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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Understanding the morphology and chemical activity of model ZrO x /Au (111) catalysts for CO 2 hydrogenation

In this study, the growth of ZrO x on Au (111) was investigated using scanning tunneling microscopy (STM) and synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Nanostructures of ZrO x (x= 1,2) at the sub-monolayer (≤ 0.3 ML) level were prepared by vapor depositing Zr metal onto Au (111) followed by oxidation with O 2 or CO 2 . At low coverages of the admetal (< 0.05 ML), the formed ZrO x nanostructures were dispersed randomly on the terraces and steps of the Au(111) substrate. Strong oxide-metal interactions prevented the formation of islands of zirconia. The ZrO x nanostructures displayed a reactivity towards CO 2 and H 2 not seen for bulk zirconia. C 1 s AP-XPS results indicated that CO 2 molecules adsorbed on Zr/ZrO x /Au(111) surfaces could undergo partial decomposition on Zr (CO 2 , gas → CO gas + O ads ), or react with oxygen sites from ZrO x to yield carbonates (Zr-CO 3, ads ). Further, after exposing ZrO 2 /Au (111) surfaces to 1:3 mixtures of CO 2 :H 2 , the formation of HCOO, CO 3 , and CH 3 O was detected in AP-XP spectra. These chemical species decomposed at temperatures in the range of 400-600 K, making them possible reaction intermediates for methanol synthesis.

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

High thermoelectric figure of merit of porous Si nanowires from 300 to 700 K.

Thermoelectrics operating at high temperature can cost-effectively convert waste heat and compete with other zero-carbon technologies. Among different high-temperature thermoelectrics materials, silicon nanowires possess the combined attributes of cost effectiveness and mature manufacturing infrastructures. Despite significant breakthroughs in silicon nanowires based thermoelectrics for waste heat conversion, the figure of merit (ZT) or operating temperature has remained low. Here, we report the synthesis of large-area, wafer-scale arrays of porous silicon nanowires with ultra-thin Si crystallite size of ~4 nm. Concurrent measurements of thermal conductivity (κ), electrical conductivity (σ), and Seebeck coefficient (S) on the same nanowire show a ZT of 0.71 at 700 K, which is more than ~18 times higher than bulk Si. This ZT value is more than two times higher than any nanostructured Si-based thermoelectrics reported in the literature at 700 K. Experimental data and theoretical modeling demonstrate that this work has the potential to achieve a ZT of ~1 at 1000 K.

36 MATERIALS SCIENCE↗
NASA NTRS2015

Toward Edge-Defined Holey Boron Nitride Nanosheets

"Holey" two-dimensional (2D) nanosheets with well-defined holy morphology and edge chemistry are highly desirable for applications such as energy storage, catalysis, sensing, transistors, and molecular transport/separation. For example, holey grapheme is currently under extensive investigation for energy storage applications because of the improvement in ion transport due to through the thickness pathways provided by the holes. Without the holes, the 2D materials have significant limitations for such applications in which efficient ion transport is important. As part of an effort to apply this approach to other 2D nanomaterials, a method to etch geometrically defined pits or holes on the basal plane surface of hexagonal boron nitride (h-BN) nanosheets has been developed. The etching, conducted via heating in ambient air using metal nanoparticles as catalysts, was facile, controllable, and scalable. Starting h-BN layered crystals were etched and subsequently exfoliated into boron nitride nanosheets (BNNSs). The as-etched and exfoliated h-BN nanosheets possessed defined pit and hole shapes that were comprised of regulated nanostructures at the edges. The current finding are the first step toward the bulk preparation of holey BNNSs with defined holes and edges.

Lin, Yi↗
DOE OSTI2023

Gradient nanostructuring via compositional means

Nanocrystalline metals are inherently unstable against thermal and mechanical stimuli, commonly resulting in significant grain growth. Also, while these metals exhibit substantial Hall-Petch strengthening, they tend to suffer from low ductility and fracture toughness. With regard to the grain growth problem, alloying elements have been employed to stabilize the microstructure through kinetic and/or thermodynamic mechanisms. And to address the ductility challenge, spatially-graded grain size distributions have been developed to facilitate heterogeneous deformation modes: high-strength at the surface and plastic deformation in the bulk. In the present work, we combine these two strategies and present a new methodology for the fabrication of gradient nanostructured metals via compositional means. Here, we have demonstrated that annealing a compositionally stepwise Pt-Au film with a homogenous microstructure results in a film with a spatial microstructural gradient, exhibiting grains which can be twice as wide in the bulk compared to the outer surfaces. Additionally, phase-field modeling was employed for the comparison with experimental results and for further investigation of the competing mechanisms of Au diffusion and thermally induced grain growth. This fabrication method offers an alternative approach for developing the next generation of microstructurally stable gradient nanostructured films.

