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Preparation and Thermoelectric Properties of IR(sub x)Co(sub 1-x)Sb(sub 2) Alloys

The preparation and characterization of the binary arsenopyrite compounds CoSb2 and IrSb2 and IrxCo1-xSb2 alloys is reported. Single crystals of CoSb2 were grown by the vertical gradient freeze technique from solution rich in antimony. Polycrystalline samples of IrSb2 and IrxCo1-xSb2 alloys were prepared by hot-pressing of prereacted elemental powders. Samples were investigated by X-ray diffractometry, microprobe analysis and density measurements. It was found that a range of solid solution exist in the system IrxCo1-xSb2 for 0.1<x<0.8. Samples were also characterized by high temperature electrical resistivity, Seebeck coefficient and thermal conductivity measurements. All materials have p-type conductivity and are semiconductors. A band gap of about 0.98 eV was calculated for IrSb2. Preliminary measurements of the thermoelectric properties of these materials showed that their potential for thermoelectric applications is limited.

Thermoelectric Properties↗

Elevated Temperature Compressive Properties of Zr-Modified Nial

Small Zr additions are known to substantially affect the deformation behavior and strength of polycrystalline NiAl, yet little information is currently available regarding the high-temperature properties of such alloys. Utilizing prealloyed powder technology, a series of four NiAl alloys have been produced containing from 0.05 to 0.7 at. pct Zr. The creep behavior of these alloys was characterized in compression between 1000 and 1400 K at strain rates ranging from approx. O.1 to 10(exp -9)/ sec. All the Zr-modified alloys were significantly stronger than binary NiAl under lower temperature and faster strain-rate conditions; however, the single-phase materials (Zr less than or equal to 0.1 at. pct) and binary NiAl had similar strengths at high temperatures and slow strain rates. The two-phase NiAl-Ni, AlZr alloys containing 0.3 and 0.7 at. pct Zr had nearly identical strengths. While the two-phase alloys were stronger than the single-phase materials at all test conditions, the degree of microstructural damage in the two-phase alloys due to internal oxidation during testing appeared to increase with Zr level. Balancing the poor oxidation behavior with the consistent strength advantage of the two-phase alloys, it is concluded that optimum elevated-temperature properties could be obtained in Heusler-strengthened NiAl containing between 0.1 and 0.3 at. pct Zr.

Whittenberger, J. Daniel↗

Thermophysical Properties of Nickel-Based Superalloys

The NASA Marshall Space Flight Center (MSFC) electrostatic levitation (ESL) laboratory has a long history of providing materials research and thermophysical property data. The lab can measure thermophysical properties such as density, surface tension, and viscosity of liquid materials, including elements, alloys, glasses, ceramics, and oxides. Nickel-based superalloys (e.g. Inconel, Hastelloy, and Waspaloy) have many high performance applications, including turbine engines for aerospace. Superalloy parts are typically manufactured by casting and forging. These processes generate both polycrystalline and monocrystalline parts. A relatively new method of fabrication of turbine disk materials is additive manufacturing, which is typically done for aerospace parts by powder-bed methods such as selective laser melting (SLM). Accurate modeling of casting and forging, as well as additively manufacturing processes, require thermophysical properties (density, surface tension, and viscosity). The thermophysical properties of liquid nickel-based superalloys, both conventional and additively manufactured, were measured at several temperatures in both undercooled and superheated condition. Surface tension and viscosity was measured using the oscillating drop method and density and thermal expansion was measured using edge detection methods.

SanSoucie, Michael P.↗

Applications of diamond films and related materials; Proceedings of the 1st International Conference, Auburn, AL, Aug. 17-22, 1991

The present conference discusses the nucleation and growth of diamond from hydrocarbons, the cutting tool performance of CVD thick-film diamond, the characterization of CVD diamond grinding powder, industrial applications of crystalline diamond-coated tools, standardized SEM tribometry of diamond-coated substrates, residual stress in CVD diamond films, the optical properties of CVD diamond films, polycrystalline diamond films for optical applications, and diamond growth on ferrous metals. Also discussed are ion beam-irradiation smoothing of diamond films, electronic circuits on diamond substrates, diamond-laminated surfaces for evaporative spray cooling, electron devices based on the unique properties of diamond, diamond cold cathodes, thin-film diamond microstructure applications, Schottky diodes from flame-grown diamond, diamond films for thermionic applications, methods of diamond nucleation and selective deposition, high-rate/large-area diamond film production, halogen-assisted diamond growth, the economics of diamond technology, and the optical and mechanical properties of diamondlike films.

