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At least 793 records · Page 44

Ultrahigh-Temperature Ceramics

Ultrahigh temperature ceramics (UHTCs) are a class of materials that include the diborides of metals such as hafnium and zirconium. The materials are of interest to NASA for their potential utility as sharp leading edges for hypersonic vehicles. Such an application requires that the materials be capable of operating at temperatures, often in excess of 2,000 C. UHTCs are highly refractory and have high thermal conductivity, an advantage for this application. UHTCs are potentially applicable for other high-temperature processing applications, such as crucibles for molten-metal processing and high-temperature electrodes. UHTCs were first studied in the 1960 s by the U.S. Air Force. NASA s Ames Research Center concentrated on developing materials in the HfB2/SiC family for a leading-edge application. The work focused on developing a process to make uniform monolithic (2-phase) materials, and on the testing and design of these materials. Figure 1 shows arc-jet models made from UHTC materials fabricated at Ames. Figure 2 shows a cone being tested in the arc-jet. Other variations of these materials being investigated elsewhere include zirconium based materials and fiber-reinforced composites. Current UHTC work at Ames covers four broad topics: monoliths, coatings, composites, and processing. The goals include improving the fracture toughness, thermal conductivity and oxidation resistance of monolithic UHTCs and developing oxidation-resistant UHTC coatings for thermal-protection-system substrates through novel coating methods. As part of this effort, researchers are exploring compositions and processing changes that have yielded improvements in properties. Computational materials science and nanotechnology are being explored as approaches to reduce materials development time and improve and tailor properties.

Johnson, Sylvia M.↗

Joining and Integration of Silicon Carbide-Based Ceramic Materials for Aerospace Applications: An Overview

In order to fully utilize silicon carbide-based ceramics and ceramic matrix composites (CMCs) for aerospace and ground based applications, advanced joining and integration technologies are critically needed for achieving large, complex shaped, and integrated components. Careful material selection of joining inter-layers needs to consider chemical and thermal compatibilities with the parent materials that are being joined. Also, optimization needs to be conducted to select the proper processing conditions for achieving robust joints that are well adhered, strong, uniform, crack free, and have minimal residual stresses. NASA GRC developed pressureless and pressure aided approaches for joining ceramics and CMCs include brazing, diffusion bonding, refractory eutectic phase joining, and Single-step Elevated Temperature (SET) Joining. For joining ceramics and CMCs to metals, several brazes have been utilized. Brazing approaches for joining ceramics and metals have also included tailored brazes with multiple interlayers and particle additions. An overview of the joining approaches will be provided. In addition, processing-microstructure-property relationships will be discussed.

Silicon carbide↗

Activity model for 36 elements in Fe-Ni-Si-S-C liquids with application to terrestrial planet accretion and mantle geochemistry: New data for Ru, Re, Pt, Os, Ti, Nb, and Ta

Understanding siderophile element partitioning between metal and silicate melts under diverse conditions can be used to place important constraints on the materials and conditions of planetary accretion and core formation, as well as post core formation processes. However, the effects of Si on the partitioning and activity coefficients for these elements are not well known, despite Si likely being one of the dominant light elements in Earth’s core. To address this gap in understanding, we have undertaken a systematic study of the highly siderophile elements Re, Pt, Os, and Ru, and the refractory lithophile elements Nb, Ta and Ti at 1600 °C and 1 GPa, to derive epsilon interaction parameters for these elements in FeSi metallic liquids. Positive epsilon interaction parameters were measured for Nb, Ta, Ti, Ru, Re, Pt, and Os, indicating that dissolved Si in Fe liquids causes a decrease in their metal/silicate partition coefficients (or ‘silicophobic’ behavior). Furthermore, ε$_{Re, Os, or Ru}^{Si}$ > ε$_{Re, Os, or Ru}^{S}$ which means Si causes a larger decrease in D(metal/silicate) than S, and the chalcophile behavior expected from some elements will be completely masked by the presence of Si in a metallic liquid. The new parameters are used to update an activity model that now includes 36 siderophile elements in Fe-Ni-Si-S-C liquids (27 trace elements considered here). Systematic assessment of these 27 elements shows which have the strongest affinity for Si, C, and S, and also how activity coefficients for these elements would vary during accretion and core formation in Earth, Mars, and Mercury of widely differing fO 2 and core compositional conditions. The activity model is combined with new partitioning expressions for Mo, W, Cr, Re Ru, Pt, and Os and applied to aspects of post core formation mantle geochemistry of Earth, Mars, and Mercury. Our updated expressions show that the BSE Mo/W ratio can easily be achieved with metal/silicate partitioning during growth of the Earth, whereas Re, Os and Ru become lower than and highly fractionated compared with BSE values during core formation and accretion, and thus nearly 99% of their BSE abundances are likely contributed by late accretion. Ru isotopes should be a very good indicator of the source material for the late accretion. The high Pt/Os and Re/Os developed in a deepening magma ocean during the growth of the Earth, indicates 186 Os and 187 Os isotopes could be coupled if this ancient material remained isolated and subsequently became entrained in mantle plumes and measured in surficial lavas. The extent to which this occurred will be limited by the low Os content of this ancient material, thus requiring mixing as a major component in plume sources. Martian mantle Hf/W ratio stays low during accretion and core formation modelling, suggesting that W isotope anomalies are more likely due to solid/liquid silicate fractionation than to core formation. Finally, Ti contents measured by MESSENGER at Mercury’s surface can be explained by segregation of either a metallic core (IW-6 to -8) or metallic core + sulfide (IW-4 to -7.5) followed by mantle melting.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