36 MATERIALS SCIENCE↗
DOE OSTI2022

3rd harmonic magnetometry assessment of NbTiN-based SIS structures

In the quest for alternative superconducting materials to bring accelerator cavity performance beyond the bulk niobium (Nb) intrinsic limits, a promising concept proposes that superconductor-insulator-superconductor (SIS) thin film structures can delay magnetic flux penetration in accelerator cavities to higher fields [1]. NbTiN is a candidate superconductor for such structures. We have demonstrated high quality NbTiN and AlN deposited by reactive direct current magnetron sputtering (DCMS), both for individual layers and multilayers. Interface quality has been assessed for bi-layer stacks with various NbTiN and AlN thicknesses from 500 and 30 nm down to 3 and 1 nm. These SIS structures show continued sharp interfaces. The Hfp enhancement of the films was examined with 3rd harmonic magnetometry. The system was designed and built in an ongoing collaboration with CEA Saclay. It can measure 1? to 2? samples on a temperature controlled stage. This contribution presents the assessment of the first penetration field enhancement with 3rd harmonic magnetometry for standalone films and multilayer nanostructures.

Valente, Anne-Marie↗
DOE OSTI2025

An unexpectedly shrunken bandgap in V2O5 nanoparticles

Synchrotron x-ray spectroscopy was employed to determine the effects of nanostructuring on electronic band structure in V2O5, a promising cathode material and widely used catalyst. V2O5nanoparticle and bulk powders were characterized via P-XRD, electron microscopy, and diffuse reflectance ultraviolet/visible/near-infrared spectroscopy to confirm the optical bandgap. X-ray emission spectroscopy revealed the nanoparticle valence band O 2pstates to be upshifted relative to the bulk, while x-ray absorption spectroscopy and resonant inelastic x-ray scattering showed the lowest V 3dconduction band states to be static. Together, these changes (in conjunction with an increased density of unoccupied lower conduction band states) produce a shrunken bandgap in the V2O5nanoparticles that defies the Burstein-Moss effect. Changes in nanoparticle band structure are generally attributed to oxygen vacancy defects. While nanostructure bandgap reduction is in line with much previous computational work, it is unexpected from most previous experimental results. To our knowledge, this is the first synchrotron x-ray spectroscopy study of a shrunken bandgap achieved in pure V2O5nanoparticles.

Anquillare, E L↗
DOE OSTI2022

Kinetics and evolution of solid-state metal dealloying in thin films with multimodal analysis

Thin-film solid-state metal dealloying (thin-film SSMD) is an emerging technique that uses self-organization to design nanostructured thin films. The resulting 3D bicontinuous nanostructures are promising for a wide range of applications, such as catalysis and energy storage. In this work, we prepared thin films by SSMD using Ti-Cu as the parent alloy and Mg as the solvent. Using a multimodal approach, we combined synchrotron X-ray spectroscopy, diffraction, and high-resolution electron-based spectroscopy and imaging to study their morphological, structural, and chemical evolution. The processing-structure relationship was analyzed as a function of parent alloy composition and dealloying temperature and time. Morphological transitions from globular, to lamellar, to bicontinuous structures, in conjunction with a ligament size evolution, were identified as functions of the parent alloy composition. The dealloying rate increased with increasing concentration of interdiffusing elements (dissolving component) in the parent alloy. The parting limit, a dealloying compositional threshold, was systematically analyzed and determined to be 30%–40%. The order of crystalline phase formation is CuMg 2 , Cu 2 Mg, and Ti; the Ti phase first shows self-reorganization during dealloying, separate from the crystallization process. The coarsening in thin-film SSMD was identified and not entirely self-similar; in addition to the increase of ligament size over time, the formation of larger globular ligaments were also observed. This work furthers our fundamental understanding of thin-film SSMD and nanostructured thin-film design, where the thermodynamic and kinetic effects differ from the bulk counterparts. The fact that dealloying and diffusion outpaces the crystallization and new phase formation also offers opportunities to utilize thin-film SSMD in certain alloy systems in which deleterious intermetallic phases need to be suppressed, that may not be possible in the bulk geometry.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Europium-doped barium chloride storage phosphor plate synthesized by pulsed laser deposition

