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At least 379 records · Page 21

Hybrid interatomic potential for Sn

To design materials for extreme applications, it is important to understand and predict phase transitions and their influence on material properties under high pressures and temperatures. Atomistic modeling can be a useful tool to assess these behaviors. However, this can be difficult due to the lack of fidelity of the interatomic potentials in reproducing this high pressure and temperature extreme behavior. Here, in this work, a hybrid EAM-R—which is the combination of embedded atom method (EAM) and rapid artificial neural network potential—for Tin (Sn) is described which is capable of accurately modeling the complex sequence of phase transitions between different metallic polymorphs as a function of pressure. This hybrid approach ensures that a basic empirical potential like EAM is used as a lower energy bound. By using the final activation function, the neural network contribution to energy must be positive, assuring stability over the whole configuration space. This implementation has the capacity to reproduce density functional theory results at 6 orders of magnitude slower than a pair potential for molecular dynamics simulation, including elastic and plastic characteristics and relative energies of each phase. Using calculations of the Gibbs free energy, it is demonstrated that the potential precisely predicts the experimentally observed phase changes at temperatures and pressures across the whole phase diagram. At 10.2 GPa, the present potential predicts a first-order phase transition between body-centered tetragonal (BCT) β-Sn and another polymorph of BCT-Sn. This structure transforms into body-centered cubic near the experimentally reported value at 33 GPa. Thus, the Sn potential developed in this paper can be used to study complex deformation mechanisms under extreme conditions of high pressure and strain rates unlike existing potentials. Moreover, the framework developed in this paper can be extended for different material systems with complex phase diagrams.

36 MATERIALS SCIENCE↗

Atomic structures determined from digitally defined nanocrystalline regions

Nanocrystallography has transformed our ability to interrogate the atomic structures of proteins, peptides, organic molecules and materials. By probing atomic level details in ordered sub-10 nm regions of nanocrystals, scanning nanobeam electron diffraction extends the reach of nanocrystallography and in principle obviates the need for diffraction from large portions of one or more crystals. Scanning nanobeam electron diffraction is now applied to determine atomic structures from digitally defined regions of beam-sensitive peptide nanocrystals. Using a direct electron detector, thousands of sparse diffraction patterns over multiple orientations of a given crystal are recorded. Each pattern is assigned to a specific location on a single nanocrystal with axial, lateral and angular coordinates. This approach yields a collection of patterns that represent a tilt series across an angular wedge of reciprocal space: a scanning nanobeam diffraction tomogram. Using this diffraction tomogram, intensities can be digitally extracted from any desired region of a scan in real or diffraction space, exclusive of all other scanned points. Intensities from multiple regions of a crystal or from multiple crystals can be merged to increase data completeness and mitigate missing wedges. It is demonstrated that merged intensities from digitally defined regions of two crystals of a segment from the OsPYL/RCAR5 protein produce fragment-based ab initio solutions that can be refined to atomic resolution, analogous to structures determined by selected-area electron diffraction. In allowing atomic structures to now be determined from digitally outlined regions of a nanocrystal, scanning nanobeam diffraction tomography breaks new ground in nanocrystallography.

36 MATERIALS SCIENCE↗

Shear Pleasure: The Structure, Formation, and Thermodynamics of Crystallographic Shear Phases

A renaissance of interest in crystallographic shear structures and our recent work in this remarkable class of materials inspired this review. We first summarize the geometrical aspects of shear plane formation and possible transformations in ReO 3 , rutile, and perovskite-based structures. Then we provide a mechanistic overview of crystallographic shear formation, plane ordering, and propagation. Next we describe the energetics of planar defect formation and interaction, equilibria between point and extended defect structures, and thermodynamic stability of shear compounds. Finally, we emphasize the remaining challenges and propose future directions in this exciting area.

