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At least 325 records · Page 18

A capillary-based microfluidic device enables primary high-throughput room-temperature crystallographic screening

A novel capillary-based microfluidic strategy to accelerate the process of small-molecule-compound screening by room-temperature X-ray crystallography using protein crystals is reported. The ultra-thin microfluidic devices are composed of a UV-curable polymer, patterned by cleanroom photolithography, and have nine capillary channels per chip. The chip was designed for ease of sample manipulation, sample stability and minimal X-ray background. 3D-printed frames and cassettes conforming to SBS standards are used to house the capillary chips, providing additional mechanical stability and compatibility with automated liquid- and sample-handling robotics. These devices enable an innovative in situ crystal-soaking screening workflow, akin to high-throughput compound screening, such that quantitative electron density maps sufficient to determine weak binding events are efficiently obtained. This work paves the way for adopting a room-temperature microfluidics-based sample delivery method at synchrotron sources to facilitate high-throughput protein-crystallography-based screening of compounds at high concentration with the aim of discovering novel binding events in an automated manner.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inexpensive high-temperature furnace for thermocouple calibration

New furnace calibrates unknown thermocouple by comparing its electrical output to a reference thermocouple /previously calibrated by optical pyrometry/, as both are heated simultaneously. Thermocouples may be radioactive, thus heat source must be accessible by remote manipulation and inspection measurements. Advantages of furnace operation are cited.

Gracey, C. M.↗

Polysulfide regulation by defect-modulated Ta 3 N 5- x electrocatalyst toward superior room-temperature sodium-sulfur batteries

Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metal-sulfur batteries. Motivated by a theoretical prediction, herein, we strategically propose nitrogen-vacancy tantalum nitride (Ta 3 N 5-x ) impregnated inside the interconnected nanopores of nitrogen-decorated carbon matrix as a new electrocatalyst for regulating sulfur redox reactions in room-temperature sodium-sulfur batteries. Through a pore-constriction mechanism, the nitrogen vacancies are controllably constructed during the nucleation of Ta 3 N 5-x . Further, the defect manipulation on the local environment enables well-regulated Ta 5d-orbital energy level, not only modulating band structure toward enhanced intrinsic conductivity of Ta-based materials, but also promoting polysulfide stabilization and achieving bifunctional catalytic capability toward completely reversible polysulfide conversion. Moreover, the interconnected continuous Ta 3 N 5-x -in-pore structure facilitates electron and sodium-ion transport and accommodates volume expansion of sulfur species while suppressing their shuttle behavior. Due to these attributes, the as-developed Ta 3 N 5-x -based electrode achieves superior rate capability of 730 mAh g -1 at 3.35 A g -1 , long-term cycling stability over 2000 cycles, and high areal capacity over 6 mAh cm -2 under high sulfur loading of 6.2mgcm -2 . This work not only presents a new sulfur electrocatalyst candidate for metal-sulfur batteries, but also sheds light on the controllable material design of defect structure in hopes of inspiring new ideas and directions for future research.

25 ENERGY STORAGE↗

Variable-Temperature Scattering and Spectroscopy Characterizations for Temperature-Dependent Solution Assembly of PffBT4T-Based Conjugated Polymers

The solution structure of conjugated polymers (CPs) from which the films are cast is critical for tailoring the thin-film morphology thus device performance. Here, we used multimodal variable-temperature scattering and spectroscopy tools to fully quantify the solution assembly of poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'''-dialkyl-2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] (PffBT4T) polymers with varying side-chain lengths at different assembly temperatures. The conformational and aggregation behaviors for PffBT4T-based CPs were found to be very sensitive to both temperature and side chain length using ultraviolet–visible (UV–vis) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dynamic light scattering (DLS), and small-angle neutron scattering (SANS). We found that with slightly increasing side chain length from 2-octyldodecyl (C8C12) to 2-nonyltridecyl (C9C13), PffBT4T-based CPs show a significant decrease in aggregation-to-dissolved chain transition temperature (10 °C), degree of aggregation, enthalpy change of aggregation, and size of the aggregates in solution. At room temperature, PffBT4T polymer strongly aggregated to form fabric structure with the film thickness of a few nanometers in thickness and hundreds of nanometers in length, as probed by atomic force microscopy (AFM), transmission electronic microscopy (TEM), and dynamic light scattering (DLS). At the elevated temperature above the aggregation-to-dissolved chain transition temperature, PffBT4T is fully dissolved and adopts a semiflexible coil conformation with the persistence length of 3.1 nm for PffBT4T-C8C12 and a slightly increased persistence length of 3.4 nm for PffBT4T-C9C13, according to temperature-dependent SANS measurements. Longer side chains of PffBT4T-C9C13 also lead to less aggregation enthalpy gain compared with PffBT4T-C8C12. This work provides a solution structure manipulating strategy of CPs and thus will inspire the molecular design and processing protocols of CPs toward higher performance electronic devices.