In computed radiography, scattering of the stimulation light by the storage phosphor crystals in the imaging plates negatively impacts spatial resolution. Storage phosphor plates with thinner phosphor layers have been developed to reduce scattering distance and increase spatial resolution, although at the expense of reduced x-ray absorption. The authors hypothesize that a transparent or translucent nanostructured film, containing a much higher percentage of storage phosphor crystals than achievable in bulk glass-ceramic materials made by conventional methods, may have acceptable photostimulated luminescence efficiency and imaging performance characteristics greater than commercial imaging plates. Films were produced via pulsed laser deposition by alternating target materials of the storage phosphor BaCl 2 :Eu 2+ and either silica or silicon. X-ray diffraction and photoluminescence characterization were conducted to confirm the presence of BaCl 2 :Eu 2+ crystallites. The films were able to store optical data and be read out to produce x-ray radiographs demonstrating 50-mu m spatial resolution. The performance of the experimental storage phosphor plates was compared to commercially available imaging plates. The authors demonstrate for the first time the synthesis of a glass-ceramic imaging plate for computed radiography by pulsed laser deposition.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Revealing aggregation of non-fullerene acceptors in intermixed phase by ultraviolet-visible absorption spectroscopy

Non-fullerene acceptor (NFA) aggregation is crucial in determining bulk-heterojunction (BHJ) organic photovoltaic (OPV) performance. However, it is still a big challenge to characterize the nanostructure of NFAs in the disordered donor-acceptor intermixed phase. Here, we demonstrate a method to characterize NFA aggregation and composition in the intermixed phase by measuring NFA concentration-dependent ultraviolet-visible (UV-vis) absorption spectroscopy of BHJ films. In various polymer:NFA films, an absorption shift as a function of increasing molecular concentration (ASIMC) phenomenon is observed, and different NFA aggregation behaviors can be distinguished. The ASIMC method was then applied to study the influence of processing conditions on the NFA concentration in the intermixed phase of devices to establish a correlation with device efficiency. The current work provides a feasible tool to study the nanostructure of NFAs in the complex polymer matrix and to understand the variations in the NFA concentration in the intermixed phase under non-equilibrium conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Depth-Dependent Emission from Silver Dopants in Single CdSe Nanoplatelets

Dopants in semiconductor nanostructures offer tremendous control over electronic, optical, and magnetic properties beyond what is achievable in bulk materials. We demonstrate that the broad dopant emission in semiconductor nanoplatelets effectively maps the electron wave function across the nanoplatelet thickness. Both the emission energy and lifetime of the dopant transition depend strongly on the depth of the dopant within the nanoplatelet. This dependence arises from the electrostatic self-interaction of the charged dopant, which varies with proximity to the dielectric discontinuity at the nanoplatelet surface. Through comprehensive single-particle spectroscopy of silver-doped CdSe nanoplatelets, we verify that acceptors near the center emit at higher energies with shorter lifetimes, while those near the surface emit at lower energies with longer lifetimes. This spatial mapping also reveals unusual two-color emission from individual nanoplatelets, with enhanced Auger recombination yielding exceptional photon antibunching (>90% purity) at room temperature, suggesting potential applications in quantum information technologies.

cadmium selenide↗
NASA NTRS2003

Nanoporous Silicon Carbide for Nanoelectromechanical Systems Applications

A major goal of this project is to produce porous silicon carbide (PSiC) via an electroless process for eventual utilization in nanoscale sensing platforms. Results in the literature have shown a variety of porous morphologies in SiC produced in anodic cells. Therefore, predictability and reproducibility of porous structures are initial concerns. This work has concentrated on producing morphologies of known porosity, with particular attention paid toward producing the extremely high surface areas required for a porous flow sensor. We have conducted a parametric study of electroless etching conditions and characteristics of the resulting physical nanostructure and also investigated the relationship between morphology and materials properties. Further, we have investigated bulk etching of SiC using both photo-electrochemical etching and inductively-coupled-plasma reactive ion etching techniques.

