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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Coupled solute effects enable anomalous high-temperature strength and stability in nanotwinned Al alloys

Nanoprecipitates or grain refinement can effectively enhance the mechanical strength of Al alloys, but the room-temperature strengths of precipitation hardened and nanocrystalline Al alloys often fall below 1 GPa. Furthermore, they are largely plagued by precipitous mechanical softening at elevated temperature below 300°C, mostly due to degraded microstructural stability. Here, we report a mechanism of coupled solute effect in nanotwinned Al-Fe-Ti alloys that enables stability of nanograins up to 400°C and an unprecedented high-temperature flow stress of ~ 1.7 GPa at 300°C. The supersaturated Fe solutes in Al act as effective grain refiner, forming superstrong solid solution alloys. More importantly, empirical evidence combined with first principle calculations indicate that the Ti solutes delay the agglomeration of Fe solutes, thereby remarkably extending the temperature window for the stability of nanograins in nanotwinned Al alloys. Finally, this study highlights the opportunity to design ultrastrong and stable nanostructured alloys for potential high temperature applications via a coupled solute effect.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Advanced Nanocarbons for Enhanced Performance and Durability of Platinum Catalysts in Proton Exchange Membrane Fuel Cells

Insufficient stability of current carbon supported Pt and Pt alloy catalysts is a significant barrier for proton-exchange membrane fuel cells (PEMFCs). As a primary degradation cause to trigger Pt nanoparticle migration, dissolution, and aggregation, carbon corrosion remains a significant challenge. Compared with enhancing Pt and PtM alloy particle stability, improving support stability is rather challenging due to carbon's thermodynamic instability under fuel cell operation. In recent years, significant efforts have been made to develop highly durable carbon-based supports concerning innovative nanostructure design and synthesis along with mechanistic understanding. Here, this review critically discusses recent progress in developing carbon-based materials for Pt catalysts and provides synthesis–structure–performance correlations to elucidate underlying stability enhancement mechanisms. The mechanisms and impacts of carbon support degradation on Pt catalyst performance are first discussed. The general strategies are summarized to tailor the carbon structures and strengthen the metal–support interactions, followed by discussions on how these designs lead to enhanced support stability. Based on current experimental and theoretical studies, the critical features of carbon supports are analyzed concerning their impacts on the performance and durability of Pt catalysts in fuel cells. Finally, the perspectives are shared on future directions to develop advanced carbon materials with favorable morphologies and nanostructures to increase Pt utilization, strengthen metal-support interactions, facilitate mass/charge transfer, and enhance corrosion resistance.

25 ENERGY STORAGE↗
DOE OSTI2021

Equilibrium distribution of point defects in Fe-Y-O as a typical representative of nanocluster-strengthened alloys

The statistical mechanic approach has been used to estimate the equilibrium defect distribution in a multiphase system by minimizing its free energy using microstructural characteristics and a finite set of defects obtained by first-principles calculations. Recently the approach was extended to take in consideration defects at the interface of the precipitate and matrix. Herein we apply the developed approach to the investigation of the stability of bcc Fe containing yttria, Y 2 O 3 , nanoclusters as a prototype of nanostructured ferritic alloys. It has been obtained that (100)Fe-O interface is unstable with respect to vacancies production. In a contrast to (100)Fe-O interface, the so called Klim interface is stable, i.e. local vacancy concentration at this interface at 600 K is below 10 -12 . It has been demonstrated that due to large defect formation energies the ODS particles are extremely stable and the main defect corresponds to Fe atoms substitute Y in Y 2 O 3 precipitate. Moreover, under thermodynamic equilibrium condition, the preexist vacancies in bulk Fe do not accumulate oxygen atom. The later observation not necessarily forbid the existence of a large amount of preexisting Fe vacancy - oxygen atom clusters at the initial stages of alloy formation far from equilibrium.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Identifying the Role of Magnesium Content in Assessing the Electrochemical Performance of (CoCuMgNiZn)O