Tzeng, Yonhua↗

Assessment of microalloying effects on the high temperature fatigue behavior of NiAl

Binary NiAl suffers from a lack of strength and poor creep properties at and above 1000 K. Poor creep resistance in turn affects low cycle fatigue (LCF) lives at low strain ranges due to the additional interactions of creep damage. One approach for improving these properties involved microalloying with either Zr or N. As an integral part of a much larger alloying program the low cycle fatigue behavior of Zr and N doped nickel aluminides produced by extrusion of prealloyed powders has been investigated. Strain controlled LCF tests were performed in air at 1000 K. The influence of these microalloying additions on the fatigue life and cyclic stress response of polycrystalline NiAl are discussed.

Noebe, R. D.↗

Effect of the microstructure on the thermoelectric properties of polycrystalline lanthanum chalcogenides

Small amounts of second phase materials can have important effects on the thermoelectric properties of polycrystalline gamma-La(3-x)X4 (X-S, Te; X in the range of 0 to 1/3). Microscopic examination by SEM of hot pressed La(3-x)Te4 samples has revealed from 1-5 vol. pct of La2O2Te, an amount which is not detected by X-ray powder diffraction measurements. This amount of La2O2Te resulting from oxygen contamination can reduce the concentration of electrons by as much as 10 to 75 percent below the electron concentration calculated for single phase La(3-x)Te4 in the composition range of greatest interest. Small amounts of second phase materials can also lower the lattice thermal conductivity by scattering low frequency phonons. These results indicate that microstructural effects should be considered when electrical and thermal properties of polycrystalline materials are analyzed.

Lockwood, A.↗

Effect of Processing Route on Strain Controlled Low Cycle Fatigue Behavior of Polycrystalline NiAl

The present investigation examines the effects of manufacturing process on the total axial strain controlled low cycle fatigue behavior of polycrystalline NiAl at 1000 K, a temperature above the monotonic Brittle-to-Ductile Transition Temperature (BDTT). The nickel aluminide samples were produced by three different processing routes: hot isostatic pressing of pre- alloyed powders, extrusion of prealloyed powders, and extrusion of vacuum induction melted ingots. The LCF behavior of the cast plus extruded material was also determined at room temperature (below the BD77) for comparison to the high temperature data. The cyclic stress response, cyclic stress-strain behavior, and strain-life relationships were influenced by the alloy preparation technique and the testing temperature. Detailed characterization of the LCF tested samples was conducted by optical and electron microscopy to determine the variations in fracture and deformation modes and to determine any microstructural changes that occurred during LCF testing. The dependence of LCF properties on processing route was rationalized on the basis of starting microstructure, brittle-to-ductile transition temperature, deformation induced changes in the basic microstructure, deformation substructure, and synergistic interaction between the damage modes.

Rao, K. Bhanu Sankara↗

Effect of composition and grain size on slow plastic flow properties of NiAl between 1200 and 1400 K

A series of about 15-micron diameter polycrystalline B2 crystal structure NiAl alloys ranging in composition from 43.9 to 52.7 Al (at. pct) have been compression tested at constant velocities in air between 1200 and 1400 K. All materials were fabricated via powder metallurgy techniques with hot extrusion as the densification process. Seven intermediate compositions were produced by blending various amounts of two master heats of prealloyed powder; in addition, a tenth alloy of identical composition, 48.25 Al, as one of the blended materials, was produced from a third master heat. Comparison of the flow stress-strain rate behavior for the two 48.25 Al alloys revealed that their properties were identical. The creep strength of materials for Al/Ni not above 1.03 was essentially equal, and deformation could be described by a single stress exponent and activation energy. Creep at low temperatures and faster strain rates is independent of grain sizes and appears to be controlled by a subgrain mechanism. However, at higher temperatures and slower strain rates, diffusional creep seems to contribute to the overall deformation rate.

