dielectric functions from which many other optical parameters can be calculated. The advantages of oxide derivatives of TiN are the continuation of similar free electron density as in TiN and the acquisition of additional features such as oxygen-dependent semiconductivity with a tunable bandgap.
Computed tomographic method and apparatus includes an electron or ion beam having a beam axis, a refractory metal disk; at least one slit in the refractory metal disk that receive the beam, wherein the slit is at an angle to the beam axis; a beam entrance opening in the slit that allows the beam to enter; an effective beam exit opening in the slit that allow the beam to exit, wherein the beam effective exit opening is smaller than the beam entrance opening; and a system for moving the beam across the refractory metal disk, wherein the beam enters the slit through the beam entrance opening and exits the slit through the effective beam exit opening; and a computed tomographic device for measuring the beam that enters and exits the slit for analyzing the beam.
A gas enclosure can include a refractory metal liner; a ceramic matrix composite cladding; and a diffusion barrier layer. The refractory metal liner is adapted to surround and enclose a gas to be contained within the gas enclosure. The diffusion barrier layer is disposed between the refractory metal liner and the ceramic matrix composite cladding.
Rhenium, with its high melting temperature, excellent elevated temperature properties, and lack of a ductile-to-brittle transition temperature (DBTT), is ideally suited for the hot gas components of the ACM (Attitude Control Motor), and other high-temperature applications. However, the high cost of rhenium makes fabricating these components using conventional fabrication techniques prohibitive. Therefore, near-net-shape forming techniques were investigated for producing cost-effective rhenium and rhenium alloy components for the ACM and other propulsion applications. During this investigation, electrochemical forming (EL-Form ) techniques were evaluated for producing the hot gas components. The investigation focused on demonstrating that EL-Form processing techniques could be used to produce the ACM flow distributor. Once the EL-Form processing techniques were established, a representative rhenium flow distributor was fabricated, and samples were harvested for material properties testing at both room and elevated temperatures. As a lower cost and lighter weight alternative to an all-rhenium component, rhenium- coated graphite and carbon-carbon were also evaluated. The rhenium-coated components were thermal-cycle tested to verify that they could withstand the expected thermal loads during service. High-temperature electroforming is based on electrochemical deposition of compact layers of metals onto a mandrel of the desired shape. Mandrels used for electro-deposition of near-net shaped parts are generally fabricated from high-density graphite. The graphite mandrel is easily machined and does not react with the molten electrolyte. For near-net shape components, the inner surface of the electroformed part replicates the polished graphite mandrel. During processing, the mandrel itself becomes the cathode, and scrap or refined refractory metal is the anode. Refractory metal atoms from the anode material are ionized in the molten electrolytic solution, and are deposited onto the cathodic mandrel by electrochemical reduction. Rotation of the mandrel ensures uniform distribution of refractory material. The EL-Form process allows for manufacturing in an inert atmosphere with deposition rates from 0.0004 to 0.002 in./h (10.2 to 50.8 m/h). Thicknesses typically range from microns to greater than 0.5 in. (13 mm). The refractory component produced is fabricated, dependably, to within one micron of the desired tolerances with no shrinkage or distortion as in other refractory metal manufacture techniques. The electroforming process has been used to produce solid, nonporous deposits of rhenium, iridium, niobium, tungsten, and their alloys.
The limitations of traditional alloys and the desire for improved performance for components is driving the increased utilization of refractory metals in tile space industry. From advanced propulsion systems to high temperature furnace components for microgravity processing, refractory metals are being used for their high melting temperatures and inherent chemical stability. Techniques have been developed to produce near net shape refractory metal components utilizing vacuum plasma spraying. Material utilization is very high, and laborious machining can be avoided. As-spray formed components have been tested and found to perform adequately. However, increased mechanical and thermal properties are needed. To improve these properties, post processing thermal treatments such as hydrogen sintering and vacuum annealing have been performed. Components formed from alloys of tungsten, rhenium, tantalum, niobium, and molybdenum are discussed and a metallurgical analyses detailing the results are presented. A qualitative comparison of mechanical properties is also included.
Electron emission properties of refractory metals for ion propulsion studies with applications to problems of voltage breakdown across vacuum gaps and cesium ionization on refractory metals
Four cast nickel-base superalloys were oxidized at 1000 and 1100 C for times up to 100 hr in static air and a Mach 1 gas stream. The oxidation resistance was judged by weight change, metal thickness loss, depletion-zone formation, and oxide formation and morphology. The alloys which formed mostly nickel aluminate (NiAl2O4) and aluminum oxide (Al2O3) (B-1900, VIA, and to a lesser extent 713C) were more oxidation resistant. Poorer oxidation resistance was associated with the appearance of chromium sesquioxide (Cr2O3) and chromite spinel (738X). Refractory metal content had little effect on oxidation resistance. Refractory metals appeared in the scale as tapiolite (NiM2O6, where M represents the refractory metal). Thermal cycling in static air appeared to supply sufficient data for the evaluation of oxidation resistance, especially for alloys which form oxides of low volatility. For alloys of higher chromium levels with high propensities toward forming a chromium-bearing scale of higher volatility, testing under conditions of high gas velocity is necessary to assess fully the behavior of the alloy.
