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At least 541 records · Page 30

Nodal hybridization in a two-dimensional heavy-fermion material

Metals with partially filled core atomic shells can form quasiparticles at a low temperature arising from the hybridization of the core level and conduction electrons. The thermodynamic and spectroscopic properties of these metals can be understood as those of a simple metal, but with a significant mass enhancement over the free electron mass—commonly referred to as heavy fermions. In most heavy-fermion materials, the hybridization is approximately isotropic in position and momentum space. However, a combination of low dimensionality and symmetry properties of the core-level wavefunctions can give rise to highly anisotropic electronic interactions with the conduction electrons. Here, in this study, we demonstrate anisotropic hybridization that vanishes along specific directions in momentum space—referred to as nodes—in a lanthanide-based two-dimensional van der Waals heavy-fermion compound, CeSiI. Quasiparticle interference measurements reveal a set of discrete hotspots with high spectral intensity on the Fermi surface. Theoretical modelling and comparison with the quasiparticle interference pattern of the non-heavy-fermion isostructural analogue LaSiI suggest that these features arise from an unconventional electron interaction involving hybridization nodes unique to CeSiI. As a result, the effective mass of the quasiparticles varies by orders of magnitude depending on their direction in momentum space.

36 MATERIALS SCIENCE↗

Magnetic Nanoparticle Extraction of Lithium from Produced Waters - CRADA 483 (Final Report)

The demand for lithium in the energy production industry is expected to increase sharply, development of simple and cost-effective techniques for lithium production and recovery from various lithium sources is essential. In this project, core/shell magnetic nanoparticles were successfully designed to selectively extract lithium from aqueous lithium sources as an extension of Pacific Northwest National Laboratory’s magnetic nanofluid extraction technology. The core/shell magnetic nanoparticles are composed of manganese oxide-based lithium ion sieve shells, which allow selective lithium uptake from brines with multiple coexisting ions, over iron oxide cores, which can respond to external magnetic fields for effective recovery and reuse of adsorbents from a liquid. The synthesized lithium ion-sieves and core/shell magnetic nanoparticles were characterized using several techniques to reveal their crystallinity and morphology. The lithium uptake properties of the lithium ion-sieves and core/shell magnetic nanoparticles were evaluated in terms of lithium adsorption capacity, removal percentage, selectivity, and cycling performance in simulated and natural brines. Magnetic properties of the core/shell magnetic nanoparticles were tested by measuring magnetic saturation, and magnetic response of colloidal solutions containing the core/shell magnetic nanoparticles was tested with permanent magnets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

G0.9 + 0.1 and the emerging class of composite supernova remnants

High-resolution, multifrequency maps of a bright extended radio source near the Galactic center have revealed it to be a classic example of a composite supernova remnant. A steep-spectrum shell of emission, about 8 arcmin in diameter, surrounds a flat-spectrum, highly polarized Crab-like core about 2 arcmin across. The two components have equal flux densities at about 6 cm, marking this source as having the highest core-to-shell ratio among the about 10 composite remnants identified to date. X-ray and far-infrared data on the source are used to constrain the energetics and evolutionary state of the remnant and its putative central pulsar. It is argued that the total energy contained in the Crab-like components requires that the pulsars powering them were all born with periods shorter than 50 ms, and that if a substantial number of neutron stars with slow initial rotation rates exist, their birthplaces have not yet been found.

