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10 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Synthesizing intermetallic thermoelectric materials using metal flux growth method

With zero energy poverty by 2050 goals, exploring innovative energy technologies is essential. Thermoelectric materials (TEMs) have the potential to harness waste heat and convert it to electricity (e.g., for spacecraft power, sensors, and cryogenic cooling). Two limitations of thermoelectric compounds are their low efficiency and limited pool of materials. Optimizing the efficiency of TEMs is challenging due to the interdependent relationship between electrical and thermal conductivity. A deeper understanding of electronic properties and lattice thermal conductivity is necessary to “understand, predict and ultimately control” the thermoelectric properties of TEMs. Understanding the influence of light-atom-doping and intrinsic defects on the electronic properties of the f-element containing TEMs are important questions that need to be answered to design and synthesize TEMs with optimal parameters. The purpose of this work is to understand how doping f-element based TEMs with light elements, such as carbon and boron, would impact the crystal structure, bond lengths, band gaps, and thermoelectric characteristics. High-quality f¬-element containing intermetallic single crystals are grown in metal flux media. In molten metal flux growth method, one or more low-melting metals such as aluminum, gallium, tin, and bismuth are used in excess as the reaction medium. As these are solution-state reactions, we can use lower temperatures than solid-state reactions and isolate the kinetic products instead of the thermodynamically stable compound. Then these are characterized using X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, magnetization, electrical and thermal conductivities, and thermoelectric power.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2025

Synthesis and characterization of rhenium chalcogenides for nuclear waste management

A new synthetic approach to binary rhenium (Re) chalcogenides was investigated to aid in the preparation of analogous technetium (Tc) compounds for Tc waste management efforts. The Boron-Chalcogen Mixture (BCM) method was utilized for the first time to prepare polycrystalline powders of ReS 2 , ReSe 2 , and Re 2 Te 5 using a perrhenate, NaReO4, as a rhenium source. Single crystals of ReS 2 were also synthesized using the combined BCM and molten flux methods by adding a K 2 CO 3 flux to the reagent mixture. Thermal analysis using TGA/DSC revealed negligible changes from ambient temperature up to ∼300 °C followed by the oxidation of the Re chalcogenides. High Temperature PXRD was used to investigate the crystallinity of ReS 2 at various temperatures revealing an increase in crystallinity up to 275 °C followed by a decrease in crystallinity due to oxidation. The research presented herein demonstrates a significant step towards technetium waste treatment efforts.

Boron chalcogen mixture (BCM) method↗
DOE OSTI2025

Understanding the Electronic Behavior of f-Element Intermetallics

Due to their partially filled f-orbitals, lanthanide and actinide intermetallic materials exhibit intriguing electronic, structural, and magnetic properties. These materials provide a unique platform to explore exotic magnetic and quantum phenomena that arise from their strongly correlated f-electrons, offering insights into f-electron behavior. Incorporating light elements such as boron and carbon can significantly impact the electronic, chemical, and physical properties of these materials, with varying influence between lanthanides and actinides due to the more localized f-electrons in lanthanides. In this work, lanthanide-based intermetallic single crystals containing light atoms were synthesized using the molten metal flux growth method. In this method, one or more low-melting metals such as aluminum, gallium, tin, and bismuth are used in excess as the reaction medium. This solution-state approach allows for lower reaction temperatures compared to solid-state reactions and enables the isolation of kinetic products rather than thermodynamically stable compounds. The synthesized crystals were analyzed using an extensive array of analytical and computational characterization techniques, including single crystal X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, magnetization measurements, and density functional theory calculations. These analyses provided detailed insights into the structural and magnetic properties of the synthesized materials.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2025

Growth of Hexagonal Boron Nitride from Molten Nickel Solutions: A Reactive Molecular Dynamics Study

Metal flux methods are excellent for synthesizing high-quality hexagonal boron nitride (hBN) crystals, but the atomic mechanisms of hBN nucleation and growth in these systems are poorly understood and difficult to probe experimentally. Here, we harness classical reactive molecular dynamics (ReaxFF) to unravel the mechanisms of hBN synthesis from liquid nickel solvent over time scales up to 30 ns. These simulations mimic experimental conditions by including relatively large liquid nickel slabs containing dissolved boron and a molecular nitrogen gas phase. Overall, the reaction takes place almost exclusively on the surface of the liquid nickel, owing to the low solubility of nitrogen in bulk nickel and the intermediate species’ preference for the metal–gas interface. The formation of hBN invariably begins by reaction of dinitrogen with nickel-solvated boron atoms at the surface, forming intermediate N–N–B species, which typically evolve into B–N–B units through a short-lived intermediate where a single nitrogen atom is coordinated by one nitrogen and two boron atoms. The resulting B–N–B units, in turn, coalesce with growing hBN nuclei and carry nitrogen between hBN nanocrystals in an Ostwald ripening process. The amount of hBN produced on the tens of nanosecond time scale depends critically on the boron concentration, while having a much weaker dependence on the N 2 pressure for the regime considered (N 2 pressures of 2.5–10 MPa, Ni–B solutions with 6–12% boron by atom fraction). The highest rate of hBN formation occurs at the lowest temperature considered (1750 K, just above the melting point of nickel), while no hBN sheets are formed at 2000 K or above. An analysis of the transition pathways for nitrogen atoms shows that the final step, incorporation of small B–N motifs into larger hBN sheets, is the rate-limiting step in the regimes considered. While raising the temperature from 1750 to 2000 K has little effect on the formation of intermediates (N–N–B, B–N–B, etc.), the lack of large hBN sheets at temperatures >1900 K is explained by decreased probability of the final step and increased probability of breakup of hBN into B–N motifs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2012