Whittenberger, J. Daniel↗

Low cycle fatigue behavior of polycrystalline NiAl at 300 and 1000 K

The low cycle fatigue behavior of polycrystalline NiAl was determined at 300 and 1000 K - temperatures below and above the brittle- to-ductile transition temperature (BDTT). Fully reversed, plastic strain-controlled fatigue tests were conducted on two differently fabricated alloy samples: hot isostatically pressed (HIP'ed) prealloyed powder and hot extruded castings. HIP'ed powder (HP) samples were tested only at 1000 K, whereas the more ductile cast-and-extruded (C+E) NiAl samples were tested at both 1000 and 300 K. Plastic strain ranges of 0.06 to 0.2 percent were used. The C+E NiAl cyclically hardened until fracture, reaching stress levels approximately 60 percent greater than the ultimate tensile strength of the alloy. Compared on a strain basis, NiAl had a much longer fatigue life than other B2 ordered compounds in which fracture initiated at processing-related defects. These defects controlled fatigue life at 300 K, with fracture occurring rapidly once a critical stress level was reached. At 1000 K, above the BDTT, both the C+E and HP samples cyclically softened during most of the fatigue tests in air and were insensitive to processing defects. The processing method did not have a major effect on fatigue life; the lives of the HP samples were about a factor of three shorter than the C+E NiAl, but this was attributed to the lower stress response of the C+E material. The C+E NiAl underwent dynamic grain growth, whereas the HP material maintained a constant grain size during testing. In both materials, fatigue life was controlled by intergranular cavitation and creep processes, which led to fatigue crack growth that was primarily intergranular in nature. Final fracture by overload was transgranular in nature. Also, HP samples tested in vacuum had a life three times longer than their counterparts tested in air and, in contrast to those tested in air, hardened continuously over half of the sample life, thereby indicating an environmentally assisted fatigue damage mechanism. The C+E samples were tested only in air. At 1000 K, NiAl exhibited a superior fatigue life when compared to most superalloys on a plastic strain basis, but was inferior to most superalloys on a stress basis.

Lerch, Bradley A.↗

Lepidocrocite to Maghemite to Hematite: A way to have Magnetic and Hematitic Martian Soil

We examined decomposition products of lepidocrocite, which were produced by heating the phase in air at temperatures up to 525 C for 3 and 300 hr, by XRD, TEM, magnetic methods, and reflectance spectroscopy (visible and near-IR). Single-crystal lepidocrocite particles dehydroxilated to polycrystalline particles of disordered maghemite which subsequently transformed to polycrystalline particles of hematite. Essentially pure maghemite was obtained at 265 and 223 C for the 3 and 300 hr heating experiments, respectively. Its saturation magnetization (J(sub s)) and mass specific susceptibility are approximately 50 A(sq m)/kg and approximately 40 cubic micrometers/kg, respectively. Because hematite is spectrally dominant, spectrally-hematitic samples (i.e., characterized bv a minimum near 860 nm and a maximum near 750 nm) could also be strongly magnetic (J(sub s) up to approximately 30 A(sq m)/kg) from the masked maghemite component. TEM analyses showed that individual particles are polycrystalline with respect to both maghemite and hematite. The spectrally-hematitic and magnetic Mh+Hm particles can satisfy the spectral and magnetic constraints for Martian surface materials over a wide range of values of Mh/(Mh+Hm) and as either pure oxide powders or (within limits) as components of multiphase particles. These experiments are consistent with lepidocrocite as the precursor of Mh+Hm assemblages on Mars, but other phases (e.g., magnetite) that decompose to Mh and Hm are also possible precursors. Simulations done with a copy of the Mars Pathfinder Magnet Array showed that spectrally hematitic Mh+Hm powders having J(sub s) equal to 20.6 A(sq m)/kg adhered to all five magnets.