High-entropy oxides (HEOs) featuring 5 or more metals in approximately equimolar ratios, such as the prototypical rock-salt-structured (CoCuMgNiZn)O, have attracted interest for their potential to display material properties superior to oxides with combinations of 4 or fewer of the component metals. In particular, (CoCuMgNiZn)O has shown promise as an anode for lithium-ion batteries with a high specific capacity retention over extended cycling. Previous studies have suggested that magnesium, despite being electrochemically inert, provides a crucial contribution to the favorable performance of this HEO by stabilizing the crystal structure through repeated charge–discharge cycles. This paper probes the extent and mechanism of the magnesium effect by using a facile microwave-assisted hydrothermal synthesis method to vary the level of Mg content. Moreover, we extensively characterized the product with techniques such as 4D-STEM and ICP-OES, which have not previously been applied in combination with this material, in order to elucidate the relationships among chemical composition, nanostructure, and performance. Here, we show that the level of Mg incorporation is positively correlated with long-term stability and negatively correlated with rate capacity, and that the latter effect yields a stronger influence upon the overall performance, with the best-performing sample possessing a Mg quantity equivalent to ∼1/5 that of an equimolar concentration. This finding demonstrates not only that the variation of individual elemental levels offers a promising and relatively unexplored avenue to optimize the electrochemical performance of HEO materials but also that it should not be assumed that equimolar compositions of constituent elements are necessarily the best.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Nanotwin formation in Ni-Mo-W alloys deposited by dc magnetron sputtering

Nanotwinned metals and alloys have an attractive suite of properties, but the formation of the underlying nanostructure is generally dependent on the alloy chemistry and processing conditions. This study was undertaken to investigate the effect of deposition rate on nanotwin formation in sputter deposited Ni 84 Mo 11 W 5 that possess ultrahigh strength and stability. Specifically, deposition rates of 0.5-2.3 nm/s were examined and the grain size, texture, twin spacing and hardness were characterized. Minimal variations in the underlying nanostructure and attendant hardness were observed, elucidating a wide processing window and the importance of chemistry on the formation of nanotwins in this alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Pit rim decomposition into multiple quantum dots on surfaces of epitaxial thin films grown on pit-patterned substrates

Here, we report results of dynamical simulations according to an experimentally validated surface morphological evolution model on the formation of regular arrays of quantum dot molecules (QDMs) consisting of 1D arrays of smaller interacting quantum dots (QDs). These QD arrays form along the sides of each pit rim on the surface of a coherently strained thin film epitaxially deposited on a semiconductor substrate, the surface of which consists of a periodic pattern of inverted prismatic pits with rectangular pit openings. We find that this complex QDM pattern results from the decomposition of the pit rim from a “quantum fortress” with four elongated QDs into four 1D arrays of multiple smaller QDs arranged along each side of the pit rim. Systematic parametric analysis indicates that varying the pit opening dimensions and the pit wall inclination directly impacts the number of QDs in the resulting QDM pattern, while varying the pit depth only affects the dimensions of the QDs in the nanostructure pattern. Therefore, the number, arrangement, and sizes of QDs in the resulting pattern of QDMs on the film surface can be engineered precisely by proper tuning of the pit design parameters. Our simulation results are supported by predictions of morphological stability analysis, which explains the pit rim decomposition into multiple QDs as the outcome of a tip-splitting instability and provides a fundamental characterization of the post-instability nanostructure pattern. Our theoretical findings can play a vital role in designing optimal semiconductor surface patterns toward enabling future nanofabrication technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Halide Ion Migration in Perovskite Nanocrystals and Nanostructures

The optical and electronic properties of metal halide perovskites provide insight into the operation of solar cells as well as their long-term operational stability. Halide mobility in perovskite films is an important factor influencing solar cell performance. One can visualize halide ion migration through halide exchange between two nanocrystal suspensions or between physically paired films of two different metal halide perovskites. The ability to tune band gap by varying halide ratios (Cl:Br or Br:I) allows the synthesis of mixed halide perovskites with tailored absorption and emission across the entire visible spectrum. Interestingly, mixed halide (e.g., MAPb(Br 0.5 I 0.5 ) 3 ) films undergo phase segregation to form Br-rich and I-rich sites under steady state illumination. Upon halting illumination, segregated phases mix to restore original mixed halide compositions. Introducing multiple cations (Cs, formamidinium) at the A site or alloying with Cl greatly suppresses halide mobilities. Long-term irradiation of MAPb(Br 0.5 I 0.5 ) 3 films also cause expulsion of iodide leaving behind Br-rich phases. Hole trapping at I-rich sites in MAPb(Br 0.5 I 0.5 ) 3 is considered to be an important step in inducing halide mobility in photoirradiated films. Finally, this Account focuses on halide ion migration in nanocrystals and nanostructured films driven by entropy of mixing in dark and phase segregation under light irradiation.