Materials Science↗

Quantized Constant-Q Gabor Atoms for Sparse Binary Representations of Cyber-Physical Signatures

Increased data acquisition by uncalibrated, heterogeneous digital sensor systems such as smartphones present new challenges. Binary metrics are proposed for the quantification of cyber-physical signal characteristics and features, and a standardized constant-Q variation of the Gabor atom is developed for use with wavelet transforms. Two different continuous wavelet transform (CWT) reconstruction formulas are presented and tested under different signal to noise ratio (SNR) conditions. A sparse superposition of Nth order Gabor atoms worked well against a synthetic blast transient using the wavelet entropy and an entropy-like parametrization of the SNR as the CWT coefficient-weighting functions. The proposed methods should be well suited for sparse feature extraction and dictionary-based machine learning across multiple sensor modalities.

46 - INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AN↗

Using Community Science to Reveal the Global Chemogeography of River Metabolomes

River corridor metabolomes reflect organic matter (OM) processing that drives aquatic biogeochemical cycles. Recent work highlights the power of ultrahigh-resolution mass spectrometry for understanding metabolome composition and river corridor metabolism. However, there have been no studies on the global chemogeography of surface water and sediment metabolomes using ultrahigh-resolution techniques. Here, we describe a community science effort from the Worldwide Hydrobiogeochemistry Observation Network for Dynamic River Systems (WHONDRS) consortium to characterize global metabolomes in surface water and sediment that span multiple stream orders and biomes. We describe the distribution of key aspects of metabolomes including elemental groups, chemical classes, indices, and inferred biochemical transformations. We show that metabolomes significantly differ across surface water and sediment and that surface water metabolomes are more rich and variable. We also use inferred biochemical transformations to identify core metabolic processes shared among surface water and sediment. Finally, we observe significant spatial variation in sediment metabolites between rivers in the eastern and western portions of the contiguous United States. Our work not only provides a basis for understanding global patterns in river corridor biogeochemical cycles but also demonstrates that community science endeavors can enable global research projects that are unfeasible with traditional research models.

54 ENVIRONMENTAL SCIENCES↗

Lifting MGARD: Construction of (pre)wavelets on the interval using polynomial predictors of arbitrary order

MGARD (MultiGrid Adaptive Reduction of Data) is an algorithm for compressing and refactoring scientific data, based on the theory of multigrid methods. The core algorithm is built around stable multilevel decompositions of conforming piecewise linear $C^0$ finite element spaces, enabling accurate error control in various norms and derived quantities of interest. In this work, we extend this construction to arbitrary order Lagrange finite elements $\mathbb{Q}_p$, $p \geq 0$, and propose a reformulation of the algorithm as a lifting scheme with polynomial predictors of arbitrary order. Additionally, a new formulation using a compactly supported wavelet basis is discussed, and an explicit construction of the proposed wavelet transform for uniform dyadic grids is described.

Reshniak, Viktor [Oak Ridge National Laboratory (O↗

An Experimental Feasibility Study on Applying Neutron Tomography to Encapsulated Spent Nuclear Fuel - 20050