Helfand, D. J.↗

Experimental Study of the Compression Response of Fluted-Core Composite Panels with Joints

Fluted-core sandwich composites consist of integral angled web members spaced between laminate face sheets, and may have the potential to provide benefits over traditional sandwich composites for certain aerospace applications. However, fabrication of large autoclave-cured fluted-core cylindrical shells with existing autoclaves will require that the shells be fabricated in segments, and joined longitudinally to form a complete barrel. Two different longitudinal fluted-core joint designs were considered experimentally in this study. In particular, jointed fluted-core-composite panels were tested in longitudinal compression because longitudinal compression is the primary loading condition in dry launch-vehicle barrel sections. One of the joint designs performed well in comparison with unjointed test articles, and the other joint design failed at loads approximately 14% lower than unjointed test articles. The compression-after-impact (CAI) performance of jointed fluted-core composites was also investigated by testing test articles that had been subjected to 6 ft-lb impacts. It was found that such impacts reduced the load-carrying capability by 9% to 40%. This reduction is dependent on the joint concept, component flute size, and facesheet thickness.

Schultz, Marc R.↗

Neutron Reflectometry Reveals Diffusion in Contrast-Matched Brush Particle Bilayers

A material system for performing layer-spread experiments on brush particle bilayers is presented and used to determine the diffusion constant of brush particles in the melt state. Selective deuteration of the core and shell of organo-silica nanoparticles grafted with poly(methyl methacrylate) was used to match the scattering length density of the core and the polymer canopy layer. This subdued the scattering of particle cores (i.e., formfactor scattering) and enabled the analysis of the interdiffusion kinetics using neutron reflectivity. For low molecular grafts, i.e., grafts with a molecular weight below the entanglement limit, the interdiffusion kinetics revealed both a sub- and Fickian diffusion regime. The former was attributed to the local dynamics that was constrained by the slow-moving cores of neighboring brush particles that acted as long-lived physical cross-links. No transition to Fickian diffusion was observed for entangled systems, even at prolonged annealing times. This suggested a higher level of kinetic restraint in entangled brush particle melts as compared to, for example, star polymers with a comparable chain length for which Fickian diffusion has been reported under similar conditions.

Diffusion, Polymer Grafted Nanoparticles, Neutron ↗

Structural Analysis of Test Flight Vehicles for Application of Multifunctional Energy Storage System

Under the NASA Aeronautics Research Mission Directorate (ARMD) Convergent Aeronautical Solutions (CAS) project, NASA Glenn Research Center has been leading Multifunctional Structures for High Energy Lightweight Load-bearing Storage (M-SHELLS) research efforts. The technology of integrating load-carrying structures with electrical energy storage capacity has the potential to reduce the overall weight of future electric aircraft. The proposed project goals were to develop M-SHELLS in the form of honeycomb coupons and subcomponents, integrate them into the structure, and conduct low-risk flight-tests onboard a remotely piloted small aircraft. Experimental M-SHELLS energy-storing coupons were fabricated and tested in the laboratory for their electrical and mechanical properties. In this report, finite element model development and structural analyses of two small test aircraft candidates are presented. The finite element analysis of the initial two-spar wing is described for strain, deflection, and weight estimation. After a test aircraft Tempest was acquired, a load-deflection test of the wing was conducted. A finite element model of the Tempest was then developed based on the test aircraft dimensions and construction detail. The component weight analyses from the finite element model and test measurements were correlated. Structural analysis results with multifunctional energy storage panels in the fuselage of the test vehicle are presented. Although the flight test was cancelled because of programmatic reasons and time constraints, the structural analysis results indicate that the mid-fuselage floor composite panel could provide structural integrity with minimal weight penalty while supplying electrical energy. To explore potential future applications of the multifunctional structure, analyses of the NASA X-57 Maxwell electric aircraft and a NASA N+3 Technology Conventional Configuration (N3CC) fuselage are presented. Secondary aluminum structures in the fuselage sub-floor and cargo area were partially replaced with reinforced five-layer composite panels with M-SHELLS honeycomb core. The N3CC fuselage weight reduction associated with each design without risking structural integrity are described. The structural analysis and weight estimation with the application of composite M-SHELLS panels to the N3CC fuselage indicate a 3.2% reduction in the fuselage structural weight, prior to accounting for the additional weight of core material required to complete the energy storage functionality.