14 SOLAR ENERGY↗
DOE OSTI2023

ATRP Enhances Structural Correlations In Polymerization–Induced Phase Separation**

Synthetic methods to control the structure of materials at sub–micron scales are typically based on the self–assembly of structural building blocks with precise size and morphology. On the other hand, many living systems can generate structure across a broad range of length scales in one step directly from macromolecules, using phase separation. Here, we introduce and control structure at the nano– and microscales through polymerization in the solid state, which has the unusual capability of both triggering and arresting phase separation. In particular, we show that atom transfer radical polymerization (ATRP) enables control of nucleation, growth, and stabilization of phase–separated poly–methylmethacrylate (PMMA) domains in a solid polystyrene (PS) matrix. ATRP yields durable nanostructures with low size dispersity and high degrees of structural correlations. Furthermore, we demonstrate that the length scale of these materials is controlled by the synthesis parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Pd/CeO2/SiC Chemical Sensors

The incorporation of nanostructured interfacial layers of CeO2 has been proposed to enhance the performances of Pd/SiC Schottky diodes used to sense hydrogen and hydrocarbons at high temperatures. If successful, this development could prove beneficial in numerous applications in which there are requirements to sense hydrogen and hydrocarbons at high temperatures: examples include monitoring of exhaust gases from engines and detecting fires. Sensitivity and thermal stability are major considerations affecting the development of high-temperature chemical sensors. In the case of a metal/SiC Schottky diode for a number of metals, the SiC becomes more chemically active in the presence of the thin metal film on the SiC surface at high temperature. This increase in chemical reactivity causes changes in chemical composition and structure of the metal/SiC interface. The practical effect of the changes is to alter the electronic and other properties of the device in such a manner as to degrade its performance as a chemical sensor. To delay or prevent these changes, it is necessary to limit operation to a temperature <450 C for these sensor structures. The present proposal to incorporate interfacial CeO2 films is based partly on the observation that nanostructured materials in general have potentially useful electrical properties, including an ability to enhance the transfer of electrons. In particular, nanostructured CeO2, that is CeO2 with nanosized grains, has shown promise for incorporation into hightemperature electronic devices. Nanostructured CeO2 films can be formed on SiC and have been shown to exhibit high thermal stability on SiC, characterized by the ability to withstand temperatures somewhat greater than 700 C for limited times. The exchanges of oxygen between CeO2 and SiC prevent the formation of carbon and other chemical species that are unfavorable for operation of a SiC-based Schottky diode as a chemical sensor. Consequently, it is anticipated that in a Pd/CeO2/SiC Schottky diode, the nanostructured interfacial CeO2 layer would contribute to thermal stability and, by contributing to transfer of electrons, would also contribute to sensitivity.

Lu, Weijie↗
DOE OSTI2026

Synergistic CuWO 4 /NiS 2 Binary Nanostructures for Efficient Photocatalytic Hydrogen Production

A viable and ecologically safe method for producing green hydrogen is photocatalytic hydrogen (H 2 ) production. However, the development of effective semiconductor materials with improved activity and long-term stability is still a major obstacle. Here, in this work, we report the development of a broadband-gap, UV light-responsive CuWO 4 /NiS 2 nanocomposite using simple hydrothermal and wet impregnation techniques. The hybrid systems, with photocatalytic presentation, were thoroughly assessed using spectroscopic, photophysical, and microscopic characterization methods. The optimized CuWO 4 /NiS 2 nanostructure demonstrated an impressive H 2 generation rate of 28.2 mmol h –1 g –1 under light irradiation, which is roughly 2.71 and 3.28 times greater than those of pristine CuWO 4 (10.4) and NiS 2 (8.6 mmol h -1 g (cat) -1 ), respectively. The enhanced presentation is ascribed to the synergetic interface between the coupled semiconductors, which facilitates the formation of a nanostructure. This arrangement inhibits electron–hole recombination and encourages effective charge carrier parting. Additionally, compared with pristine CuWO 4 and NiS 2 , respectively, the CuWO 4 /NiS 2 composite showed a noticeably greater photocurrent density. The developed nanostructured CuWO 4 /NiS 2 displayed a 28.6% quantum efficiency at 450 nm. These outcomes validate CuWO 4 /NiS 2 ’s significant aptitude as a non-noble-metal photocatalyst for the production of sustainable hydrogen.