Hossain, T.↗
DOE OSTI2022

Understanding Synthesis and Structural Variation of Nanomaterials Through In Situ/Operando XAS and SAXS

Nanostructured materials with high surface area and low coordinated atoms present distinct intrinsic properties from their bulk counterparts. However, nanomaterials' nucleation/growth mechanism during the synthesis process and the changes of the nanomaterials in the working state are still not thoroughly studied. As two indispensable methods, X-ray absorption spectroscopy (XAS) provides nanomaterials' electronic structure and coordination environment, while small-angle X-ray scattering (SAXS) offers structural properties and morphology information. Here, a combination of in situ/operando XAS and SAXS provides high temporal and spatial resolution to monitor the evolution of nanomaterials. This review gives a brief introduction to in situ/operando SAXS/XAS cells. In addition, the application of in situ/operando XAS and SAXS in preparing nanomaterials and studying changes of working nanomaterials are summarized.

25 ENERGY STORAGE↗
DOE OSTI2022

Probing electrolyte–silica interactions through simulations of the infrared spectroscopy of nanoscale pores

The structural and dynamical properties of nanoconfined solutions can differ dramatically from those of the corresponding bulk systems. Understanding the changes induced by confinement is central to controlling the behavior of synthetic nanostructured materials and predicting the characteristics of biological and geochemical systems. A key outstanding issue is how the molecular-level behavior of nanoconfined electrolyte solutions is reflected in different experimental, particularly spectroscopic, measurements. This is addressed here through molecular dynamics simulations of the OH stretching infrared (IR) spectroscopy of NaCl, NaBr, and NaI solutions in isotopically dilute HOD/D 2 O confined in hydroxylated amorphous silica slit pores of width 1–6 nm and pH ~2. In addition, the water reorientation dynamics and spectral diffusion, accessible by pump–probe anisotropy and two-dimensional IR measurements, are investigated. In this work, the aim is to elucidate the effect of salt identity, confinement, and salt concentration on the vibrational spectra. It is found that the IR spectra of the electrolyte solutions are only modestly blue-shifted upon confinement in amorphous silica slit pores, with both the size of the shift and linewidth increasing with the halide size, but these effects are suppressed as the salt concentration is increased. This indicates the limitations of linear IR spectroscopy as a probe of confined water. However, the OH reorientational and spectral diffusion dynamics are significantly slowed by confinement even at the lowest concentrations. The retardation of the dynamics eases with increasing salt concentration and pore width, but it exhibits a more complex behavior as a function of halide.

Mesoporous material↗
DOE OSTI2021

Microstructure and Hard Magnetic Properties of Sm 1-x Zr x (Fe,Co) 11.3-y Ti 0.7 By Ingots and Thick Melt-Spun Ribbons

Permanent magnets made from Sm(Fe,Co) 12 -based compounds are being actively pursued through nanostructuring and powder metallurgy. This study was aimed at the development of hard magnetic properties in bulk as-cast alloys and in melt-spun alloys for very low wheel speeds. Slower solidification rates and alloying with Zr promote the tetragonal ThMn 12 -type crystal structure, whereas higher solidification rates and alloying with B replace the ThMn 12 structure type with the TbCu 7 structure type. When introduced simultaneously, Zr and B dramatically reduce the alloy solidification rates required for both the refinement of the 1:12 crystallites and their replacement with the 1:7 phase. In bulk arc-melted alloys, this allowed for a microstructure of separated 1:12 crystallites 1–3 μm in size, although, because of the ferromagnetic nature of a minority phase, the coercivity of these fine-grained alloys reached only 0.73 kOe. A moderately accelerated solidification further refined the 1:12 crystallites and increased the coercivity; a Sm 0.7 Zr 0.4 (Fe,Co) 10.8 Ti 0.7 B 0.5 alloy exhibited a coercivity of 1.5 kOe and a maximum energy product of 3.4 MGOe when it was melt-spun into a 0.26-mm-thick ribbon. A more rapid solidification suppressed the 1:12 phase and after annealing at 800–850 °C, the alloys modified with Zr and B developed reasonably high coercivity and maximum energy product even when melt-spun at a wheel speed of 6 m/s. For the above-mentioned alloy, these values were 4.1 kOe and 7.8 MGOe, respectively. Further, a similarly processed very-Sm-lean Sm 0.5 Zr 0.6 (Fe,Co) 10.6 Ti 0.7 B 0.7 alloy exhibited a remanence of 8.8 kG and an energy product of 7.4 MGOe.