A Correlative Electron Microscopy Study of a Ru-rich Metal Grain from a Calcium-aluminum-rich Inclusion

Calcium-aluminum-rich inclusions (CAIs) are sub-mm to cm-sized objects composed of highly refractory Ca- and Al-rich mineral phases, hosted in chondritic meteorites. The component minerals of CAIs were thermodynamically predicted to be condense at high temperatures in the cooling solar nebula. Isotopic analyses place the age of these objects at 4.567 Ga, making them the first formed solids in our solar system. The chemical compositions and crystal structures of the Ca- and Al-rich minerals serve as imprints of the thermochemical environments in which they formed. Therefore, detailed microstructural analyses of CAIs can provide insight into the processes that prevailed in the early solar system.

Tarunika Ramprasad↗

Development and Testing of a Refractory Millimeter-Wave Absorbent Heat Exchanger

Central to the Millimeter-Wave Thermal Launch System (MTLS) is the millimeter-wave absorbent heat exchanger. We have developed metallic and ceramic variants, with the key challenge being the millimeter-wave absorbent coatings for each. The ceramic heat exchanger came to fruition first, demonstrating for the first time 1800 K peak surface temperatures under illumination by a 110 GHz Gaussian beam. Absorption efficiencies of up to 80 are calculated for mullite heat exchanger tubes and up to 50 are calculated for alumina tubes. These are compared with estimates based on stratified layer and finite element analyses. The problem of how to connect the 1800 K end of the ceramic tubes to a graphite outlet manifold and nozzle is solved by press fitting, or by threading the ends of the ceramic tubes and screwing them into place. The problem of how to connect the ceramic tubes to a metallic or nylon inlet pipe is solved by using soft compliant PTFE and PVC tubes that accommodate thermal deformations of the ceramic tubes during startup and operation. We show the resulting heat exchangers in static tests using argon and helium as propellants.

propulsion↗

Microgravity containerless processing in long drop tubes

Extensive experience in utilizing long drop tubes for studying effects of microgravity on the solidification of alloys was obtained. While some modifications are necessary to improve versatility, the facility proved to be most useful. Both an electron beam furnace and an electromagnetic levitation furnace can be used. The electron beam furnace is used with vacuum environments (0.00001 torr), whereas the levitation furnace is presently used only in inert gas environments (above 100 torr). Experiments are best applied to refractory alloys because of the sensitivity of the detectors now being used to observe solidification. Processing of lower melting point metals and alloys simply cannot be recorded. On the other hand, expected improvements in detector sensitivity will allow experimentation with relatively low melting alloys. In such cases, solidification will occur in flight only if higher inert gas pressure is used (100 to 760 torr) to increase heat loss by convection. Under these conditions microgravity conditions no longer apply. However, as shown by results to date, it is not microgravity as such that is important in drop tube solidification. Instead it is the containerless nature of the process that is significant, leading to large degrees of undercooling before solidification and therefore to unique alloys.