36 MATERIALS SCIENCE↗

Room-Temperature Mechanical Resonator with a Single Added or Subtracted Phonon

A room-temperature mechanical oscillator undergoes thermal Brownian motion with an amplitude much larger than the amplitude associated with a single phonon of excitation. This motion can be read out and manipulated using laser light using a cavity-optomechanical approach. By performing a strong quantum measurement (i.e., counting single photons in the sidebands imparted on a laser), we herald the addition and subtraction of single phonons on the 300 K thermal motional state of a 4 GHz mechanical oscillator. Further, to understand the resulting mechanical state, we implement a tomography scheme and observe highly non-Gaussian phase-space distributions. Using a maximum likelihood method, we infer the density matrix of the oscillator, and we confirm the counterintuitive doubling of the mean phonon number resulting from phonon addition and subtraction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Pore-scale visualization of natural hydrate-bearing sediments

Accurate modeling of gas hydrate reservoir productivity and geomechanical risks associated with subsurface dissociation of natural gas hydrates (NGH) requires the determination of model parameters through physical testing on natural hydrate-bearing sediments (HBS). This involves investigating the hydro-mechanical behavior of undisturbed hydrate samples from nature under in situ conditions using pressure core characterization and analysis, which provides a unique opportunity for research. By employing state-of-the-art micro computed tomography imagery on cryogenically preserved, hydrate-bearing sediment samples, we can determine hydrate saturation as well as permeability with and without the presence of hydrates in the sediment. Furthermore, utilizing a machine learning based image segmentation technique, it is possible to extract pore space and grain information. Subsections of the entire image volume were used to determine anisotropic permeabilities using a finite-difference method Stokes solver (FDMSS). Additionally, permeability measurements on whole pressure and temperature preserved hydrate-bearing core were analyzed by utilizing the National Energy Technology Laboratory’s (NETL) Pressure Core Characterization and X-ray CT Visualization Tool (PCXT) to manipulate, cut, and analyze pressure preserved sediment. Permeabilities were measured under a broad range of vertical stress states to simulate expected pressure changes during production scenarios, and the results show that permeabilities derived from images are in agreement with those from traditional core derived experiments. The collected stress-dependent permeability, permeability anisotropy, and corresponding gas hydrate saturations provide valuable input into numerical simulations of reservoir productivity. These properties have been proven to be key parameters determining a long-term reservoir response under depressurization.

Liu, Mengwei [Oak Ridge Institute for Science and ↗

Enhanced Magnetism and Anomalous Hall Transport through Two-Dimensional Tungsten Disulfide Interfaces

The magnetic proximity effect (MPE) has recently been explored to manipulate interfacial properties of two-dimensional (2D) transition metal dichalcogenide (TMD)/ferromagnet heterostructures for use in spintronics and valleytronics. However, a full understanding of the MPE and its temperature and magnetic field evolution in these systems is lacking. In this study, the MPE has been probed in Pt/WS 2 /BPIO (biphase iron oxide, Fe 3 O 4 and α-Fe 2 O 3 ) heterostructures through a comprehensive investigation of their magnetic and transport properties using magnetometry, four-probe resistivity, and anomalous Hall effect (AHE) measurements. Density functional theory (DFT) calculations are performed to complement the experimental findings. We found that the presence of monolayer WS 2 flakes reduces the magnetization of BPIO and hence the total magnetization of Pt/WS 2 /BPIO at T > ~120 K—the Verwey transition temperature of Fe 3 O 4 (T V ). However, an enhanced magnetization is achieved at T < T V . In the latter case, a comparative analysis of the transport properties of Pt/WS 2 /BPIO and Pt/BPIO from AHE measurements reveals ferromagnetic coupling at the WS 2 /BPIO interface. Our study forms the foundation for understanding MPE-mediated interfacial properties and paves a new pathway for designing 2D TMD/magnet heterostructures for applications in spintronics, opto-spincaloritronics, and valleytronics.