A thermal spray process is being used to build up refractory metals and ceramics into a containment cartridge for high temperature, single crystal semiconductor growth experiments. This process uses high energy plasma inside a low pressure (100-200 torr) inert environment to apply layers of material onto a removable mandrel. A variety of materials are being characterized and evaluated against a demanding set of requirements, including high service temperature (1700 C), oxidation resistance, and resistance to liquid metal attack. Techniques to spray form refractory metals (tungsten, molybdenum, niobium, tantalum) and ceramics (alumina, boron nitride) are being developed in the Plasma Spray Cell at Marshall Space Flight Center. These plasma spray formed materials have been evaluated for mechanical properties, density, microstructure, and resistance to liquid metal attack. Forming techniques and the resultant mechanical and metallurgical properties will be presented.
A thermal spray process is being used to build up refractory metals and ceramics into a containment cartridge for high temperature, single crystal semiconductor growth experiments. This process uses high energy plasma inside a low pressure (100-200 torr) inert environment to apply layers of material onto a removable mandrel. A variety of materials are being characterized and evaluated against a demanding set of requirements, including high service temperature (1700 C), oxidation resistance, and resistance to liquid metal attack. Techniques to spray form refractory metals (tungsten, molybdenum, niobium, tantalum) and ceramics (alumina, boron nitride) are being developed in the Plasma Spray Cell at Marshall Space Flight Center. These plasma spray formed materials have been evaluated for mechanical properties, density, microstructure, and resistance to liquid metal attack. Forming techniques and the resultant mechanical and metallurgical properties are presented.
A hybrid manufacturing approach, integrating additive manufacturing (AM) with powder methodology via electric field-assisted sintering (EFAS), was developed for the fabrication of high-temperature compact heat exchangers (CHX) from refractory metals. The methodology employed additively manufactured sacrificial channel molds (SCMs) as shapeholders for CHX channels, which were embedded in metal powders using EFAS. Following embedding, the SCMs were chemically dissolved to form the internal channel network. SCMs were fabricated using both digital light processing (DLP) and direct ink writing (DIW) from chemically reactive, calcium-based ceramic feedstocks with varying ratios of Al2O3 reinforcement. The microstructure, phase composition, and dissolution behavior of both as-printed and embedded SCMs were investigated. The shrinkage behavior of the SCMs embedded in refractory metals, as well as the interfacial characteristics between the SCMs and metal matrix, were studied. The results showed that the SCMs containing sufficient chemical reactive ceramics dissolved effectively before and after embedding. The as-printed SCMs retained the phase composition of their feedstocks, but the embedded SCMs containing calcium-based ceramics and Al2O3 exhibited the formation of calcium aluminates due to high temperature exposure during embedding. Most SCMs exhibited a cellular Al2O3 network filled with Ca-rich ceramics. Shrinkage after embedding was strongly dependent on SCM density, with lower density SCMs exhibiting greater shrinkage. A thin SCM-affected zone was observed at the metal matrix surface, characterized by increased porosity compared to the bulk matrix. This effect was attributed to infiltration of the SCM materials into powder particle boundaries under pressure, followed by their removal during dissolution. This study demonstrates the feasibility of manufacturing CHXs from hard-to-process refractory metals for use in harsh environments.
Advancement of U.S. scientific, security, and economic interests through a robust space exploration program requires high performance propulsion systems to support a variety of robotic and crewed missions beyond low Earth orbit. Past studies, in particular those in support of the Space Exploration Initiative (SEI), have shown nuclear thermal propulsion systems provide superior performance for high mass high propulsive delta-V missions. The recent NASA Design Reference Architecture (DRA) 5.0 Study re-examined mission, payload, and transportation system requirements for a human Mars landing mission in the post-2030 timeframe. Nuclear thermal propulsion was again identified as the preferred in-space transportation system. A common nuclear thermal propulsion stage with three 25,000-lbf thrust engines was used for all primary mission maneuvers. Moderately lower thrust engines may also have important roles. In particular, lower thrust engine designs demonstrating the critical technologies that are directly extensible to other thrust levels are attractive from a ground testing perspective. An extensive nuclear thermal rocket technology development effort was conducted from 1955-1973 under the Rover/NERVA Program. Both graphite and refractory metal alloy fuel types were pursued. Reactors and engines employing graphite based fuels were designed, built and ground tested. A number of fast spectrum reactor and engine designs employing refractory metal alloy fuel types were proposed and designed, but none were built. The Small Nuclear Rocket Engine (SNRE) was the last engine design studied by the Los Alamos National Laboratory during the program. At the time, this engine was a state-of-the-art graphite based fuel design incorporating lessons learned from the very successful technology development program. The SNRE was a nominal 16,000-lbf thrust engine originally intended for unmanned applications with relatively short engine operations and the engine and stage design were constrained to fit within the payload volume of the then planned space shuttle. The SNRE core design utilized hexagonal fuel elements and hexagonal structural support elements. The total number of elements can be varied to achieve engine designs of higher or lower thrust levels. Some variation in the ratio of fuel elements to structural elements is also possible. Options for SNRE-based engine designs in the 25,000-lbf thrust range were described in a recent (2010) Joint Propulsion Conference paper. The reported designs met or exceeded the performance characteristics baselined in the DRA 5.0 Study. Lower thrust SNRE-based designs were also described in a recent (2011) Joint Propulsion Conference paper. Recent activities have included parallel evaluation and design efforts on fast spectrum engines employing refractory metal alloy fuels. These efforts include evaluation of both heritage designs from the Argonne National Laboratory (ANL) and General Electric Company GE-710 Programs as well as more recent designs. Results are presented for a number of not-yet optimized fast spectrum engine options.
Refractory-metal heater base wound with a thin refractory metal wire increases the longevity of oxide-coated cathodes. The wire-wound unit is impregnated with the required thickness of metal oxide. This cathode is useful in magnetohydrodynamic systems and in electron tubes.