Morris, Richard V.↗

Flow and fracture behavior of NiAl in relation to the brittle-to-ductile transition temperature

NiAl has only three independent slip systems operating at low and intermediate temperatures whereas five independent deformation mechanisms are required to satisfy the von Mises criterion for general plasticity in polycrystalline materials. Yet, it is generally recognized that polycrystalline NiAl can be deformed extensively in compression at room temperature and that limited tensile ductility can be obtained in extruded materials. In order to determine whether these results are in conflict with the von Mises criterion, tension and compression tests were conducted on powder-extruded, binary NiAl between 300 and 1300 K. The results indicate that below the brittle-to-ductile transition temperature (BDTT) the failure mechanism in NiAl involves the initiation and propagation of cracks at the grain boundaries which is consistent with the von Mises analysis. Furthermore, evaluation of the flow behavior of NiAl indicates that the transition from brittle to ductile behavior with increasing temperature coincides with the onset of recovery mechanisms such as dislocation climb. The increase in ductility above the BDTT is therefore attributed to the climb of the 001 line type dislocations which in combination with dislocation glide enable grain boundary compatibility to be maintained at the higher temperatures.

Noebe, R. D.↗

1200 K Compressive Properties of N-Containing Nial

As part of a series of experiments to understand the role of N on the strength of NiAl, a heat of NiAl was enriched with N by melting and atomization to powder in a nitrogen atmosphere. Following consolidation of the powder by hot extrusion, 1200 K compressive properties were measured in air. Within the range of strain rates examined, 10 exp -3 to 10 exp -9/s, the strength of the N-enriched NiAl was greater than that of a simple 15 micron grain size polycrystalline, binary NiAl alloy. For the most part the overall improvement in strength is ascribed to the fine grain size of the N-doped NiAl rather than the alloy chemistry; however, the alloy displayed a complex behavior exhibiting both weakening effects as well as strengthening ones.

Whittenberger, J. D.↗

The 1200 K compressive properties of N-containing NiAl

As part of a series of experiments to understand the role of N on the strength of NiAl, a heat of NiAl was enriched with N by melting and atomization to powder in a nitrogen atmosphere. Following consolidation of the powder by hot extrusion, 1200 K compressive properties were measured in air. Within the range of strain rates examined, 10(exp -3) to 10(exp -9) s(exp -1), the strength of the N-enriched NiAl was greater than that of a simple 15 micron grain size polycrystalline, binary NiAl alloy. For the most part the overall improvement in strength is ascribed to the fine grain size of the N-doped NiAl rather than the alloy chemistry; however, the alloy displayed a complex behavior exhibiting both weakening effects as well as strengthening ones.

Whittenberger, J. Daniel↗

A 3D Printable Alloy Designed for Extreme Environments

Multiprincipal-element alloys are an enabling class of materials owing to their impressive mechanical and oxidation-resistant properties, especially in extreme environments. Here we develop a new oxide-dispersion-strengthened NiCoCr-based alloy using a model-driven alloy design approach and laser-based additive manufacturing. This oxide-dispersion-strengthened alloy, called GRX-810, uses laser powder bed fusion to disperse nanoscale Y 2 O 3 particles throughout the microstructure without the use of resource-intensive processing steps such as mechanical or in situ alloying. We show the successful incorporation and dispersion of nanoscale oxides throughout the GRX-810 build volume via high-resolution characterization of its microstructure. The mechanical results of GRX-810 show a twofold improvement in strength, over 1,000-fold better creep performance and twofold improvement in oxidation resistance compared with the traditional polycrystalline wrought Ni-based alloys used extensively in additive manufacturing at 1,093 °C. The success of this alloy highlights how model-driven alloy designs can provide superior compositions using far fewer resources compared with the ‘trial-and-error’ methods of the past. These results showcase how future alloy development that leverages dispersion strengthening combined with additive manufacturing processing can accelerate the discovery of revolutionary materials.

Timothy M. Smith↗

Correlation of deformation mechanisms with the tensile and compressive behavior of NiAl and NiAl(Zr) intermetallic alloys

To identify the mechanisms controlling strength and ductility in powder-extruded NiAl and NiAl + 0.05 at. pct Zr, tensile and compressive testing was performed from 300 to 1300 K for several grain sizes. Grain size refinement significantly increased yield stress in both alloys and, in some cases, slightly lowered the ductile-to-brittle transition temperature (DBTT), although no room-temperature tensile ductility was observed even in the finest grain size specimens. The small Zr addition increased the DBTT and changed the low-temperature fracture mode from intergranular in NiAl to a combination of intergranular and transgranular in the Zr-doped alloy. Scanning electron microscopy of compression specimens deformed at room temperature revealed the presence of grain-boundary cracks in both alloys. These cracks were due to the incompatibility of strain in the polycrystalline material, owing to the lack of five independent slip systems. The tendency to form grain-boundary cracks, in addition to the low fracture stress of these alloys, contributed to the lack of tensile ductility at low temperatures.