36 MATERIALS SCIENCE↗

A three-dimensional model of co-rotating streams in the solar wind. 2: Hydrodynamic streams

Theoretical aspects of corotating solar wind dynamics on a global scale are explored by means of numerical simulations executed with a nonlinear, inviscid, adiabatic, single-fluid, three-dimensional (3-D) hydrodynamic formulation. A simple, hypothetical 3-D stream structure is defined on a source surface located at 35 solar radius and carefully documents its evolution to 1 AU under the influence of solar rotation. By manipulating the structure of this prototype configuration at the source surface, it is possible to elucidate the factors most strongly affecting stream evolution: (1) the intrinsic correlations among density, temperature, and velocity existing near the source; (2) the amplitude of the stream; (3) the longitudinal breadth of the stream; (4) the latitudinal breadth of the stream; and (5) the heliographic latitude of the centroid of the stream.

Pizzo, V. J.↗

Alaskan carbon-climate feedbacks will be weaker than inferred from short-term manipulations: Alaskan Benchmark Data and Model runs

This submission aimed to assess differences in short-term step warming manipulations and long-term chronic response to climate change in Alaskan ecosystems. Briefly, climate warming is occurring fastest at high latitudes. Based on short-term field experiments, this warming is projected to stimulate soil organic matter decomposition, and promote a positive feedback to climate change. We show here that the tightly coupled, nonlinear nature of high-latitude ecosystems implies that short-term (< 10 year) warming experiments produce emergent ecosystem carbon stock temperature sensitivities inconsistent with emergent multi-decadal responses. We first demonstrate that a well-tested mechanistic ecosystem model accurately represents observed carbon cycle and active layer depth responses to short-term summer warming in four diverse Alaskan sites. We then show that short-term warming manipulations do not capture the non-linear, long-term dynamics of vegetation, and thereby soil organic matter, that occur in response to thermal, hydrological, and nutrient transformations belowground. Our results demonstrate significant spatial heterogeneity in multi-decadal Arctic carbon cycle trajectories and argue for more mechanistic models to improve predictive capabilities.The model used in the current study is available publicly (https://github.com/jinyun1tang/ECOSYS), and the current submission contains the python/ matlab codes for analyzing output from the model (includng a readme file to explain the codes). The benchmark data, also enclosed, was collected from a range of published and publicly available sources (extracted using GRABIT: https://www.mathworks.com/matlabcentral/fileexchange/7173-grabit). These sources describe warming induced changes in tundra/ boreal ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Oxide Semiconductor Sensors for Monitoring Advanced Energy Conversion and Manufacturing Processes at High Temperature

To optimize the operation and functionality of high temperature systems such as slagging gasifiers, coal boilers and glass/steel smelters, it is important to monitor temperature, corrosion and erosion of the refractory used in such systems. Both thermocouple and failure sensors (and arrays of these) would be useful to monitor the health of any refractory or coatings in these systems. Many of such type of sensors are installed into the systems through open access ports within the refractory; however, there are some disadvantages of this approach where corrosive/erosive gas and molten materials can penetrate and compromise the system. The current work presents the development and performance of refractory with embedded high temperature sensors such as thermocouples, thermistors, and various spallation/crack monitoring sensors, which may be used within a variety of refractory brick in different high temperature processes and applications. The objective of our work is to develop high-temperature sensors composed of electroceramic materials that are chemically stable at high temperatures (750°-1500°C) and high pressures (up to 1000 psi) that can be used in monitoring temperature, corrosion and erosion process in refractory used in high energy systems. The high-temperature sensors investigated in this work were composed of various oxide composites directly embedded into the refractory oxides. The composites used for this work were synthesized by a mixed-oxide route. Metal oxides were inserted within a matrix material composed of refractory oxides (Al2O3, ZrO2, etc.). The physical and electrical properties were specifically manipulated by altering the level of percolation of the conductive species (metal oxides) within the refractory constituent (refractory oxide). An example of one of these embedded sensors consisted of an electroceramic-based thermocouple fabricated with two separate oxide composite compositions which were patterned to produce a couple within the interior of a refractory matrix. The thermocouple successfully displayed thermoelectric voltage trend (as a function of temperature), and the voltage was 220.0 mV near 1400 °C. In addition, corrosion tests on the refractory embedded sensors were performed. To evaluate corrosion in the refractory was exposed to high-temperature glass compositions over a 90 h period. The penetration of the glass through the refractory could be monitored by both an amperometric and voltametric based sensor. With this experiment, it was demonstrated that the embedded sensor could dynamically monitor the corrosion process, and thus, provide real-time feedback on both temperature and the refractory health.