Modeling of Melt Growth During Carbothermal Processing of Lunar Regolith

The carbothermal processing of lunar regolith has been proposed as a means to produce carbon monoxide and ultimately oxygen to support human exploration of the moon. In this process, gaseous methane is pyrolyzed as it flows over the hot surface of a molten zone of lunar regolith and is converted to carbon and hydrogen. Carbon gets deposited on the surface of the melt, and mixes and reacts with the metal oxides in it to produce carbon monoxide that bubbles out of the melt. Carbon monoxide is further processed in other reactors downstream to ultimately produce oxygen. The amount of oxygen produced crucially depends on the amount of regolith that is molten. In this paper we develop a model of the heat transfer in carbothermal processing. Regolith in a suitable container is heated by a heat flux at its surface such as by continuously shining a beam of solar energy or a laser on it. The regolith on the surface absorbs the energy and its temperature rises until it attains the melting point. The energy from the heat flux is then used for the latent heat necessary to change phase from solid to liquid, after which the temperature continues to rise. Thus a small melt pool appears under the heated zone shortly after the heat flux is turned on. As time progresses, the pool absorbs more heat and supplies the energy required to melt more of the regolith, and the size of the molten zone increases. Ultimately, a steady-state is achieved when the heat flux absorbed by the melt is balanced by radiative losses from the surface. In this paper, we model the melting and the growth of the melt zone with time in a bed of regolith when a portion of its surface is subjected to a constant heat flux. The heat flux is assumed to impinge on a circular area. Our model is based on an axisymmetric three-dimensional variation of the temperature field in the domain. Heat transfer occurs only by conduction, and effects of convective heat transport are assumed negligible. Radiative heat loss from the surface of the melt and the regolith to the surroundings is permitted. We perform numerical computations to determine the shape and the mass of the melt at steady state and its time evolution. We first neglect the volume change upon melting, and subsequently perform calculations including it. Predictions from our model are compared to test data to determine the effective thermal conductivities of the regolith and the melt that are compatible with the data

Balasubramaniam, R.↗
NASA NTRS2019

Molten Target Sputtering: Non-Conventional Method for High Mobility Si0.15Ge0.85 Growth at 500°C

Since electrons travel over 100 times faster in Silicon-Germanium (SiGe) than in pure Si due to the low effective masses associated with Ge and SiGe-based devices continue to replace Si-based solid-state electronic devices. SiGe thin film on sapphire was successfully grown at 890°C, using a magnetron sputtering system within heteroepitaxial framework. However, SiGe growth at 890oC is a costly and difficult process to produce as a uniform wafer for semiconductor device manufacturing due to thermal soak times, and geometric thermal shadowing from the wafer holder. To leverage the semiconducting capabilities of SiGe, novel processing techniques for SiGe film growth with decreased thermal loading are required. This paper introduces the Molten Target Sputtering (MTS) method that produces high mobility SiGe on sapphire below 500°C. This non-conventional method has the advantage of high kinetic energy, high-energy latency, and high flux density of sputtered atoms by combining benefits of both magnetron sputtering and thermal evaporation. For the MTS method, a 1~2 mm (depth and width) ring-shaped groove was cut between the center magnet and surrounded by electromagnets creating a circular cavity between the copper plate and source target materials that melt the target material. The SiGe grown from the MTS shows continuous morphology and 99.7% single crystal Si0.15Ge0.85 films. The Hall electron mobilities of the Si0.15Ge0.85 are 456 sq. cmV(exp -1)s(exp -1) and 123.9 sq. cmV(exp -1)s(exp -1) at 5.59 x 10(exp 18) cubic cm and 3.5 x 10(exp 20) cubic cm carrier concentration at 22.38°C, respectively. This is approximately 5.5 times higher than that of Si and similar to the Ge value at equivalent carrier concentrations and temperatures.