36 MATERIALS SCIENCE↗
NASA NTRS2003

Atomistic Modeling of Nanostructures via the BFS Quantum Approximate Method

Ideally, computational modeling techniques for nanoscopic physics would be able to perform free of limitations on the type and number of elements, while providing comparable accuracy when dealing with bulk or surface problems. Computational efficiency is also desirable, if not mandatory, for properly dealing with the complexity of typical nano-strucured systems. A quantum approximate technique, the BFS method for alloys, which attempts to meet these demands, is introduced for the calculation of the energetics of nanostructures. The versatility of the technique is demonstrated through analysis of diverse systems, including multi-phase precipitation in a five element Ni-Al-Ti-Cr-Cu alloy and the formation of mixed composition Co-Cu islands on a metallic Cu(III) substrate.

Bozzolo, Guillermo↗
DOE OSTI2021

On the Origin of Room-Temperature Amplified Spontaneous Emission in CsPbBr 3 Single Crystals

CsPbBr 3 is an all-inorganic halide perovskite with excellent photoluminescence (PL) properties for laser applications. Amplified spontaneous emission (ASE) is a prerequisite for lasing and typically observed from low-dimensional CsPbBr3 nanostructures, where quantum confinement enhances ASE. However, a gain medium for lasing should be prepared into a robust bulk form that works under intense light illumination. Here, we demonstrate that bulk CsPbBr 3 single crystals exhibit highly efficient ASE with a threshold of 46 MWcm -2 at 520 nm, if PL reabsorption via the indirect Rashba gap is properly suppressed by thickness control. Based on a series of spectroscopic and microscopic measurements, we show that this below-the-gap absorption can significantly alter the PL feature and even the apparent color of the crystal depending on the crystal size. Our results show that a thin CsPbBr 3 single crystal can be utilized for lasing applications when engineered into a submillimeter thickness for effective light–matter interaction.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Vertically Aligned Single-Crystalline CoFe 2 O 4 Nanobrush Architectures with High Magnetization and Tailored Magnetic Anisotropy

Micrometer-tall vertically aligned single-crystalline CoFe 2 O 4 nanobrush architectures with extraordinarily large aspect ratio have been achieved by the precise control of a kinetic and thermodynamic non-equilibrium pulsed laser epitaxy process. Direct observations by scanning transmission electron microscopy reveal that the nanobrush crystal is mostly defect-free by nature, and epitaxially connected to the substrate through a continuous 2D interface layer. In contrast, periodic dislocations and lattice defects such as anti-phase boundaries and twin boundaries are frequently observed in the 2D interface layer, suggesting that interface misfit strain relaxation under a non-equilibrium growth condition plays a critical role in the self-assembly of such artificial architectures. Further, magnetic property measurements have found that the nanobrushes exhibit a saturation magnetization value of 6.16 μB/f.u., which is much higher than the bulk value. The discovery not only enables insights into an effective route for fabricating unconventional high-quality nanostructures, but also demonstrates a novel magnetic architecture with potential applications in nanomagnetic devices.

36 MATERIALS SCIENCE↗
NASA NTRS2009

Prediction of Material Properties of Nanostructured Polymer Composites Using Atomistic Simulations

Atomistic models of epoxy polymers were built in order to assess the effect of structure at the nanometer scale on the resulting bulk properties such as elastic modulus and thermal conductivity. Atomistic models of both bulk polymer and carbon nanotube polymer composites were built. For the bulk models, the effect of moisture content and temperature on the resulting elastic constants was calculated. A relatively consistent decrease in modulus was seen with increasing temperature. The dependence of modulus on moisture content was less consistent. This behavior was seen for two different epoxy systems, one containing a difunctional epoxy molecule and the other a tetrafunctional epoxy molecule. Both epoxy structures were crosslinked with diamine curing agents. Multifunctional properties were calculated with the nanocomposite models. Molecular dynamics simulation was used to estimate the interfacial thermal (Kapitza) resistance between the carbon nanotube and the surrounding epoxy matrix. These estimated values were used in a multiscale model in order to predict the thermal conductivity of a nanocomposite as a function of the nanometer scaled molecular structure.

Hinkley, J.A.↗