20 FOSSIL-FUELED POWER PLANTS↗

Thermodynamics and kinetics of solution combustion synthesis: Ni(NO 3 ) 2 + fuels systems

Solution combustion synthesis (SCS) utilizes exothermic self-propagating reactions to prepare nanoscale materials that can be used widely in energy, electronics, and biomedical technologies and other applications. SCS is a specific variety of a more general combustion synthesis (CS) method. Investigations of the thermodynamics, kinetics, and the mechanisms of SCS reactions, are not as well studied as the other CS processes. This work reports on a systematic study of the thermodynamics and kinetics of SCS reactions involving Ni(NO 3 ) 2 , an oxidizer, and either glycine (C 2 H 5 NO 2 ) or hexamethylenetetramine (HMT, C 6 H 12 N 4 ) as fuels. A thermodynamic modeling approach, based on the Gibbs free energy minimization principle, is applied to the simultaneous calculations of the adiabatic temperatures and compositions of the equilibrium products. Our calculations reveal the influence of fuel-to-oxidizer ratio, amount of water, and the oxygen in air on the combustion temperature under adiabatic conditions and the composition of the resulting products. We have, in turn, measured the combustion temperature and phase composition of products and compared them with the calculations. Variations of drying times for the solutions yield precursor gels with varying water contents. This approach enables the manipulation of combustion parameters and confirms the use of calculated activation energies for reactions using the Merzhanov-Khaikin method. Here, the results show that SCS reactions in fuel-lean solutions producing NiO have higher activation energy in contrast to reactions with fuel-rich solutions that form Ni. Reduction of activation energies due to the increase in the fuel-to-oxidizer ratio could be related to the observed change of the rate-limiting stages of the endothermic decomposition of the individual reactants to the exothermic decomposition of coordinate compounds formed between the reactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge density wave modulation in superconducting BaPb O 3 / BaBi O 3 superlattices

The isotropic, nonmagnetic doped BaBiO 3 superconductors maintain some similarities to high-T c cuprates, while also providing a cleaner system for isolating charge density wave (CDW) physics that commonly competes with superconductivity. Artificial layered superlattices offer the possibility of engineering the interaction between superconductivity and CDW. Here we stabilize a low-temperature, fluctuating short-range CDW order by using artificially layered epitaxial (BaPbO 3 ) 3m /(BaBiO 3 ) m (m = 1-10 unit cells) superlattices that are not present in the optimally doped BaPb 0.75 Bi 0.25 O 3 alloy with the same overall chemical formula. Charge transfer from BaBiO 3 to BaPbO 3 effectively dopes the former and suppresses the long-range CDW; however, as the short-range CDW fluctuations strengthen at low temperatures charge appears to localize and superconductivity is weakened. The monolayer structural control demonstrated here provides compelling implications to access controllable, local density wave orders absent in bulk alloys and manipulate phase competition in unconventional superconductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Near-Monochromatic Tuneable Cryogenic Niobium Electron Field Emitter

We report creating, manipulating, and detecting coherent electrons is at the heart of future quantum microscopy and spectroscopy technologies. Leveraging and specifically altering the quantum features of an electron beam source at low temperatures can enhance its emission properties. Here, we describe electron field emission from a monocrystalline, superconducting niobium nanotip at a temperature of 5.9 K. The emitted electron energy spectrum reveals an ultranarrow distribution down to 16 meV due to tunable resonant tunneling field emission via localized band states at a nanoprotrusion’s apex and a cutoff at the sharp low-temperature Fermi edge. This is an order of magnitude lower than for conventional field emission electron sources. The self-focusing geometry of the tip leads to emission in an angle of 3.7°, a reduced brightness of 3.8 × 10 8 A/(m 2 srV), and a stability of hours at 4.1 nA beam current and 69 meV energy width. This source will decrease the impact of lens aberration and enable new modes in low-energy electron microscopy, electron energy loss spectroscopy, and high-resolution vibrational spectroscopy.

