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At least 739 records · Page 41

Overcoming ammonia synthesis scaling relations with plasma-enabled catalysis

Correlations between the energies of elementary steps limit the rates of thermally catalysed reactions at surfaces. Here, we show how these limitations can be circumvented in ammonia synthesis by coupling catalysts to a non-thermal plasma. We postulate that plasma-induced vibrational excitations in N 2 decrease dissociation barriers without influencing subsequent reaction steps. We develop a density-functional-theory-based microkinetic model to incorporate this effect, and parameterize the model using N 2 vibrational excitations observed in a dielectric-barrier-discharge plasma. We predict plasma enhancement to be particularly great on metals that bind nitrogen too weakly to be active thermally. Ammonia synthesis rates observed in a dielectric-barrier-discharge plasma reactor are consistent with predicted enhancements and predicted changes in the optimal metal catalyst. The results provide guidance for optimizing catalysts for application with plasmas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Amyloid structure exhibits polymorphism on multiple length scales in human brain tissue

Although aggregation of Aβ amyloid fibrils into plaques in the brain is a hallmark of Alzheimer's Disease (AD), the correlation between amyloid burden and severity of symptoms is weak. One possible reason is that amyloid fibrils are structurally polymorphic and different polymorphs may contribute differentially to disease. However, the occurrence and distribution of amyloid polymorphisms in human brain is poorly documented. Here we seek to fill this knowledge gap by using X-ray microdiffraction of histological sections of human tissue to map the abundance, orientation and structural heterogeneities of amyloid within individual plaques; among proximal plaques and in subjects with distinct clinical histories. A 5 µ x-ray beam was used to generate diffraction data with each pattern arising from a scattering volume of only ~ 450 µ3 , making possible collection of dozens to hundreds of diffraction patterns from a single amyloid plaque. X-ray scattering from these samples exhibited all the properties expected for scattering from amyloid. Amyloid distribution was mapped using the intensity of its signature 4.7 Å reflection which also provided information on the orientation of amyloid fibrils across plaques. Margins of plaques exhibited a greater degree of orientation than cores and orientation around blood vessels frequently appeared tangential. Variation in the structure of Aβ fibrils is reflected in the shape of the 4.7 Å peak which usually appears as a doublet. Variations in this peak correspond to differences between the structure of amyloid within cores of plaques and at their periphery. Examination of tissue from a mismatch case - an individual with high plaque burden but no overt signs of dementia at time of death - revealed a diversity of structure and spatial distribution of amyloid that is distinct from typical AD cases. As a result, we demonstrate the existence of structural polymorphisms among amyloid within and among plaques of a single individual and suggest the existence of distinct differences in the organization of amyloid in subjects with different clinical presentations.

59 BASIC BIOLOGICAL SCIENCES↗

In situ microscopy across scales for the characterization of crystal growth mechanisms: The case of europium oxalate

A better understanding of how production pathway affects the final product is required in order to produce targeted syntheses, but many of the classical ex situ techniques used for studying nanoparticle growth are unsuitable as stand-alone methods for identifying and characterizing growth mechanisms. Using a combination of high resolution transmission electron microscopy (TEM), cryogenic TEM, and fluid cell scanning electron microscopy, we monitor europium oxalate growth over the range of nanometers to tens of micrometers and identify potential crystal growth pathways. We also compare the effects of stirring during crystal growth as an example of how changing processing conditions changes growth mechanisms.

in situ SEM, Cryo TEM, lanthanide, crystal growth↗

Large-scale experimental validation of thermochemical water-splitting oxides discovered by defect graph neural networks

Thermochemical water-splitting (TCH) based on 2-step thermal redox cycles in metal oxides is a promising approach to generating H 2 , but state-of-the-art (SOTA) CeO 2 has several practical limitations, which has motivated continued materials discovery efforts in this field. Here, in this study, we improve upon a SOTA defect graph neural network (dGNN) surrogate model's oxygen vacancy predictions and combine them with materials project phase diagrams to down-select and discover structurally diverse, experimentally known metal oxides whose TCH performance was previously unknown. Amongst twelve candidates selected based on our high-throughput screening and down-selection criteria, we achieved ∼80% accuracy in identifying materials with stable redox cycling and hydrogen production in stagnation flow reactor water-splitting experiments. Closer to 100% accuracy can be achieved if higher-accuracy, hybrid DFT-predicted vacancy formation energies were computed and used in lieu of the most uncertain dGNN-based screening predictions, as they correct false positives to true negatives. Notably, two discovered candidates, Sr 3 PrMn 2 O 8 and Ba 2 Fe 2 O 5 , display hydrogen yields greater than CeO 2 under specific redox conditions. In conclusion, these results demonstrate our ability to computationally predict and experimentally validate promising candidate TCH materials that have the potential to compete with CeO 2 .