Visual inspection makes easier to ensure the integrity and safety of spent nuclear fuel (SNF) than any classical techniques. Various classical techniques have been applied but there are no reliable methods to qualitatively and quantitatively verify spent fuel in dry storage. Thus, the present authors have developed the prototype safeguards apparatus for dry storage employing the array of He-4 gas scintillation detectors (S670E, Arktis Radiation Detectors Ltd., Switzerland), newly designed to simultaneously measure thermal and fast neutrons without any moderators. The S670E detector has a cylindrical shape with a diameter of 52 mm and active length of 600 mm (total length: 875 mm). The detector is filled by He-4 gas with an approximate pressure of 180 bar for fast neutron detection, and its inner wall is coated by Li-6 for thermal neutron detection. The scintillation lights generated via Li-6 nuclear reaction and elastic scattering are collected by 24 SiPMs linearly paired at the center of the detector. The detector delivers a TTL (Transistor-Transistor Logic) output for pulse readout and UART (Universal Asynchronous Receiver Transmitter) for device control. In order to assess feasibility of the apparatus, an experimental system has been designed, built, and optimized via computational studies. Cf-252 neutron sources and linearly arrayed detectors, working as a single detector, were occupied for this study due to the difficulties in working with SNF. The laboratory scale cask (diameter: 0.67 m, height: 1.5 m), minimized by a factor of 10 compared to the actual thickness of a commercial TN-32 cask, was also manufactured. The detector array was designed to rotate the lab-scale cask and obtain 36 image profiles at every 10 degrees. All profiles were aligned in single frame image called a sinogram, and the cross-sectional image was then fabricated by the inverse radon transform algorithm. These experiments have been repeated with different configurations and numbers of sources. Some gamma-ray sources were also measured with neutron sources in order to distinguish between neutron and gamma-ray pulses. Basically, a He-4 detector is designed to run on Linux OS so it is difficult to directly apply to Windows-based equipment widely used in S. Korea. Therefore, a new data acquisition board working on Windows OS was designed and built. The board mainly consists of FPGA (Field Programmable Gate Array) and SoC (System on Chip) for TTL pulse readout, sorting measured data, and transferring data to a user interface. In conclusion, the tomographic system at lab-scale has shown considerable potential to detect a partial or gross defect of encapsulated assemblies in dry storage. Next steps of this study will be to 1) repeatedly carry out experiments to demonstrate scientific reliability and validity, and 2) numerically integrate signals with weight factors to enhance the image quality since the suggested system based on passive interrogation method requires longer measurement time. Finally, the system will apply to a commercial dry storage phased out soon in S. Korea. (authors)

07 ISOTOPE AND RADIATION SOURCES↗

Directional finite difference method for directly solving 3D gyrokinetic field equations with enhanced accuracy

The gyrokinetic (GK) field equation is a three-dimensional (3D) elliptic equation, but it is often simplified to a set of two-dimensional (2D) equations by assuming that the field does not vary along a specific direction. However, this simplification can introduce inevitable 0th-order numerical errors, as nonlinear mode coupling in toroidal geometry can produce undesirable harmonic modes that violate the assumption. In this work, we propose a novel directional finite difference method (FDM) with a local coordinate transformation to better resolve the target field of interest. The directional FDM can accurately solve 3D GK field equations without simplifications, which can overcome the limitations of conventional methods. The accuracy and efficiency of different FDMs are analyzed in great detail for a variety of geometries, from simple 2D Cartesian coordinates to realistic 3D curvilinear coordinates. The 0th-order numerical errors of simplified 2D GK equations were found to be more problematic for low-harmonic modes and low aspect ratio geometries such as spherical tokamaks. On the other hand, the directional 3D FDM can accurately resolve a much wider range of harmonic modes aligned to the direction of interest, including the low-harmonic modes. In conclusion, we demonstrate that the directional 3D FDM is a highly effective algorithm for solving the 3D GK field equations, achieving accuracy improvements of 10 to 100 times or more, particularly for low-harmonic modes in spherical tokamaks.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Transformation of an Embedded Five-Membered Ring in Polycyclic Aromatic Hydrocarbons via the Hydrogen-Abstraction–Acetylene-Addition Mechanism: A Theoretical Study