CuWO4/NiS2↗
DOE OSTI2020

Unraveling the structural stability and the electronic structure of ThO 2 clusters

Unraveling the correlations between the geometry, the relative energy and the electronic structure of metal oxide nanostructures is crucial for a better control of their size, shape and properties. Here, we investigated these correlations for stoichiometric thorium dioxide clusters ranging from ThO 2 to Th 8 O 16 using a chemically-driven geometry search algorithm in combination with state-of-the-art first principles calculations. This strategy allows us to homogeneously screen the potential energy surface of actinide oxide clusters for the first time. It is found that the presence of peroxo and superoxo groups tends to increase the total energy of the system by at least 3.5 eV and 7 eV, respectively. For the larger clusters, the presence of terminal oxygen atoms increases the energy by about 0.5 eV. Regarding the electronic structure, it is found that the HOMO–LUMO gap is larger in systems containing only bridging oxygen atoms (~2–3.5 eV) than for systems containing oxo groups (~1–3 eV), peroxo groups (~0–2 eV), and superoxo groups (~0–1 eV). Furthermore, while the LUMO is always dominated by thorium orbitals, the composition of the HOMO changes in the presence or the absence of oxo, peroxo and/or superoxo groups: in the presence of peroxo groups, it is dominated by thorium orbitals, in all other cases, it is dominated by oxygen orbitals, and is rather localized in the presence of terminal oxo or superoxo groups. These correlations are of great interest for synthesizing clusters with tailored properties, especially for applications in the field of nuclear energy and heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Interpretable design of Ir-free trimetallic electrocatalysts for ammonia oxidation with graph neural networks

The electrochemical ammonia oxidation to dinitrogen as a means for energy and environmental applications is a key technology toward the realization of a sustainable nitrogen cycle. The state-of-the-art metal catalysts including Pt and its bimetallics with Ir show promising activity, albeit suffering from high overpotentials for appreciable current densities and the soaring price of precious metals. Herein, the immense design space of ternary Pt alloy nanostructures is explored by graph neural networks trained on ab initio data for concurrently predicting site reactivity, surface stability, and catalyst synthesizability descriptors. Among a few Ir-free candidates that emerge from the active learning workflow, Pt 3 Ru-M (M: Fe, Co, or Ni) alloys were successfully synthesized and experimentally verified to be more active toward ammonia oxidation than Pt, Pt 3 Ir, and Pt 3 Ru. More importantly, feature attribution analyses using the machine-learned representation of site motifs provide fundamental insights into chemical bonding at metal surfaces and shed light on design strategies for high-performance catalytic systems beyond the d-band center metric of binding sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Enhancing hyperspectral EELS analysis of complex plasmonic nanostructures with pan-sharpening

Nanoscale hyperspectral techniques—such as electron energy loss spectroscopy (EELS)—are critical to understand the optical response in plasmonic nanostructures, but as systems become increasingly complex, the required sampling density and acquisition times become prohibitive for instrumental and specimen stability. As a result, there has been a recent push for new experimental methodologies that can provide comprehensive information about a complex system, while significantly reducing the duration of the experiment. In this work, we present a pan-sharpening approach to hyperspectral EELS analysis, where we acquire two datasets from the same region (one with high spatial resolution and one with high spectral fidelity) and combine them to achieve a single dataset with the beneficial properties of both. This work outlines a straightforward, reproducible pathway to reduced experiment times and higher signal-to-noise ratios, while retaining the relevant physical parameters of the plasmonic response, and is generally applicable to a wide range of spectroscopy modalities.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Lead halide perovskite nanowires stabilized by block copolymers for Langmuir-Blodgett assembly

The rapid development of solar cells based on lead halide perovskites (LHPs) has prompted very active research activities in other closely-related fields. Colloidal nanostructures of such materials display superior optoelectronic properties. Especially, one-dimensional (1D) LHPs nanowires show anisotropic optical properties when they are highly oriented. However, the ionic nature makes them very sensitive to external environment, limiting their large scale practical applications. Here, we introduce an amphiphilic block copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-P4VP), to chemically modify the surface of colloidal CsPbBr 3 nanowires. Finally, the resulting core-shell nanowires show enhanced photoluminescent emission and good colloidal stability against water. Taking advantage of the stability enhancement, we further applied a modified Langmuir-Blodgett technique to assemble monolayers of highly aligned nanowires, and studied their anisotropic optical properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Accelerating Manufacturing of Powder-Processed Strong, Lightweight and Thermally Stable Bulk Nanocrystalline Al Alloys via Engineered Interface States

