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At least 757 records · Page 42

Time-resolved chemically-selective spectroscopic investigation of the redox reaction between hematite and aluminium

Thermite reactions –highly energetic redox processes between a metal and an oxide—are used in welding, propulsion, and the fabrication of advanced materials. When reduced to the nanoscale, these reactions exhibit enhanced energetic performance, but their ultrafast dynamics remain poorly understood. Gaining insight into charge transfer during these processes is essential for advancing applications in energy conversion and materials design. Here we show that the reaction between aluminium and hematite, a common iron oxide, can be tracked with femtosecond resolution using extreme ultraviolet (EUV) time-resolved absorption spectroscopy at the Fe M 2,3 and Al L 2,3 edges. By exciting the system with an ultrashort optical pulse and probing element-specific absorption changes, we observe an early spectral shift that reveals the formation of localized charge carriers (polarons). Comparing samples with different supporting substrates highlights ultrafast electron transfer from aluminium to hematite. These results demonstrate an approach to investigating charge flow in energetic materials and provide a basis for studying fast chemical reactions with chemical specificity.

Electron transfer↗

Mimicking Natural Photosynthesis: Designing Ultrafast Photosensitized Electron Transfer into Multiheme Cytochrome Protein Nanowires

Efficient nanomaterials for artificial photosynthesis require fast and robust unidirectional electron transfer (ET) from photosensitizers through charge-separation and accumulation units to redox-active catalytic sites. We explored the ultrafast time-scale limits of photo-induced charge transfer between a Ru(II)tris(bipyridine) derivative photosensitizer and PpcA, a 3-heme c-type cytochrome serving as a nanoscale biological wire. Four covalent attachment sites (K28C, K29C, K52C, and G53C) were engineered in PpcA enabling site-specific covalent labeling with expected donor-acceptor (DA) distances of 4–8 Å. X-ray scattering results demonstrated that mutations and chemical labeling did not disrupt the structure of the proteins. Time-resolved spectroscopy revealed three orders of magnitude difference in charge transfer rates for the systems with otherwise similar DA distances and the same number of covalent bonds separating donors and acceptors. All-atom molecular dynamics simulations provided additional insight into the structure-function requirements for ultrafast charge transfer and the requirement of van der Waals contact between aromatic atoms of photosensitizers and hemes in order to observe sub-nanosecond ET. This work demonstrates opportunities to utilize multi-heme c-cytochromes as frameworks for designing ultrafast light-driven ET into charge-accumulating biohybrid model systems, and ultimately for mimicking the photosynthetic paradigm of efficiently coupling ultrafast, light-driven electron transfer chemistry to multi-step catalysis within small, experimentally versatile photosynthetic biohybrid assemblies.

36 MATERIALS SCIENCE↗

Proton-rich Production of Lanthanides: The vi Process

The astrophysical origin of the lanthanides is an open question in nuclear astrophysics. Besides the widely studied s, i, and r processes in moderately to strongly neutron-rich environments, an intriguing alternative site for lanthanide production could in fact be robustly proton-rich matter outflows from core-collapse supernovae under specific conditions—in particular, high-entropy winds with enhanced neutrino luminosity and fast dynamical timescales. In this environment, excess protons present after charged-particle reactions have ceased can continue to be converted to neutrons by (anti)neutrino interactions, producing a neutron-capture reaction flow up to A ∼ 200. This scenario, christened the νi process in a recent paper, has previously been discussed as a possibility. Here, we examine the prospects for the νi process through the lenses of stellar abundance patterns, bolometric light curves, and galactic chemical evolution models, with a particular focus on hypernovae as candidate sites. We identify specific lanthanide signatures for which the νi process can provide a credible supplement to the r/i processes.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Applications of activation analysis to geochemical, meteoritic and lunar studies.

The application of activation analysis techniques to the analysis of cosmological materials, i.e., terrestrial, tektitic, meteoritic, and lunar matter, is reviewed. Elemental determinations can be made by instrumental fast-neutron and thermal-neutron activation analysis, photonuclear and charged-particle activation analysis, and by radiochemical neutron activation analysis. Partition-coefficient methods, autoradiography studies, gamma-gamma coincidence counting, and age determination by neutron activation are discussed. Attention is given to K-Ar and I-Xe dating of meteorites.