Five-membered rings are constituents of many polycyclic aromatic hydrocarbons (PAHs) and their presence on the edges of large PAHs has been repeatedly observed experimentally. However, modern kinetic combustion models often do not consider the growth of PAHs through the transformation of the five-membered rings. Here, in connection with the above, we carried out a theoretical study of the mechanism of Hydrogen-Abstraction-aCetylene-Addition (HACA) transformation of an embedded five-membered ring on the armchair PAH edge to a six-membered ring, considering cyclopenta[d,e,f]phenanthrene (4,5-methylenephenanthrene) as a prototype system for this process. The potential energy surface for the reactions of cyclopenta[d,e,f]phenanthrenyl radicals produced by direct H abstractions from cyclopenta[d,e,f]phenanthrene with acetylene has been compiled at the G3(MP2,CC)//B3LYP/6-311G(d,p) level of theory including zero-point vibrational energy corrections. The computed energies and molecular parameters were then used to solve the Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) in order to calculate reaction rate at various pressures and temperatures, which were fitted to modified Arrhenius equation for further kinetic modeling. The results show that the HACA transformation of the embedded five-membered ring to a six-membered ring is possible, albeit slow. The most viable reaction mechanism involves the R2 + C 2 H 2 reaction, where the acetylene molecules adds to a σ-radical in the six-membered ring adjacent to the five-membered ring via a low entrance barrier. The predominant product of R2 + C 2 H 2 is predicted to be 3 ethynyl 4H cyclopenta[def]phenanthrene Pr5 via immediate H elimination from the initial addition complex. Next, Pr5 undergoes H-assisted isomerization to 4aH-pentaleno[4,3,2,1-cdef]phenanthrene Pr4, and the latter adds an H atom eventually forming the 1-pyrenylmethyl radical Pr3: R2 + C 2 H 2 ⇌ 3 ethynyl 4H cyclopenta[def]phenanthrene (Pr5) + H ⇌ 4aH-pentaleno[4,3,2,1-cdef]phenanthrene (Pr4) + H Pr5 + H ⇌ Pr4 + H Pr4 + H → 1-pyrenylmethyl (Pr3) This HACA sequence may be competitive with the methyl radical addition to the R1 radical formed by H abstraction from the CH 2 group in the five-membered ring of cyclopenta[d,e,f]phenanthrene, which provides a pathway to pyrene following two H atom losses. Relative contributions of the two mechanisms of the five- to six-membered ring transformation would strongly depend on the branching ratios of the R1 and R2 radicals produced by the H abstractions and the available concentration of C 2 H 2 vs. CH 3 and hence differ in different flames.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radiation-Enhanced Anion Transport in Hematite

The influence of radiation-induced (1 MeV energy H+ to ~0.1 dpa at 450°C), non-equilibrium point defect populations on mass transport is studied with an integrated campaign of experimental and theoretical methods. Using epitaxial thin films of hematite with embedded 18O tracer layers and nanoscale atom probe tomography measurements, it is shown that anion self-diffusion is enhanced by at least 2 orders of magnitude under irradiation compared to thermal diffusion alone. Complementary scanning transmission electron microscopy of vacuum annealed specimens, reveals associated microstructural changes in the oxide films, including local phase transformation to Fe3O4 and the development of nanoscale voids from vacancy coalescence. Point defect formation and migration energies were computed from density functional theory and applied within the context of chemical rate theory to analyze contributions from both interstitial and vacancy mechanisms to self-diffusion in thermal and irradiation conditions. Comparisons are made between calculated, literature and newly measured self-diffusion values, revealing good agreement on the magnitude of radiation-enhanced anion diffusion. Further, the model suggests a transition from vacancy to interstitialcy mechanisms at low temperatures and high oxygen activity, consistent with the varied activation energies reported from prior studies.

iron oxides, isotopic tracers, atom probe tomograp↗

A Reduced-Temperature Process for Preparing Atomically Clean Si(100) and SiGe(100) Surfaces with Vapor HF

Silicon processing techniques such as atomic precision advanced manufacturing (APAM) and epitaxial growth require surface preparations that activate oxide desorption (typically >1000 °C) and promote surface reconstruction toward atomically clean, flat, and ordered Si(100)-2 × 1. Here, in this study, we compare the aqueous and vapor phase cleaning of Si and Si/SiGe surfaces to prepare APAM-ready and epitaxy-ready surfaces at lower temperatures. Angle resolved X-ray photoelectron spectroscopy (ARXPS) and Fourier transform infrared (FTIR) spectroscopy indicate that vapor hydrogen fluoride (VHF) cleans dramatically reduce carbon surface contamination and allow the chemically prepared surface to reconstruct at lower temperatures, 600 °C for Si and 580 °C for a Si/Si 0.7 Ge 0.3 heterostructure, into an ordered atomic terrace structure indicated by scanning tunneling microscopy (STM). After thermal treatment and vacuum hydrogen termination, we demonstrate STM hydrogen desorption lithography (HDL) on VHF-treated Si samples, creating reactive zones that enable area-selective chemistry by using a thermal budget similar to CMOS process flows. We anticipate that these results will establish new pathways to integrate APAM with Si foundry processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The structure of high-Mg alkali-bearing aluminosilicate glasses investigated in situ at ambient and high pressure by multi-angle energy dispersive X-ray diffraction and infrared microspectroscopy