36 MATERIALS SCIENCE↗

Prolate and oblate chiral liquid crystal spheroids

Liquid crystals are known to exhibit intriguing textures and color patterns, with applications in display and optical technologies. This work focuses on chiral materials and examines the palette of morphologies that arises when microdroplets are deformed into nonspherical shapes in a controllable manner. Specifically, geometrical confinement and mechanical strain are used to manipulate orientational order, phase transitions, and topological defects that arise in chiral liquid crystal droplets. Inspired by processes encountered in nature, where insects and animals often rely on strain and temperature to alter the optical appearance of dispersed liquid crystalline elements, chiral droplets are dispersed in polymer films and deformation induced by uniaxial or biaxial stretching. Our measurements are interpreted by resorting to simulations of the corresponding systems, thereby providing an in-depth understanding of the morphologies that arise in these materials. The reported structures and assemblies offer potential for applications in smart coatings, smart fabrics, and wearable sensors.

42 ENGINEERING↗

EXFILE: A program for compiling irradiation data on UN and UC fuel pins

A FORTRAN-4 computer program for handling fuel pin data is described. Its main features include standardized output, easy access for data manipulation, and tabulation of important material property data. An additional feature allows simplified preparation of input decks for a fuel swelling computer code (CYGRO-2). Data from over 300 high temperature nitride and carbide based fuel pin irradiations are listed.

Mayer, J. T.↗

Black-silicon as a Wideband Infrared Absorber for the Space Instruments: Fabrication, Modeling, and Characterization

The uniform black silicon (BSI) cryogenically etched has been demonstrated as a superior absorber in par with other ultra-absorbers such as carbon nano tubes in the visible and near-infrared spectrum. In this work, we discuss the fabrication, modeling, and characterization of the BSI aiming at the 2.5-5 microns range. We investigated a series of cryogenic parameters such as temperature, pressure, oxygen flowrate, power, and etching duration and fabricated a series of uniformly etched wafers. Additionally, we established at hree-dimensional mathematical model of a unit cell and manipulated the silicon needle geometry and shape. Our preliminary fabrication results show silicon needles of 8 micron height have five orders of magnitude specular reflectance in the infrared region. The modeling efforts how longer pillar heights could be better absorbers as the wavelength increases.

Wideband absorber↗

The Deep Eutectic Solvent Precipitation Synthesis of Metastable Zn 4 V 2 O 9

A precipitation method involving a deep eutectic solvent (DES)–a mixture of hydrogen bond donor and acceptor–is used to synthesize a ternary metal oxide. Without toxic reagents, precipitates consisting of Zn 3 (OH) 2 V 2 O 7 ·nH 2 O and Zn 5 (OH) 6 (CO 3 ) 2 are obtained by simply introducing deionized H 2 O to the DES solution containing dissolved ZnO and V 2 O 5 . Manipulation of the synthetic conditions demonstrates high tunability in the size/morphology of the two-dimensional nanosheets precipitated during the dynamic equilibrium process. According to differential scanning calorimetry and high-temperature powder X-ray diffraction, Zn 3 V 2 O 8 and ZnO obtained by the annealing of the precipitate are intermediates in the reaction pathway toward metastable Zn 4 V 2 O 9 . Intimate mixing of the metal precursors achieved by the precipitation method allows access to the metastable zinc-rich vanadate with unusually rapid heat treatment. Furthermore, the UV–vis and surface photovoltage spectra reveal the presence of sub-band gap states, stemming from the reduced vanadium (V 4+ ) center. Photoelectrochemical measurements confirm weak photoanodic currents for water and methanol oxidation. For the first time, this work shows the synthesis of a metastable oxide with the DES-precipitation route and provides insight into the structure–property relationship of the zinc-rich vanadate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Erbium-Implanted WS 2 Flakes with Room-Temperature Photon Emission at Telecom Wavelengths

Optically addressable spin impurities in crystals along with device engineering provide an attractive route to realizing quantum technologies in the solid state, but reconciling disparate emitter and host material constraints for a given target application is often challenging. Rare-earth ions in two-dimensional (2D) materials could mitigate this problem given the atomic-like transitions of the emitters and the versatile nature of van der Waals systems. Here we combine ion implantation, confocal microscopy, and ab initio calculations to examine the photon emission of Er-doped WS 2 flakes. Optical spectroscopy reveals narrow, long-lived photoluminescence lines in the telecom band, which we activate after low-temperature thermal annealing. Spectroscopic and polarization-selective measurements show a uniform response across the ensemble, while the fluorescence brightness remains mostly unchanged with temperature, suggesting nonradiative relaxation channels are inefficient. Our results create opportunities for novel solid state devices coupling 2D-hosted, telecom-band emitters to photonic heterostructures separately optimized for photon manipulation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