08 HYDROGEN↗

Pulsed-coil magnet systems for applying uniform 10–30 T fields to centimeter-scale targets on Sandia's Z facility

Sandia has successfully integrated the capability to apply uniform, high magnetic fields (10–30 T) to high energy density experiments on the Z facility. This system uses an 8-mF, 15-kV capacitor bank to drive large-bore (5 cm diameter), high-inductance (1–3 mH) multi-turn, multi-layer electromagnets that slowly magnetize the conductive targets used on Z over several milliseconds (time to peak field of 2–7 ms). This system was commissioned in February 2013 and has been used successfully to magnetize more than 30 experiments up to 10 T that have produced exciting and surprising physics results. These experiments used split-magnet topologies to maintain diagnostic lines of sight to the target. We describe the design, integration, and operation of the pulsed coil system into the challenging and harsh environment of the Z Machine. We also describe our plans and designs for achieving fields up to 20 T with a reduced-gap split-magnet configuration, and up to 30 T with a solid magnet configuration in pursuit of the Magnetized Liner Inertial Fusion concept.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Maximizing neutron yields by scaling hollow diameter of a dense plasma focus anode [Neutron yield maximization and anode surface damage characterization by scaling hollow diameters of a DPF anode]

Experiments were performed to maximize the neutron yield from a 2 kJ dense plasma focus (DPF) and characterize the amount of copper sputtered from the surface of an anode by varying the diameter of the anodes’ on-axis hollow. The hollow is a void in the copper material along the longitudinal axis of the anode. All the anodes had an outer diameter of 1.2 in. and the diameter of the hollow varied from 0 in. (no hollow) to 1 in. The anodes with a hollow produced a greater number of neutrons per discharge than the anode without a hollow. Over 40 discharges, the hollow anode that yielded the most neutrons (9.1±0.4×10 6 neutrons per discharge produced with the 0.75 in. hollow) produced >6 times more neutrons than the anode with no hollow. A qualitative observation of the anodes after 130 discharges showed less surface damage on anodes with a larger hollow. Quantitative sputter measurements were performed by characterizing the amount of copper sputtered onto on-axis quartz targets for three newly machined anodes, each with a particular hollow diameter. The quantitative results matched the qualitative observations: the copper sputter was reduced using larger hollows. Finally, the largest hollow sputtered 17±1.0 nm/sr/discharge of copper, a reduction of 69% compared to the anode with the most damage.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DEEP CHANDRA, HST-COS, AND MEGACAM OBSERVATIONS OF THE PHOENIX CLUSTER: EXTREME STAR FORMATION AND AGN FEEDBACK ON HUNDRED KILOPARSEC SCALES

We present new ultraviolet, optical, and X-ray data on the Phoenix galaxy cluster (SPT-CLJ2344-4243). Deep optical imaging reveals previously undetected filaments of star formation, extending to radii of ∼50–100 kpc in multiple directions. Combined UV-optical spectroscopy of the central galaxy reveals a massive (2 × 10{sup 9} M{sub ⊙}), young (∼4.5 Myr) population of stars, consistent with a time-averaged star formation rate of 610 ± 50 M{sub ⊙} yr{sup −1}. We report a strong detection of O vi λλ1032,1038, which appears to originate primarily in shock-heated gas, but may contain a substantial contribution (>1000 M{sub ⊙} yr{sup −1}) from the cooling intracluster medium (ICM). We confirm the presence of deep X-ray cavities in the inner ∼10 kpc, which are among the most extreme examples of radio-mode feedback detected to date, implying jet powers of 2–7 × 10{sup 45} erg s{sup −1}. We provide evidence that the active galactic nucleus inflating these cavities may have only recently transitioned from “quasar-mode” to “radio-mode,” and may currently be insufficient to completely offset cooling. A model-subtracted residual X-ray image reveals evidence for prior episodes of strong radio-mode feedback at radii of ∼100 kpc, with extended “ghost” cavities indicating a prior epoch of feedback roughly 100 Myr ago. This residual image also exhibits significant asymmetry in the inner ∼200 kpc (0.15R{sub 500}), reminiscent of infalling cool clouds, either due to minor mergers or fragmentation of the cooling ICM. Taken together, these data reveal a rapidly evolving cool core which is rich with structure (both spatially and in temperature), is subject to a variety of highly energetic processes, and yet is cooling rapidly and forming stars along thin, narrow filaments.