Bayuzick, R. J.↗

Modelling of Equilibrium Between Mantle and Core: Refractory, Volatile, and Highly Siderophile Elements

Siderophile elements have been used to constrain conditions of core formation and differentiation for the Earth, Mars and other differentiated bodies [1]. Recent models for the Earth have concluded that the mantle and core did not fully equilibrate and the siderophile element contents of the mantle can only be explained under conditions where the oxygen fugacity changes from low to high during accretion and the mantle and core do not fully equilibrate [2,3]. However these conclusions go against several physical and chemical constraints. First, calculations suggest that even with the composition of accreting material changing from reduced to oxidized over time, the fO2 defined by metal-silicate equilibrium does not change substantially, only by approximately 1 logfO2 unit [4]. An increase of more than 2 logfO2 units in mantle oxidation are required in models of [2,3]. Secondly, calculations also show that metallic impacting material will become deformed and sheared during accretion to a large body, such that it becomes emulsified to a fine scale that allows equilibrium at nearly all conditions except for possibly the length scale for giant impacts [5] (contrary to conclusions of [6]). Using new data for D(Mo) metal/silicate at high pressures, together with updated partitioning expressions for many other elements, we will show that metal-silicate equilibrium across a long span of Earth s accretion history may explain the concentrations of many siderophile elements in Earth's mantle. The modeling includes refractory elements Ni, Co, Mo, and W, as well as highly siderophile elements Au, Pd and Pt, and volatile elements Cd, In, Bi, Sb, Ge and As.

Righter, K.↗

Single-particle chemical analysis reveals organic-rich detonation soot products

The detonation of high explosives produces a wide variety of particulate matter (PM) with distinct properties, not all of which are traditionally studied for chemical composition, formation processes, and forensic applications. We report particle-resolved measurements of Composition B detonation soot using soot particle aerosol mass spectrometry (SP-AMS), identifying carbonaceous species and metals not previously characterized on a single-particle basis. Results are combined with scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) to enhance source-dependent signatures. Black carbon, including graphitic carbon and detonation nanodiamonds, contributed 50.5-71.4% of PM 2.5 mass, while 22.5-43.4% was non-refractory organic carbon, a previously overlooked component that exhibited a complex and varying composition. Detonations were performed with and without PMMA confinement and under steady and overdriven conditions. Distinct particles enriched with polycyclic aromatic hydrocarbons (PAHs) were observed in experiments utilizing confinement, with quantities dependent on manufacturing method. SEM-EDS validated SP-AMS findings of metals internally mixed with carbonaceous species and extended the particle size range to 100 µm. This work makes detecting non-refractory organics using single-particle techniques more feasible for detonation forensics and understanding high-energy soot formation. While this analysis uses offline sample collection, SP-AMS could be deployed for in-situ measurements of detonation PM 2.5 transported in the atmosphere.

36 MATERIALS SCIENCE↗

Synthesis and structure of high-purity BaCe 0.25 Mn 0.75 O 3 : an improved material for thermochemical water splitting

Solar thermochemical hydrogen production (STCH) via redox-active metal oxides is an approach for direct solar-driven hydrogen generation typically using a high-temperature redox cycle involving refractory oxides and steam. Typical cycles involve high-temperature reduction of oxides to form oxygen vacancies, followed by lower temperature reaction between oxygen vacancies and steam where the oxide is re-oxidized and the steam is reduced to hydrogen. Only a few materials have demonstrated reversible cycling under the typically harsh STCH conditions (e.g. 1500°C reduction, 900°C re-oxidation) and critical questions remain on the true reversibility of non-stoichiometric multi-cation oxide systems, significantly hampered by the lack of single-phase samples for these material systems. To date, most STCH processes have relied on CeO 2 as a benchmark active material, but more recently, the 12R phase of BaCe 0.25 Mn 0.75 O 3 (BCM) has demonstrated greater hydrogen-generation potential at lower peak temperatures. However, previous reports of 12R-BCM have included large fractions, > 10 wt%, of secondary phases, which complicate analysis of the stability and performance. A comprehensive understanding of the redox mechanism and reversibility of the process in BCM can only be achieved with nearly single-phase samples which, to date, have been difficult to produce. Here two approaches to BCM synthesis are reported: solid state and sol–gel-based routes. It is demonstrated that both routes can be tuned to produce the 12R structure with > 97 wt% yield when annealed ≥1450°C. Herein synchrotron-based diffraction measurements of rhombohedral 12R-BCM enabled characterization of the anisotropy between thermal expansion along the c-axis and within the ab plane. The impact of high-temperature redox cycling on the stability and phase fraction of the 12R-BCM polytype was also investigated. Our results offer two viable routes for synthesis of high-purity 12R-BCM critically needed for evaluating the efficacy of BCM as a STCH material and validate its ability to split water at lower temperatures over extended numbers of redox cycles.