Showalter, D. L.↗

Shuttle electrodynamic tether system

The Shuttle Electrodynamic Tether System (SETS), an investigation of the interaction of a tethered satellite, a conducting tether, and the Orbiter with each other and with their environments is discussed. The historical development of SETS and its objectives are reviewed. The SETS instrumentation is described, including the Tether Current and Voltage Monitor, Fast Pulse Electron Gun, Spherical Retarding Potential Analyzer and Langmuir Probe, Charge Current Probe, Digital Control and Interface Unit, and Dedicated Experiment Processor. The measurements to be made by SETS are examined, and its operations are briefly addressed.

Williamson, P. R.↗

Spaceflight Validation of Hzetrn Code

HZETRN is being developed as a fast deterministic radiation transport code applicable to neutrons, protons, and multiply charged ions in the space environment. It was recently applied to 50 hours of IMP8 data measured during the August 4, 1972 solar event to map the hourly exposures within the human body under several shield configurations. This calculation required only 18 hours on a VAX 4000 machine. A similar calculation using the Monte Carlo method would have required two years of dedicated computer time. The code has been benchmarked against well documented and tested Monte Carlo proton transport codes with good success. The code will allow important trade studies to be made with relative ease due to the computational speed and will be useful in assessing design alternatives in an integrated system software environment. Since there are no well tested Monte Carlo codes for HZE particles, we have been engaged in flight validation of the HZETRN results. To date we have made comparison with TEPC, CR-39, charge particle telescopes, and Bonner spheres. This broad range of detectors allows us to test a number of functions related to differing physical processes which add to the complicated radiation fields within a spacecraft or the human body, which functions can be calculated by the HZETRN code system. In the present report we will review these results.

Wilson, J. W.↗

Energy and Mass Transport of Magnetospheric Plasmas during the November 2003 Magnetic Storm

Intensive energy and mass transport from the solar wind across the magnetosphere boundary is a trigger of magnetic storms. The storm on 20-21 November 2003 was elicited by a high-speed solar wind and strong southward component of interplanetary magnetic field. This storm attained a minimum Dst of -422 nT. During the storm, some of the solar wind particles enter the magnetosphere and eventually become part of the ring current. At the same time, the fierce solar wind powers strong outflow of H+ and O+ from the ionosphere, as well as from the plasmasphere. We examine the contribution of plasmas from the solar wind, ionosphere and plasmasphere to the storm-time ring current. Our simulation shows, for this particular storm, ionospheric O+ and solar wind ions are the major sources of the ring current particles. The polar wind and plasmaspheric H+ have only minor impacts. In the storm main phase, the strong penetration of solar wind electric field pushes ions from the geosynchronous orbit to L shells of 2 and below. Ring current is greatly intensified during the earthward transport and produces a large magnetic depression in the surface field. When the convection subsides, the deep penetrating ions experience strong charge exchange loss, causing rapid decay of the ring current and fast initial storm recovery. Our simulation reproduces very well the storm development indicated by the Dst index.

Fok, Mei-Chging↗

Plasma Deflection Test Setup for E-Sail Propulsion Concept

The Electronic Sail or E-Sail is a novel propulsion concept based on momentum exchange between fast solar wind protons and the plasma sheath of long positively charged conductors comprising the E-Sail. The effective sail area increases with decreasing plasma density allowing an E-Sail craft to continue to accelerate at predicted ranges well beyond the capabilities of existing electronic or chemical propulsion spacecraft. While negatively charged conductors in plasmas have been extensively studied and flown, the interaction between plasma and a positively charged conductor is not well studied. We present a plasma deflection test method using a differential ion flux probe (DIFP). The DIFP measures the angle and energy of incident ions. The plasma sheath around a charged body can measured by comparing the angular distribution of ions with and without a positively charged test body. These test results will be used to evaluate numerical calculations of expected thrust per unit length of conductor in the solar wind plasma. This work was supported by a NASA Space Technology Research Fellowship.