Mukhopadhyay, Vivek↗

Structural Analysis of Test Flight Vehicles with Multifunctional Energy Storage

Under the NASA Aeronautics Research Mission Directorate (ARMD) Convergent Aeronautical Solutions (CAS) project, NASA Glenn Research Center has been leading Multifunctional Structures for High Energy Lightweight Load-bearing Storage (M-SHELLS) research efforts. The technology of integrating load-carrying structures with electrical energy storage capacity has the potential to reduce the overall weight of future electric aircraft. The proposed project goals were to develop M-SHELLS in the form of honeycomb coupons and subcomponents, integrate them into the structure, and conduct low-risk flight tests onboard a remotely piloted small aircraft. Experimental M-SHELLS energy-storing coupons were fabricated and tested in the laboratory for their electrical and mechanical properties. In this paper, finite element model development and structural analyses of two small test aircraft candidates are presented. The finite element analysis of the initial two-spar wing is described for strain, deflection, and weight estimation. After a test aircraft Tempest was acquired, a load- deflection test of the wing was conducted. A finite element model of the Tempest was then developed based on the test aircraft dimensions and construction detail. The component weight analysis from the finite element model and test measurements were correlated. Structural analysis results with multifunctional energy storage panels in the fuselage of the test vehicle are presented. Although the flight test was cancelled because of programmatic reasons and time constraints, the structural analysis results indicate that the mid-fuselage floor composite panel could provide structural integrity with minimal weight penalty while supplying electrical energy. To explore potential future applications of the multifunctional structure, analyses of the NASA X-57 Maxwell electric aircraft and a NASA N+3 Technology Conventional Configuration (N3CC) fuselage are presented. Secondary aluminum structure in the fuselage sub-floor and cargo area were partially replaced with reinforced five-layer composite panels with M-SHELLS honeycomb core. The N3CC fuselage weight reduction associated with each design without risking structural integrity are described. The structural analysis and weight estimation with the application of composite M-SHELLS panels to the N3CC fuselage indicate a 3.2% reduction in the fuselage structural weight, prior to accounting for the additional weight of core material required to complete the energy storage functionality.

Mukhopadhyay, Vivek↗

Mg and Ti isotopes in presolar Al2O3

Oxygen isotopic compositions and initial Al-26/Al-27 ratios were reported for two presolar Al2O3 grains, Orgueil B and Bishunpur B39. In Orgueil B, O-17/O-16 is about twice the solar value but O-18/O-16 is normal. In B39, O-17/O-16 is approximately 7x higher than solar and O-18/O-16 is 0.6x the solar value. Spectroscopic observations of red giant stars show similar O compositions, which result when material that has experienced partial H burning is mixed into the stellar envelope by the first dredge-up. The O-17/O-16 ratios indicate that Orgueil B originated around a star of approximately 1.5 solar mass, while B39 formed around either a approximately 2 solar mass or 4-7 solar mass star. Both grains formed with Al-26/Al-27 ratios of approximately 10(exp -3). Aluminum-26 is produced in the H shell after core H burning has ceased and first dredge-up has occurred. It is spread through the envelope by the third dredge-up, which occurs in low- and intermediate-mass stars as a series of mixing events driven by thermal pulses in the He shell. In intermediate-mass stars (3-8 solar mass), Al-26 can also be brought to the surface by the second dredge-up, which occurs at the end of core He burning. We have measured Ti isotopes by ion probe in Orgueil B and Bishunpur B39, looking for evidence of He-shell nucleosynthesis. Stars of approximately 1.5 solar mass do not experience second dredge-up, so the Al-26 in Orgueil B must have been mixed outward during third dredge-up, which also supplies He-shell material to the envelope. The size of the isotopic shifts in Ti and Mg suggest that Orgueil B contains approximately 5-10x more material from the He-shell than from the H-shell. In contrast, the lack of measurable Mg and Ti anomalies in B39 imply little or no He-shell contribution. This indicates that Al-26 in B39 was supplied by second dredge-up prior to He-shell ignition and points to a parent star of 4-7 solar mass.