High mobility SiGe↗
NASA NTRS2005

Monitoring Eruptive Activity at Mount St. Helens with TIR Image Data

Thermal infrared (TIR) data from the MASTER airborne imaging spectrometer were acquired over Mount St. Helens in Sept and Oct, 2004, before and after the onset of recent eruptive activity. Pre-eruption data showed no measurable increase in surface temperatures before the first phreatic eruption on Oct 1. MASTER data acquired during the initial eruptive episode on Oct 14 showed maximum temperatures of similar to approximately 330 C and TIR data acquired concurrently from a Forward Looking Infrared (FLIR) camera showed maximum temperatures similar to approximately 675 C, in narrow (approximately 1-m) fractures of molten rock on a new resurgent dome. MASTER and FLIR thermal flux calculations indicated a radiative cooling rate of approximately 714 J/m(exp 2)/s over the new dome, corresponding to a radiant power of approximately 24 MW. MASTER data indicated the new dome was dacitic in composition, and digital elevation data derived from LIDAR acquired concurrently with MASTER showed that the dome growth correlated with the areas of elevated temperatures. Low SO2 concentrations in the plume combined with sub-optimal viewing conditions prohibited quantitative measurement of plume SO2. The results demonstrate that airborne TIR data can provide information on the temperature of both the surface and plume and the composition of new lava during eruptive episodes. Given sufficient resources, the airborne instrumentation could be deployed rapidly to a newly-awakening volcano and provide a means for remote volcano monitoring.

thermal emissions↗
NASA NTRS1985

Bulk Formation of Metallic Glasses and Amorphous Silicon from the Melt

By using metallic glass compositions with a high relative glass transition temperature, such as Pd40Ni40P20, homogeneous nucleation also becomes negligible. Large (5g) masses of this alloys were obtained using a molten B2O3 flux. Presently, bulk glass formation in iron based glasses is being investigated. It is expected that if an undercooling of about 250K can be achieved in a Ge or Si melt, formation of the amorphous semiconductor phase (rather than the crystal) may be kinetically favored. The volumetric behavior of undercooled liquid Ga droplet dispersion is investigated by dilatometry. A theoretical model (both analytical and numerical) was developed for transient nucleation in glass forming melts. The model, originally designed for isothermal conditions, was extended to continuous quenching. It is being applied to glass formation in various metallic and oxide systems. A further refinement will be the inclusion of diffusion controlled interfacial rearrangements governing the growth of the crystal embryos.

Spaepen, F.↗
DOE OSTI2024

Flux Synthesis of A-site Disordered Perovskite La 0.5 M 0.5 TiO 3 (M$=$Li, Na, K) Nanorods Tailored for Solid Composite Electrolytes

Inorganic fillers play an important role in improving the ionic conductivity of solid composite electrolytes (SCEs) for Li-ion batteries. Among inorganic fillers, perovskite-type lithium lanthanum titanate (LLTO) stands out for its high bulk Li + conductivity on the order of 10 -3 S cm -1 at room temperature. According to a literature survey, the optimal LLTO filler should possess the following characteristics: i) a single-crystal structure to minimize grain boundaries; ii) a small particle size to increase the filler/polymer interface area; iii) a 1D morphology for efficient interface channels; and iv) cubic symmetry to facilitate rapid bulk Li + diffusion within the filler. However, the synthesis of single crystal, 1D LLTO nanomaterials with cubic symmetry is challenging. Herein, a flux strategy is developed to synthesize La 0.5 M 0.5 TiO 3 (LMTO, M$=$Li, Na, and K) single-crystal nanorods with an A-site-disordered, cubic perovskite phase. The flux media promotes the oriented growth of nanorods, prevents nanorods from sintering, and provides multiple alkali metal ion doping at M sites to stabilize the cubic phase. SCEs compositing the Li + -conducting LMTO nanorods as fillers and poly[vinylene carbonate- co -lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] matrix exhibit more than twice the conductivity of the neat polymer electrolyte (30.6 vs 14.0 µS cm -1 at 303 K).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2006

Evolution and Control of 2219 Aluminum Microstructural Features through Electron Beam Freeform Fabrication

Electron beam freeform fabrication (EBF3) is a new layer-additive process that has been developed for near-net shape fabrication of complex structures. EBF3 uses an electron beam to create a molten pool on the surface of a substrate. Wire is fed into the molten pool and the part translated with respect to the beam to build up a 3-dimensional structure one layer at a time. Unlike many other freeform fabrication processes, the energy coupling of the electron beam is extremely well suited to processing of aluminum alloys. The layer-additive nature of the EBF3 process results in a tortuous thermal path producing complex microstructures including: small homogeneous equiaxed grains; dendritic growth contained within larger grains; and/or pervasive dendritic formation in the interpass regions of the deposits. Several process control variables contribute to the formation of these different microstructures, including translation speed, wire feed rate, beam current and accelerating voltage. In electron beam processing, higher accelerating voltages embed the energy deeper below the surface of the substrate. Two EBF3 systems have been established at NASA Langley, one with a low-voltage (10-30kV) and the other a high-voltage (30-60 kV) electron beam gun. Aluminum alloy 2219 was processed over a range of different variables to explore the design space and correlate the resultant microstructures with the processing parameters. This report is specifically exploring the impact of accelerating voltage. Of particular interest is correlating energy to the resultant material characteristics to determine the potential of achieving microstructural control through precise management of the heat flux and cooling rates during deposition.

Taminger, Karen M.↗