Andersen, Allen↗

Operando Contactless EFISH Study of the Rate-Determining Step of Light-Driven Water Oxidation on TiO 2 Photoanodes

For many slow solar-fuel-forming reactions, the accumulation of photogenerated minority carriers on the photoelectrode surface leads to light-induced band edge unpinning, affecting the junction properties by decreasing band bending in the semiconductor space charge layer and increasing the driving force of surface reactions in the electric double layer. In this study, we demonstrate a contactless operando electric field-induced second harmonic generation (EFISH) method for measuring the band bending change (δΔΦ SCR L ) on photoelectrodes upon photoexcitation. For ndoped rutile TiO 2 water oxidation photoanodes at pH 7, δΔΦ SCR L increases at more positive potentials or higher illumination power density until it reaches saturation values. We show that under fast mass transport conditions, δΔΦ SCR L is exclusively attributed to the accumulated charged rate-determining species that can be regarded as temporary surface states, and the relationship between the photocurrent and δΔΦ SCR L can be well modeled by assuming that hole trap states function as the reaction center. Kinetic isotope experiments identify proton-coupled electron transfer as the rate-determining step and suggest a possible chemical nature of the key intermediate. We demonstrate that light-induced band edge unpinning is a beneficial feature under high illumination conditions for oxygen evolution reaction on TiO 2 because it maintains the photon-to-current conversion efficiency by enhancing the surface reaction driving force, shedding light on the actual device application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Contactless measurement of the photovoltage in BiVO 4 photoelectrodes

The power output of photoelectrochemical devices for solar energy-to-fuel conversion is determined by the photovoltage of the junction under illumination. In the presence of fast redox couples, the photovoltage can be obtained directly from current–voltage measurements of the device. However, for slow redox couples (H + /H 2 , O 2 /H 2 O) used in solar fuel photoelectrodes, photovoltage measurements are not straightforward, due to the kinetic overpotentials during charge transfer. Here we show that the photovoltage of BiVO 4 electrodes in contact with fast electron donors KI, Na 2 SO 3 or H 2 O 2 or K 4 Fe(CN) 6 can be measured in a contactless way with vibrating Kelvin probe surface photovoltage (SPV) spectroscopy. The photovoltage varies with illumination wavelength and intensity and matches the open circuit potential of the electrodes, obtained separately from electrochemical measurements. Plots of the photovoltage versus irradiance can be used to predict the oxidizing power of each electrode under zero applied bias. Except for K 4 Fe(CN) 6 , which causes shunting in the BiVO 4 electrode, photovoltage values correlate well with the built-in potential of each junction. Furthermore, the ability to obtain photovoltage information through contactless SPV measurements will be useful in the search for solid–liquid junctions with superior energy conversion properties.

14 SOLAR ENERGY↗

Large-scale variations of solar wind elemental composition and charge states with heliospheric latitude

The Solar Wind Ion Composition Spectrometer (SWICS) onboard Ulysses allows determination of the elemental composition of the solar wind and the charge states of all major solar wind ion species. Ulysses left the ecliptic plane in early 1992, crossed the Sun's south polar region in late 1994 and made a fast approach back towards the ecliptic in the first half of 1995. Data from this period were investigated for long-term variations in the solar wind composition. At midlatitudes Ulysses encountered periodically the fast solar wind stream emerging from the south coronal hole. As a consequence, dramatic variations in the charge-states arise, between high charge-states dominating in the current sheet solar wind and low charge states in the coronal hole stream. However, the initial analysis indicates that from midlatitudes onwards, with Ulysses permanently immersed in the coronal hole stream, the charge state and elemental abundance ratios of the major solar wind ion species stayed essentially constant. This implies that the temperature profile in the coronal hole at solar wind source altitudes exhibit no variation with solar latitude. It confirms that the south coronal hole is essentially unstructured down to scale lengths of several degrees in solar latitude.