The overarching goal of this program is to develop an integrated materials by design framework enabling a simple, scalable, and efficient manufacturing route for thermally stable nanocrystalline Al-based alloys with high specific strength over a range of service temperatures. The central scientific principle underpinning this program is the elucidation, and ultimately implementation in novel alloy design, of unique interfacial structures and chemistries driven by segregation in multi-component systems that give rise to unprecedented processability and properties. This program targeted nanocrystalline Al-based ternary alloys produced by mechanical alloying of powders followed by compaction and sintering with hot pressing, which are inherently scalable and inexpensive manufacturing routes, but when applied to nanocrystalline alloys are usually plagued by low density and/or poor retention of the intended nanostructures during processing. This program successfully demonstrated manufacturing of a bulk (>1 cm 3 ) nanocrystalline Al-based alloy with a combination of thermal stability, high temperature strength retention, and specific strength that exceeds the current-state-of-the-art of Al alloys. It is anticipated that the greatest technological impact will occur by demonstration of rapid and scalable manufacturing of bulk nanocrystalline Al alloys with exceptional thermal stability and mechanical performance, thus enabling increased energy efficiency in high performance power generation systems via: (i) replacement of existing components with lightweight Al-based alloys and (ii) increasing operating temperatures with property retention. The program focused on the development of a simple and efficient manufacturing route for thermally stable nanocrystalline Al-based alloys with high specific strength over a range of service temperatures. The program is expected to have direct impact on scalable and economic manufacturing of bulk nanocrystalline alloys. This program profited from the recent discovery by the project team of segregation-driven amorphous intergranular films in nanocrystalline metallic alloys that can be kinetically frozen-in at sub-solidus temperatures. These interfacial states (also known as amorphous complexions) comprise a large fraction of the total material in nanocrystalline alloys and are responsible for two beneficial characteristics that anchor the proposed work: (1) activated sintering leading to high density and (2) retained nanostructures leading to high strengths that approach a substantial fraction of the theoretical limit. More specifically, these engineered interfaces led to a three-fold benefit: (i) high-throughput materials processing with low energy budget and cost, (ii) exceptional thermal stability, and (iii) high specific strength at both room temperature and intermediate temperatures experienced during service.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

All-Sputtered, Superior Power Density Thin-Film Solid Oxide Fuel Cells with a Novel Nanofibrous Ceramic Cathode

Thin film solid oxide fuel cells (TF-SOFCs) are attracting attention due to their ability to operate at comparatively lower temperatures (400–650 °C) that are unattainable for conventional anode-supported SOFCs (650–800 °C). However, limited cathode performance and cell scalability remain persistent issues. Here, we report a new approach of fabricating yttria-stabilized zirconia (YSZ)-based TF-SOFCs via a scalable magnetron sputtering process. Notable is the development and deposition of a porous La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 2.95 (LSCF)-based cathode with a unique fibrous nanostructure. This all-sputtered cell shows an open-circuit voltage of ~1.0 V and peak power densities of ~1.7 and ~2.5 W/cm 2 at 600 and 650 °C, respectively, under hydrogen fuel and air along with showing stable performance in short-term testing. The power densities obtained in this work are the highest among YSZ-based SOFCs at these low temperatures, which demonstrate the feasibility of fabricating exceptionally high-performance TF-SOFC cells with distinctive dense or porous nanostructures for each layer, as desired, by a sputtering process. This work illustrates a new, potentially low-cost, and scalable platform for the fabrication of next-generation TF-SOFCs with excellent power output and stability.

25 ENERGY STORAGE↗
DOE OSTI2021

Galvanic Transformation Dynamics in Heterostructured Nanoparticles

Corrosion is a significant problem for the stability of structural metals and potentially for functional nanomaterials in operating environments. When two metals with different electrochemical potentials form a junction, galvanic corrosion occurs, resulting in the sacrificial dissolution of the metal with a higher oxidation potential (lower electrode potential). In this report it is shown that bimetallic hetero-nanostructures composed of phase-segregated metals undergo galvanic corrosion in aqueous environments. Such selective etching of the sacrificial metal in heterojunction particles leads to the formation of unusual and kinetically stabilized half-spheroid particles. By using a fluid cell and in situ scanning transmission electron microscopy, a two-stage corrosion process can be observed where the Cu experiences a fractal breakdown before the Ag corrodes due to the lack of a protective oxide layer. However, when treated with a mild Ar plasma, the stability of these structures against corrosion is enhanced due to the conversion of the amorphous native oxide to a denser, thin layer of CuO on the Cu surface. Taken together, this work highlights the importance of considering the effects of galvanic corrosion on the stability of multicomponent nanoparticles, and it shows how mass transport in a nanoscale system is influenced by redox processes.

36 MATERIALS SCIENCE↗