79 ASTRONOMY AND ASTROPHYSICS↗

BICEP2/KECK ARRAY V: MEASUREMENTS OF B-MODE POLARIZATION AT DEGREE ANGULAR SCALES AND 150 GHz BY THE KECK ARRAY

The Keck Array is a system of cosmic microwave background polarimeters, each similar to the Bicep2 experiment. In this paper we report results from the 2012 to 2013 observing seasons, during which the Keck Array consisted of five receivers all operating in the same (150 GHz) frequency band and observing field as Bicep2. We again find an excess of B-mode power over the lensed-ΛCDM expectation of >5σ in the range 30 < ℓ < 150 and confirm that this is not due to systematics using jackknife tests and simulations based on detailed calibration measurements. In map difference and spectral difference tests these new data are shown to be consistent with Bicep2. Finally, we combine the maps from the two experiments to produce final Q and U maps which have a depth of 57 nK deg (3.4 μK arcmin) over an effective area of 400 deg{sup 2} for an equivalent survey weight of 250,000 μK{sup −2}. The final BB band powers have noise uncertainty a factor of 2.3 times better than the previous results, and a significance of detection of excess power of >6σ.

79 ASTRONOMY AND ASTROPHYSICS↗

NEAR-ULTRAVIOLET SPECTROSCOPY OF STAR-FORMING GALAXIES FROM eBOSS: SIGNATURES OF UBIQUITOUS GALACTIC-SCALE OUTFLOWS

We present rest-frame near-ultraviolet (NUV) spectroscopy of star-forming galaxies (SFGs) at 0.6 < z < 1.2 from the Extended Baryon Oscillation Spectroscopic Survey (eBOSS) in SDSS-IV. One of the eBOSS programs is to obtain 2″ (about 15 kpc) fiber spectra of about 200,000 emission-line galaxies (ELGs) at redshift z ≳ 0.6. We use the data from the pilot observations of this program, including 8620 spectra of SFGs at 0.6 < z < 1.2. The median composite spectra of these SFGs at 2200 Å < λ < 4000 Å feature asymmetric, preferentially blueshifted non-resonant emission, Fe ii*, and blueshifted resonant absorption, e.g., Fe ii and Mg ii, indicating ubiquitous outflows driven by star formation at these redshifts. For the absorption lines, we find a variety of velocity profiles with different degrees of blueshift. Comparing our new observations with the literature, we do not observe the non-resonant emission in the small-aperture (<40 pc) spectra of local star-forming regions with the Hubble Space Telescope, and find the observed line ratios in the SFG spectra to be different from those in the spectra of local star-forming regions, as well as those of quasar absorption-line systems in the same redshift range. We introduce an outflow model that can simultaneously explain the multiple observed properties and suggest that the variety of absorption velocity profiles and the line ratio differences are caused by scattered fluorescent emission filling in on top of the absorption in the large-aperture eBOSS spectra. We develop an observation-driven, model-independent method to correct the emission infill to reveal the true absorption profiles. Finally, we show that the strengths of both the non-resonant emission and the emission-corrected resonant absorption increase with [O ii] λλ3727, 3730 rest equivalent width and luminosity, with a slightly larger dependence on the former. Our results show that the eBOSS and future dark-energy surveys (e.g., Dark Energy Spectroscopic Instrument survey and Prime Focus Spectrograph survey) will provide rich data sets of rest-frame NUV spectroscopy for astrophysical applications.

79 ASTRONOMY AND ASTROPHYSICS↗