Woch, J.↗

Low-temperature sprayed SnO x nanocomposite films with enhanced hole blocking for efficient large area perovskite solar cells

Scalable fabrication of charge transport layers with high uniformity and compactness is essential for the commercialization of perovskite solar cells (PSCs). Cost-effective deposition of high-quality electron transport layers (ETLs) is a particularly important step to achieve low-cost, efficient and large-area PSCs. Here, an open-air (relative humidity of 40–50%) and low-temperature (≤100 °C) ultrasonic spray coating of tin oxide (SnO 2 ) nanocomposite films incorporating nanocrystalline SnO 2 nanoparticles in an amorphous SnO x matrix is demonstrated to fabricate large-area ETLs for planar PSCs. The optimized SnO 2 /SnO x nanocomposite exhibits significantly enhanced hole-blocking and high-power conversion efficiencies of 18% and 16% for planar PSCs with an active area of 0.2 cm 2 and 1 cm 2 , respectively. More importantly, the devices show little current–voltage hysteresis as well as good shelf-life stability by maintaining ~90% of the initial performance without encapsulation after 2500 hours storage under inert conditions. Additionally, high voltages of >6.0 V have been obtained for solar modules of 2.1 cm 2 aperture area comprising six sub-cells in series, suggesting that the low-temperature, open-air and fast spray coating is suitable and transferable to deposit large-area charge transport layers for scalable PSCs or other optoelectronic devices.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Charge collection study with the ATLAS ITk prototype silicon strip sensors ATLAS17LS

The inner tracker of the ATLAS detector is scheduled to be replaced by a completely new silicon-based inner tracker (ITk) for the Phase-II of the CERN LHC (HL-LHC). The silicon strip detector covers the volume 40 < R < 100 cm in the radial and | z | < 300 cm in the longitudinal directions. The silicon sensors for the detector will be fabricated using the n + -on-p 6-inch wafer technology, for a total of 22,000 wafers. Here, intensive studies were carried out on the final prototype sensors ATLAS17LS fabricated by Hamamatsu Photonics (HPK). The charge collection properties were examined using penetrating 90 Sr β -rays and the ALIBAVA fast readout system for the miniature sensors of 1 cm × 1 cm in area. The samples were irradiated by protons in the 27 MeV Birmingham Cyclotron, the 70 MeV CYRIC at Tohoku University, and the 24 GeV CERN-PS, and by neutrons at Ljubljana TRIGA reactor for fluence values up to 2 × 10 15 n eq /cm 2 . The change in the charge collection with fluence was found to be similar to the previous prototype ATLAS12, and acceptable for the ITk. Sensors with two active thicknesses, 300 μ m (standard) and 240 μ m (thin), were compared and the difference in the charge collection was observed to be small for bias voltages up to 500 V. Some samples were also irradiated with gamma radiation up to 2 MGy, and the full depletion voltage was found to decrease with the dose. This was caused by the Compton electrons due to the 60 Co gamma radiation. To summarize, the design of the ATLAS17LS and technology for its fabrication have been verified for implementation in the ITk. We are in the stage of sensor pre-production with the first sensors already delivered in January of 2020.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Additive manufacturing of high explosives with inert dilution for wave shaping and detonation velocity grading

The performance of a high explosive charge is highly influenced by the detonation velocity and any inherent internal structure. Additively manufactured (AM) high explosive charges allow for a precisely engineered internal structure and the selective placement of discrete or graded volumes of a tailored material, which are unachievable by conventional means. The dilution of a solid explosive by an inert additive for detonation velocity reduction is herein evaluated for a method of material extrusion called a direct-ink-write AM, where an 1,3,5,7-tetranitro-1,3,5,7-tetrazoctane-based ultraviolet -curable energetic-binder paste explosive was diluted by the inert density mock 5-iodo-2′-deoxyuridine for use in the manufacture of multi-material explosive charges. The explosive ink was characterized for printing by rheological and particle size measurements, and the detonation velocities for 0–40 wt. % inert diluent were found to have a continuous linear reduction in detonation velocity down to 14.3% difference. A two-component 3D plane wave explosive lens with 8.038 km/s “fast” and 7.491 km/s “slow” diluted ink in an internal cone demonstrated a reduced time of breakout at the output face from 361 to 53 ns. A linearly graded “fast–slow–fast” cylinder was successfully printed and fired, showing engineered control along the length of the charge as the detonation velocity dropped from 7.851 to 6.700 km/s and then recovered to 7.241 km/s. The extreme control over the internal composition of a high explosive charge via a dual-material extruder/mixer challenges conventional manufacturing approaches and opens new avenues for engineered detonation wavefronts, high explosive charge performance, and new applications.