Huss, G. R.↗

Multi-zone shell and tube heat exchanger

A shell and tube heat exchanger has elongated shell having first and second opposing ends and an open interior. A core divides the open interior of the shell into first and second enclosed portions. The shell has first and second tube fluid openings at opposing ends. End plates divide the first and second enclosed portions into manifold portions and enclosed shell chamber portions. Tubes extend from the end plates, through the enclosed shell chambers to the core. Shell fluid openings are at sides of the elongated shell, a first fluid opening communicating with the first shell chamber, and a second fluid opening communicating with the second shell chamber. The shell has a long axis, and the end plates are angled relative to the long axis. The tubes are polygonal with rounded corners and straight sides. The heat exchanger can be used for both evaporation and condensation processes.

Sabau, Adrian S.↗

Correlative analysis of structure and chemistry of Li x FePO 4 platelets using 4D-STEM and X-ray ptychography

Lithium iron phosphate (Li x FePO 4 ), a cathode material used in rechargeable Li-ion batteries, phase separates upon de/lithiation under equilibrium. The interfacial structure and chemistry within these cathode materials affects Li-ion transport, and therefore battery performance. Here, correlative imaging of Li x FePO 4 was performed using four-dimensional scanning transmission electron microscopy (4D-STEM), scanning transmission X-ray microscopy (STXM), and X-ray ptychography in order to analyze the local structure and chemistry of the same particle set. Over 50,000 diffraction patterns from 10 particles provided measurements of both structure and chemistry at a nanoscale spatial resolution (16.6–49.5 nm) over wide (several micron) fields-of-view with statistical robustness. Li x FePO 4 particles at varying stages of delithiation were measured to examine the evolution of structure and chemistry as a function of delithiation. In lithiated and delithiated particles, local variations were observed in the degree of lithiation even while local lattice structures remained comparatively constant, and calculation of linear coefficients of chemical expansion suggest pinning of the lattice structures in these populations. Partially delithiated particles displayed broadly core–shell-like structures, however, with highly variable behavior both locally and per individual particle that exhibited distinctive intermediate regions at the interface between phases, and pockets within the lithiated core that correspond to FePO 4 in structure and chemistry. The results provide insight into the Li x FePO 4 system, subtleties in the scope and applicability of Vegard’s law (linear lattice parameter-composition behavior) under local versus global measurements, and demonstrate a powerful new combination of experimental and analytical modalities for bridging the crucial gap between local and statistical characterization.

25 ENERGY STORAGE↗

Auger Recombination Lifetime Scaling for Type I and Quasi-Type II Core/Shell Quantum Dots

Having already achieved near-unity quantum yields, with promising properties for light-emitting diode, lasing, and charge separation applications, colloidal core/shell quantum dots have great technological potential. The shell thickness and band alignment of the shell and core materials are known to influence the efficiency of these devices. In many such applications, improving the efficiency requires a deep understanding of multiexcitonic states. In this paper, we elucidate the shell thickness and band alignment dependencies of the biexciton Auger recombination lifetime for quasi-type II CdSe/CdS and type I CdSe/ZnS core/shell quantum dots. We find that the biexciton Auger recombination lifetime increases with the total nanocrystal volume for quasi-type II CdSe/CdS core/shell quantum dots and is independent of the shell thickness for type I CdSe/ZnS core/shell quantum dots. To perform these calculations and compute Auger recombination lifetimes, we developed a low-scaling approach based on the stochastic resolution of identity. The numerical approach provided a framework for studying the scaling of the biexciton Auger recombination lifetimes in terms of the shell thickness dependencies of the exciton radii, Coulomb couplings, and density of final states in quasi-type II CdSe/CdS and type I CdSe/ZnS core/shell quantum dots.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Description of the Proton-Decaying 0 2 + Resonance of the α Particle