08 HYDROGEN↗

Clearance of short circuited ion optics electrodes by capacitive discharge

The ion optics electrodes of low specific impulse (3000 sec) mercury electron bombardment ion thrusters are vulnerable to short circuits by virtue of their relatively small interelectrode spacing (0.5 mm). Metallic flakes from backsputtered deposits are the most probable cause of such 'shorts' and 'typical' flakes have been simulated here using refractory wire that has a representative, but controllable, cross section. Shorting wires can be removed by capacitive discharge without significant damage to the electrodes. This paper describes an evaluation of 'short' removal versus electrode damage for several combinations of capacitor voltage, stored energy, and short circuit conditions.

Poeschel, R. L.↗

Nickel-rich, volatile depleted iron meteorites: Relationships and formation processes

Ungrouped iron meteorites Tishomingo, Willow Grove, and Chinga, and group IVB iron meteorites, are Ni-rich. Similarities include enrichments of 10–100 × CI for some refractory siderophile elements, and equivalent depletions in more volatile siderophile elements. Superimposed on the overall enrichment/depletion trend, certain siderophile elements (P, W, Fe, Mo) are depleted relative to elements of similar volatility. All three ungrouped irons derive from parent bodies formed in the early Solar System. Willow Grove and Chinga are characterized by cosmic ray exposure corrected 182 W/ 184 W consistent with metal-silicate segregation on their parent bodies within 1–3 Myr of Solar System formation, within the age range determined for segregation of magmatic iron meteorite parent bodies, including group IVB irons. Tishomingo is characterized by a younger model age 4–5 Myr subsequent to Solar System formation, reflecting either late stage melting resulting from 26 Al decay, or an impact resetting. The discovery of stishovite in Tishomingo, indicating exposure to a minimum shock pressure of 8–9 GPa, is consistent with the latter. Stishovite in Tishomingo and chromite included in troilite-daubréelite in IVB irons allows oxygen isotopic composition comparison between these meteorites. Different mass independent oxygen isotopic compositions of IVB irons and Tishomingo indicate genetically distinct parent bodies. By contrast, mass independent Mo isotopic compositions overlap within analytical uncertainties, indicating a similar, carbonaceous chondrite (CC) type genetic heritage. Molybdenum and 183 W isotopic data for Chinga and Willow Grove indicate derivation from CC type parent bodies. Willow Grove shares Mo and 183 W isotopic compositions with the Ni-rich South Byron Trio (SBT) grouplet and the Milton pallasite. These Ni-rich meteorites likely formed in the same general nebular environment as other CC planetesimals, likely the outer Solar System. Highly siderophile element (HSE) abundances of Willow Grove and Tishomingo are similar to some IVB meteorites, consistent with formation by moderate degrees of fractional crystallization from initial metallic melts with low S and P, and modestly fractionated HSE. The comparable HSE abundances of Tishomingo and Willow Grove to some IVB irons, yet substantially higher Ni concentrations, indicate formation on parent bodies with lower bulk HSE abundances or HSE concentration in proportionally smaller volumes of metal. HSE abundances in Chinga are considerably lower than in IVB irons, highly fractionated, and processes responsible for these remain elusive. For IVB irons and these ungrouped irons, high temperature condensation likely dominated the enrichment and depletion of the refractory and volatile siderophile elements, respectively. Parent body degassing may have also played a role. Relative depletion of volatile siderophile elements is not, however, a universal feature of high-Ni meteorites. The SBT and Milton pallasite are Ni-rich, but less depleted in the more volatile siderophile elements. Nickel enrichment was likely driven by oxidation of Fe metal during parent body accretion or core segregation. Oxidation of the Tishomingo and Willow Grove parent bodies may have occurred at ~ IW + 1, indicated by relative Mo and W depletions due to metal/water reaction during differentiation. Late-stage reduction, indicated by the presence of Cr-bearing sulfides in Tishomingo and IVB irons, may have resulted from exhaustion of the oxidant.

36 MATERIALS SCIENCE↗

Design for high-temperature /1800 deg F/ liquid metal pressure transducer

Thermionic diode sensor is used as a pressure transducer in advanced space power systems using liquid metals as working and heat transfer media at temperatures up to 1800 deg F. The sensor converts the motion of a pressure actuated refractory alloy capsule into a suitable electrical output.