36 MATERIALS SCIENCE↗

Direct current response of a thin scCVD diamond detector under increased applied field to 14.1 MeV neutrons

An avalanche effect yielding inherent gain can be exploited in thin, single-crystal chemical vapor deposition (scCVD) diamond. It occurs when a high enough bias is applied across the diamond thickness while avoiding breakdown. This charge multiplication effect was studied previously with alpha particles and heavy ions either by using the transient current technique or by measuring the energy spectrum. The measurements we obtained to evaluate the charge multiplication performance of a 10 μm thick scCVD diamond detector used a novel approach—we employed an electrometer to characterize the response of the detector by performing directly coupled current measurements (time-averaged charge, at 1 Hz sampling) when exposed to 14.1 MeV neutrons from deuterium-tritium fusion. We measured both the dark and irradiated currents from the detector over a range of applied displacement field values from 2 to 75 V/μm. A histogram method with central mean and standard deviation width was used to determine the current over each measurement duration typically from 100 to 300 seconds. The dark-subtracted irradiated current (i.e., contrast) was used to evaluate the gain of the detector at each applied displacement field. The contrast at an applied displacement field between 15 and 20 V/μm was higher than the expected linear increase in contrast proportional to the increased applied bias, indicating the possible presence of avalanche events in the diamond. The detector response also indicated possible polarization and charge depletion effects. These results provide an opportunity to further explore the use of thin scCVD diamond as a fast neutron current mode detector with inherent gain.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Advanced LiFSI-LiPF6 Electrolyte for Wide-Temperature and Thermally Stable Lithium-Ion Batteries

A new optimized LiFSI–LiPF6 dual-salt controlled-solvation electrolyte (E-DS) is demonstrated to enable practical graphite||LiNi0.8Mn0.1Co0.1O2 cells (˜4.0 mAh cm?²) to achieve exceptional performance and safety under extreme conditions. By optimizing anion coordination with the smaller, more dissociating FSI? anion, the E-DS forms ultrathin, dense, and inorganic-rich electrode/electrolyte interphases that dramatically suppress solvent decomposition, transition-metal dissolution, and surface reconstruction compared to the conventional LiPF6/carbonate electrolyte. Consequently, E-DS cells deliver >78% capacity retention after 300 cycles at 60 °C, retain fast discharging capacity at 30 °C, and operate effectively at -20 °C. Most strikingly, fully charged full cells with E-DS, even under overcharging to 4.8 V, show a lower heat evolution in stable formulations — transforming a traditionally unstable high-voltage/high-temperature configuration into an intrinsically safe state. This work establishes a new benchmark for carbonate-containing electrolytes, simultaneously achieving high energy density, fast-discharging capability, wide-temperature operation (-20 to 60 °C), and outstanding thermal safety in nickel-rich lithium-ion batteries.

electrode/electrolyte interphase↗

Dose Calibration of the ISS-RAD Fast Neutron Detector

The ISS-RAD instrument has been fabricated by Southwest Research Institute and delivered to NASA for flight to the ISS in late 2015 or early 2016. ISS-RAD is essentially two instruments that share a common interface to ISS. The two instruments are the Charged Particle Detector (CPD), which is very similar to the MSL-RAD detector on Mars, and the Fast Neutron Detector (FND), which is a boron-loaded plastic scintillator with readout optimized for the 0.5 to 10 MeV energy range. As the FND is completely new, it has been necessary to develop methodology to allow it to be used to measure the neutron dose and dose equivalent. This talk will focus on the methods developed and their implementation using calibration data obtained in quasi-monoenergetic (QMN) neutron fields at the PTB facility in Braunschweig, Germany. The QMN data allow us to determine an approximate response function, from which we estimate dose and dose equivalent contributions per detected neutron as a function of the pulse height. We refer to these as the "pSv per count" curves for dose equivalent and the "pGy per count" curves for dose. The FND is required to provide a dose equivalent measurement with an accuracy of 10% of the known value in a calibrated AmBe field. Four variants of the analysis method were developed, corresponding to two different approximations of the pSv per count curve, and two different implementations, one for real-time analysis onboard ISS and one for ground analysis. We will show that the preferred method, when applied in either real-time or ground analysis, yields good accuracy for the AmBe field. We find that the real-time algorithm is more susceptible to chance-coincidence background than is the algorithm used in ground analysis, so that the best estimates will come from the latter.

Zeitlin, C.↗