The structural properties of synthetic high-Mg alkali-bearing aluminosilicate glasses analogues of natural picritic-to-komatiitic magmas were investigated in situ by multiangle energy dispersive X-ray diffraction at 2.1 GPa and ambient pressure and by Fourier Transform infrared spectroscopy up to 5.4 GPa in a cycle of compression and decompression experiments. Our results show that the intermediate range ordering of the glass structure at 2.1 GPa is 3.14 Å, increasing to 3.19 Å when decompressed. The local structure shows T-O lengths of 1.66 Å (2.1 GPa) and 1.65 Å (ambient pressure), T-T distances of 3.19 Å at high pressure, which lengthen to 3.21 Å at ambient pressure, causing the T-O-T angle of 147° determined at 2.1 GPa to widen to 154° upon decompression. The deconvoluted infrared spectra result in the presence of Q 1 , Q 2 , Q 3 populations in the aluminosilicate spectral region, whose proportions remain relatively unchanged up to 5.4 GPa. The structural response of the investigated glasses to cold-compression does not involve changes in polymerization, but rather a shrinking and compaction of the structure as evidenced by the Qn species shifting to higher wavenumbers as a function of pressure. The structural properties determined from X-ray diffraction for this glass composition are discussed together with those of glasses emerging from previous studies to highlight a compositional dependence mainly dictated by the amount of SiO 2 and Al 2 O 3 .

glass structure↗

In situ formed partially disordered phases as earth-abundant Mn-rich cathode materials

Abstract Earth-abundant cathode materials are urgently needed to enable scaling of the Li-ion industry to multiply terawatt hours of annual production, necessitating reconsideration of how good cathode materials can be obtained. Irreversible transition metal migration and phase transformations in Li-ion cathodes are typically believed to be detrimental because they may trigger voltage hysteresis, poor kinetics and capacity degradation. Here we challenge this conventional consensus by reporting an unusual phase transformation from disordered Li- and Mn-rich rock salts to a new phase (named δ ), which displays partial spinel-like ordering with short coherence length and exhibits high energy density and rate capability. Unlike other Mn-based cathodes, the δ phase exhibits almost no voltage fade upon cycling. We identify the driving force and kinetics of this in situ cathode formation and establish design guidelines for Li- and Mn-rich compositions that combine high energy density, high rate capability and good cyclability, thereby enabling Mn-based energy storage.

25 ENERGY STORAGE↗

Rapid solidified ductile Cu-Al-Mn ribbon and its elastocaloric potential

Abstract Cu-Al-Mn alloys display martensitic transformation over a wide range of temperatures. In addition to low cost, this alloy is known for its low transformation stress with reasonable latent heat favoring elastocaloric applications. However, the ductility of Cu-Al-Mn can be limited owing to ordering and intergranular fracture. Through rapid solidification by melt spinning, we show that Cu-Al-Mn ribbon can be made highly ductile (greater than 8% tensile strain in the as-spun state and 10% tensile strain after heat treatment). The ductility of the melt-spun ribbon is related to the suppression of L2 1 ordering that is characterized through magnetic property measurement. Heat treatment of the ribbon promotes bamboo grain formation, and the latent heat is increased to 6.4 J g −1 . Under tensile conditions, we show that the ribbon exhibited about 4 °C temperature change (4.4 °C on heating and 4.2 °C on cooling from 6.3% strain).