The recent precise experimental determination of the monopole transition form factor from the ground state of 4 He to its $0$$^{+}_{2}$ resonance via electron scattering has reinvigorated discussions about the nature of this first excited state of the α particle. The $0$$^{+}_{2}$ state has been traditionally interpreted in the literature as the isoscalar monopole resonance (breathing mode) or, alternatively, as a particle-hole shell-model excitation. To better understand the nature of this state, which lies only ~410 keV above the proton emission threshold, we employ the coupled-channel representation of the no-core Gamow shell model. By considering the [ 3 H + p], [ 3 He + n], and [ 2 H + 2 H] reaction channels, we explain the excitation energy and monopole form factor of the $0$$^{+}_{2}$ state. Furthermore, we argue that the continuum coupling strongly impacts the nature of this state, which carries characteristics of the proton decay threshold.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Recent developments in Pt–Co catalysts for proton-exchange membrane fuel cells

Development of Pt-based oxygen reduction reaction catalysts with high efficiency and high durability is central to the application of proton-exchange membrane fuel cell systems. Pt–Co bimetallic catalysts have drawn extensive attention owing to their capability of delivering high performance and long lifetime for fuel cell applications including light-duty and heavy-duty vehicles. However, further improvements in durability and performance are needed to meet market requirements. To fully exploit the potential of Pt–Co catalysts, new insights into the relationship between catalyst properties and fuel cell performance and durability are needed, and more effective methods to tailor the features of Pt–Co catalysts need to be developed. This review provides a summary and perspective on recent efforts, including work on customizing the Pt shell and Pt:Co ratio, tailoring the crystal structure, and improving carbon support properties, with a particular emphasis on mechanisms leading to enhancement of mass activity, power density, and durability in membrane electrode assembly testing.

25 ENERGY STORAGE↗

Uncertainties in ab initio nuclear structure calculations with chiral interactions

We present theoretical ground state energies and their uncertainties for p -shell nuclei obtained from chiral effective field theory internucleon interactions as a function of chiral order, fitted to two- and three-body data only. We apply a Similary Renormalization Group transformation to improve the numerical convergence of the many-body calculations, and discuss both the numerical uncertainties arising from basis truncations and those from omitted induced many-body forces, as well as chiral truncation uncertainties. With complete Next-to-Next-to-Leading (N 2 LO) order two- and three-body interactions, we find significant overbinding for the ground states in the upper p -shell, but using higher-order two-body potentials, in combination with N 2 LO three-body forces, our predictions agree with experiment throughout the p -shell to within our combined estimated uncertainties. The uncertainties due to chiral order truncation are noticeably larger than the numerical uncertainties, but they are expected to become comparable to the numerical uncertainties at complete N 3 LO.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Thermal Stability of Au Rhombic Dodecahedral Nanocrystals Can Be Greatly Enhanced by Coating Their Surface with an Ultrathin Shell of Pt

Rhombic dodecahedral nanocrystals have been considered particularly difficult to synthesize because they are enclosed by {110}, a low-index facet with the greatest surface energy. Recently, we demonstrated the use of seed-mediated growth for the facile and robust synthesis of Au rhombic dodecahedral nanocrystals (AuRD). While the unique shape and surface structure of AuRD are desirable for potential applications in plasmonics and catalysis, respectively, their high surface energy makes them highly susceptible to thermal degradation. Here we demonstrate that it is feasible to greatly improve the thermal stability with some sacrifice to the plasmonic properties of the original AuRD by coating their surface with an ultrathin shell made of Pt. Our in situ electron microscopy analysis indicates that the ultrathin Pt coating can increase the thermal stability from 60 up to 450 °C, a trend that is also supported by the results from a computational study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of luminescent core/shell α-Zn 3 P 2 /ZnS quantum dots