Engdahl, R. E.↗

Bi‐Continuous W‐Rich Refractory High Entropy Alloy‐Cu Composite: Toward Material Innovation of Nuclear Reactor Coolant System

Abstract Refractory high‐entropy alloys (RHEAs) are considered promising candidate materials for next‐generation nuclear reactors due to their superior mechanical strength, irradiation resistance, and thermal stability at high temperatures. However, the significant positive heat of mixing between refractory alloying elements and Cu, commonly used in cooling systems, poses challenges in forming composite structures. This study addresses the issue using a liquid metal dealloying (LMD) process. A precursor alloy (WTaVTi) with a directional dendrite‐interdendrite structure is fabricated and reacted with molten Cu at 1200 °C for 96 h. This approach produced a RHEA‐Cu composite with a stable interface between RHEA (W 31.5 Ta 30.9 V 21.4 Ti 14.3 ) and Cu, featuring a spontaneously formed W‐rich interlayer that enhances interfacial bonding. The composite showed excellent irradiation resistance, with 30% less swelling under α‐ion irradiation than pure W. It also exhibited low thermal conductivity at room temperature, but reached ≈120 W m −1 ·K −1 at ≈650 °C, surpassing pure W. This temperature‐dependent rise in κ, with a positive gradient of +0.075 W m −1 ·K − 2 , is attributed to decreasing diffuse mismatch at elevated temperatures. The large‐scale reaction and stable microstructure achieved through LMD process highlight its industrial potential. This work offers a strategy for developing high‐performance materials by combining RHEA's radiation resistance with Cu's thermal conductivity for extreme environments.

Chemistry↗

Observations of Metallic Species in Mercury's Exosphere

From observations of the metallic species sodium (Na), potassium (K), and magnesium (Mg) in Mercury's exosphere, we derive implications for source and loss processes. All metallic species observed exhibit a distribution and/or line width characteristic of high to extreme temperature - tens of thousands of degrees K. The temperatures of refractory species, including magnesium and calcium, indicate that the source process for the atoms observed in the tail and near-planet exosphere are consistent with ion sputtering and/or impact vaporization of a molecule with subsequent dissociation into the atomic form. The extended Mg tail is consistent with a surface abundance of 5-8% Mg by number, if 30% of impact-vaporized Mg remains as MgO and half of the impact vapor condenses. Globally, ion sputtering is not a major source of Mg, but locally the sputtered source can be larger than the impact vapor source. We conclude that the Na and K in Mercury's exosphere can be derived from a regolith composition similar to that of Luna 16 soil (or Apollo 17 orange glass), in which the abundance by number is 0.0027 (0.0028) for Na and 0.0006 (0.0045) for K.

Killen, Rosemary M.↗

Effect of Tungsten L-PBF Feedstock Modification on Performance in Bending

Additively manufactured tungsten is a candidate refractory material for high-temperature aerospace and nuclear fusion/fission applications. The printability of pure tungsten is challenged by cracking defects arising from the metal’s high ductile-to-brittle transition temperature and low solubility of interstitial impurities. Furthermore, the cast microstructure inherent to the laser powder bed fusion (L-PBF) process has limited strength compared to worked microstructures common in wrought tungsten. Aside from process-related techniques to mitigate defects and increase strength (e.g., heated build chambers, multi-laser systems, low oxygen environmental control, etc.), micro-alloying additions can positively influence tungsten printability. In this work, pure tungsten L-PBF feedstock was modified with 1 wt% additions of ceramic compound nano-powders. Wrought and printed bars were evaluated in four-point bending. Flexural strength and fractography were primary means of comparison to assess the effect of the feedstock modification on printed tungsten mechanical performance.

Tungsten-based alloys↗

Bending Performance of Tungsten Printed Via Laser Powder Bed Fusion With Ceramic Dispersion Modified Powder Feedstock

Additively manufactured tungsten is a candidate refractory material for high-temperature aerospace and nuclear fusion/fission applications. The printability of pure tungsten is challenged by cracking defects arising from the metal’s high brittle-to-ductile transition temperature and low solubility of interstitial impurities. Furthermore, the cast microstructure inherent to the laser powder bed fusion (L-PBF) process has limited strength compared to worked microstructures common in wrought tungsten. Aside from process-related techniques to mitigate defects and increase strength (e.g., heated build chambers, multi-laser systems, low oxygen environmental control, etc.), micro-alloying additions can positively influence tungsten printability and strength. In this work, pure tungsten L-PBF feedstock was modified with 1 wt% additions of ceramic compound nano-powders. Wrought and printed bars were evaluated in four-point bending. Flexural strength and fractography were primary means of comparison to assess the effect of the feedstock modification on printed tungsten mechanical performance.

Additive Manufacturing↗