36 MATERIALS SCIENCE↗

Two-dimensional silk

Despite the promise of silk-based devices, the inherent disorder of native silk limits performance. Here, we report highly ordered two-dimensional silk fibroin (SF) films grown epitaxially on van der Waals (vdW) substrates. Using atomic force microscopy, nano–Fourier transform infrared spectroscopy, and molecular dynamics, we show that the films consist of lamellae of SF molecules that exhibit the same secondary structure as the nanocrystallites of native silk. Increasing the SF concentration results in multilayers that grow either by direct assembly of SF molecules into the lamellae or, at high concentrations, along a two-step pathway beginning with a disordered monolayer that then crystallizes. Scanning Kelvin probe measurements show that these films substantially alter the surface potential; thus, they provide a platform for silk-based electronics on vdW solids.

36 MATERIALS SCIENCE↗

Harmonic cancellation within AC low voltage distribution for a realistic office environment

An increase of non-linear loads, primarily from power electronics, has substantially increased current harmonics in commercial buildings, which contributes to decreased transformer efficiency / lifespan and poor power quality. This study uses recorded power consumption data from common miscellaneous electric loads (MELs) seen in offices, combined with detailed characterizations of example MELs, to simulate harmonic cancellation within building circuits. Typically, harmonic cancellation studies assume that AC converters operate across their rated power range. However, this study finds that common MELs operate below 40% of rated power the majority of the time when not quiescent; 89% of sampled devices never operated above 60% of rated power. Simulations using these more realistic power levels indicate current-harmonic cancellation (3rd to 13th harmonic) is significantly lower than that predicted when using full-range power assumptions, resulting in minor errors for low-order harmonics and larger errors for higher order harmonics. Furthermore, increased MELs load diversity increases harmonic cancellation, but insufficiently to eliminate errors. In contrast, blending lighting loads with MELs on the secondaries of distribution transformers improves harmonic cancellation to near those predicted by traditional methods. These results indicate that realistic power levels, as well as better characterization of harmonics from typical MELs, should be used to estimate harmonic cancellation.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Quaternary Charge-Transfer Complex Enables Photoenzymatic Intermolecular Hydroalkylation of Olefins

Intermolecular C–C bond-forming reactions are underdeveloped transformations in the field of biocatalysis. Here we report a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent ‘ene’-reductases. Radical initiation occurs via photoexcitation of a rare high-order enzyme-templated charge-transfer complex that forms between an alkene, α-chloroamide, and flavin hydroquinone. This unique mechanism ensures that radical formation only occurs when both substrates are present within the protein active site. Here, this active site can control the radical terminating hydrogen atom transfer, enabling the synthesis of enantioenriched γ-stereogenic amides. This work highlights the potential for photoenzymatic catalysis to enable new biocatalytic transformations via previously unknown electron transfer mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reversible Disorder-to-Order Transition Induced by Aqueous Lithiation in Vanadate Electrode Materials

Vanadium-based oxides are intriguing electrode materials in aqueous electrochemical systems owing to their low cost and high theoretical capacity for alkali storage, especially lithium (Li) ions. However, a sequence of phase transformations and irreversible structure distortion upon Li-ion intercalation causes structural instability and has been a lingering problem for vanadium oxide electrodes. Here, in this work, we investigate lithium vanadate (Li–V 3 O 8 ) for aqueous Li-ion intercalation and deintercalation processes. Unlike its crystalline V 2 O 5 polymorph, Li–V 3 O 8 retains monophasic lithiation, which is attributed to its disordered crystalline nature and large interplanar distance. Importantly, we show a unique and reversible sequence of disorder-to-order structural transition induced by the extent of lithiation, which indicates sequential interlayer and intralayer lithiation process, and vice versa in delithiation process, supported by electrokinetic analysis, in situ X-ray diffraction (XRD), and Debye scattering simulations. The absence of distortive phase transitions and multilithiation pathways facilitates Li-ion diffusion across the vanadate electrode materials to improve storage capacity. This work opens a new dimension for vanadium-based disordered oxides, accelerating the development of low-cost, aqueous electrochemical systems.

36 MATERIALS SCIENCE↗