Bowman, R. R.↗

Phosphate Textural Diversity in CI Chondrites and C-Type Asteroids

Introduction: Apatite, Ca 5 (PO 4 ) 3 (CL/F/OH-), is a ubiquitous phosphate found throughout the solar system, including the most primitive solids, CI-chondrites [1,2] and related samples of carbonaceous asteroids Ryugu [3] and Bennu [4], returned by JAXA’s Hayabusa2 and NASA’s OSIRIS-REx missions, respectively. Apatite in these primitive solids is found as individual grains or mineral clusters and has been inferred to form from the hydrothermal sequence during cooling of their respective parent body or bodies. To better understand the formation history and reworking of these early phosphates we have undertaken a highly coordinated study of phosphate microstructures, geochemistry and U/Pb geochronology from a suite of CI meteorites and carbonaceous asteroid samples. These data have identified novel phosphate microstructures and complex relationships across a suite of apatite grains from the early solar system, indicating multiple episodes of growth and modification on the CI parent body(ies). Methods: Samples of CI chondrites, Alais, Ivuna, Orgueil, Oued Chebeika 002, Yamato (Y) 82162, Y980115, Y980134, and two chips of Hayabusa2 Ryugu particles (A0262 and C0263) have been acquired for analysis. The bulk texture of the samples were first scanned by X-ray Computed Tomography (XCT) using the Nikon XT H 320 within the XFACT facility at NASA JSC or the Xradia 620 Versa at the UTCT facility. Based on the identification of petrofabrics or features of interest from the XCT data, samples were chipped, oriented, potted in epoxy and thick sections were prepared. After anhydrously polishing the samples with silicon carbide and dry diamond powder down to 1 µm, the samples were ion polished using a Hitachi ArBlade. Energy dispersive Xray spectrometry (EDS) maps were collected to ID phosphates of interest using a JEOL 7900F SEM. The internal microstructures of identified phosphates were then mapped by electron backscatter diffraction (EBSD) using the JEOL 7900F. Based on the EDS and EBSD data, domains of interest were targeted for quantitative chemical analyses using a JEOL 8530 EPMA. Subsequently, in situ U-Pb and 207 Pb/ 206 Pb ages will be collected using a Cameca ims1290 secondary ion mass spectrometer at UCLA across a range of microstructures. Results: Apatite grains are ubiquitous throughout the CI chondrites and carbonaceous asteroid materials, found as individual grains, disseminated clusters or grain aggregates. Apatite grains are associated with serpentine, magnet-ite, and/or carbonate. Of particular interest, we have identified individual and aggregate polycrystalline grains ex-hibiting an internal ‘honeycomb’ texture (Fig. 1). Some of these grains appear overprinted by subsequent alteration while others remain unaltered. Apatite halogen sites are dominated by the missing component, assumed to be OH, and F, comparable to published values from Bennu, Ryugu and CM-chondrites [3-5]. However, the Yamato CI-like meteorites show a broader range of Cl values, and one grain from Alais is dominated by CL. Summary: Apatite growth features indicate a protracted and complex growth history, consistent with precipitation from an evolving fluid system. The ‘honeycomb’ texture identified in some CI meteorites is, to the best of our knowledge, the first report of such a microstructure in meteoritic phosphate. The microtextures and zoning will guide subsequent age analyses, to better constrain the formation and reworking of phosphate in CI(-like) materials. Acknowledgments: We thank the National Institute of Polar Research, Japan for samples of Y82162, 980115 and 980134 meteorites, ASU’s Buseck Center for Meteorite Studies for samples of Ivuna and Alais meteorites, and JAXA curation for chips of Ryugu material. This work was funded by NASA ROSES LARS grant 24-LARS24-0014. References: [1] Morlok et al., 2016, GCA 70:5371-5394. [2] Alfin g et al., 2019, Geochemistry 79:125532. [3] Nakamura et al. (2022) Science 379:1-15. [4] Seifert et al. (2026) MAPS 61:504-521. [5] Piralla et al. (2021) MAPS 56:809-828.

CI chondrites↗