Metal chalcogenide nanoparticles offer vast control over their optoelectronic properties via size, shape, composition, and morphology which has led to their use across fields including optoelectronics, energy storage, and catalysis. While cadmium and lead-based nanocrystals are prevalent in applications, concerns over their toxicity have motivated researchers to explore alternate classes of nanomaterials based on environmentally benign metals such as zinc and tin. The goal of this research is to identify material systems that offer comparable performance to existing metal chalcogenide systems from abundant, recyclable, and environmentally benign materials. With band gaps that span the visible through the infrared, II–V direct band gap semiconductors such as tetragonal zinc phosphide (α-Zn 3 P 2 ) are promising candidates for optoelectronics. To date, syntheses of α-Zn 3 P 2 nanoparticles have been hindered because of the toxicity of zinc and phosphorus precursors, surface oxidation, and defect states leading to carrier trapping and low photoluminescence quantum yield. Here, we report a colloidal synthesis of quantum confined α-Zn 3 P 2 nanoparticles from common phosphorus precursor tris(trimethylsilyl)phosphine and environmentally benign zinc carboxylates. Shelling of the nanoparticles with zinc sulfide is shown as a method of preventing oxidation and improving the optical properties of the nanoparticles. These results show a route to stabilizing α-Zn 3 P 2 nanoparticles for optoelectronic device applications.

25 ENERGY STORAGE↗

Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies

Recent reports on hydride-doped noble metal nanoclusters strongly suggest that the encapsulated hydride is a part of the superatom core, but no accurate location of the hydride could be experimentally proved, so far. Here, we report herein a hydride-doped eight-electron platinum/silver alloy nanocluster in which the position of four-coordinated hydride was determined by neutron diffraction for the first time. X-ray structures of [PtHAg 19 (dtp/desp) 12 ] (dtp = S 2 P(O n Pr) 2 , 1; dsep = Se 2 P(O i Pr) 2 , 2) describe a central platinum hydride (PtH) unit encapsulated within a distorted Ag 12 icosahedron, the resulting (PtH)@Ag 12 core being stabilized by an outer sphere made up of 7 capping silver atoms and 12 dichalcogenolates. Solid-state structures of 1 and 2 differ somewhat in the spatial configuration of their outer spheres, resulting in overall different symmetries, C 1 and C 3 , respectively. Whereas the multi-NMR spectra of 2 in solution at 173 K reveal that the structure of C 3 symmetry is the predominant one, 1 H and 195 Pt NMR spectra of 1 at the same temperature disclose the presence of isomers of both C 1 and C 3 symmetry. DFT calculations found both isomers to be very close in energy, supporting the fact that they co-exist in solution. They also show that the [PtH@Ag 12 ] 5+ kernel can be viewed as a closed-shell superatomic core, the μ4-hydride electron contributing to its eight-electron count. On the other hand, the 1s(H) orbital contributes only moderately to the superatomic orbitals, being mainly involved in the building of a Pt–H bonding electron pair with the 5d z 2 (Pt) orbital.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Infrared Imaging Using Thermally Stable HgTe/CdS Nanocrystals

Transferring nanocrystals (NCs) from the laboratory environment toward practical applications has raised new challenges. HgTe appears as the most spectrally tunable infrared colloidal platform. Its low-temperature synthesis reduces the growth energy cost yet also favors sintering. Once coupled to a read-out circuit, the Joule effect aggregates the particles, leading to a poorly defined optical edge and large dark current. Here, in this study, we demonstrate that CdS shells bring the expected thermal stability (no redshift upon annealing, reduced tendency to form amalgams, and preservation of photoconduction after an atomic layer deposition process). The electronic structure of these confined particles is unveiled using k.p self-consistent simulations showing a significant exciton binding energy of ~ 200 meV. After shelling, the material displays a p-type behavior that favors the generation of photoconductive gain. The latter is then used to increase the external quantum efficiency of an infrared imager, which now reaches 40% while presenting long-term stability.

77 NANOSCIENCE AND NANOTECHNOLOGY↗