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At least 1,549 records · Page 86

In Situ Visualization of Local Distortions in the High- T c Molecule-Intercalated Li x (C 5 H 5 N) y Fe 2– z Se 2 Superconductor

A time-resolved synchrotron X-ray total scattering study sheds light on the evolution of the different structural length scales involved during the intercalation of the layered iron–selenide host by organic molecular donors, aiming at the formation of the expanded-lattice Li x (C 5 H 5 N) y Fe 2– z Se 2 hybrid superconductor. The intercalates are found to crystallize in the tetragonal ThCr 2 Si 2 -type structure at the average level, however, with an enhanced interlayer iron–selenide spacing ( d = 16.2 Å) that accommodates the heterocyclic molecular spacers. Quantitative atomic pair distribution function (PDF) analysis at variable times suggests distorted FeSe 4 tetrahedral local environments that appear swollen with respect to those in the parent β-FeSe. Simultaneously acquired in situ synchrotron X-ray powder diffraction data disclose that secondary phases (α-Fe and Li 2 Se) grow significantly when a higher lithium concentration is used in the solvothermal reaction or when the solution is aged. These observations are in line with the strongly reducing character of the intercalation medium’s solvated electrons that mediate the defect chemistry of the expanded-lattice superconductor. In the latter, intralayer correlated local distortions indicate electron-donating aspects that reflect in somewhat enlarged Fe–Se bonds. Additionally, they also reveal a degree of relief of chemical pressure associated with a large distance between Fe and Se sheets (“taller” anion height) and a stretched Fe–Fe square planar topology. The elongation of the latter, derived from the in situ PDF study, speaks for a plausible increase in the Fe-site vacancy concentration. The evolution of the local structural parameters suggests an optimum reaction window where kinetically stabilized phases resemble the distortions of the edge-sharing Fe–Se tetrahedra, required for a high- T c in expanded-lattice iron-chalcogenides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The hierarchical structure of organic mixed ionic–electronic conductors and its evolution in water

Polymeric organic mixed ionic–electronic conductors underpin several technologies in which their electrochemical properties are desirable. These properties, however, depend on the microstructure that develops in their aqueous operational environment. We investigated the structure of a model organic mixed ionic–electronic conductor across multiple length scales using cryogenic four-dimensional scanning transmission electron microscopy in both its dry and hydrated states. Four-dimensional scanning transmission electron microscopy allows us to identify the prevalent defects in the polymer crystalline regions and to analyse the liquid crystalline nature of the polymer. The orientation maps of the dry and hydrated polymers show that swelling-induced disorder is mostly localized in discrete regions, thereby largely preserving the liquid crystalline order. Therefore, the liquid crystalline mesostructure makes electronic transport robust to electrolyte ingress. Furthermore, this study demonstrates that cryogenic four-dimensional scanning transmission electron microscopy provides multiscale structural insights into complex, hierarchical structures such as polymeric organic mixed ionic–electronic conductors, even in their hydrated operating state.

36 MATERIALS SCIENCE↗

Microscale Observation via High-Speed X-ray Diffraction of Alloy 718 During In Situ Laser Melting

The laser melting process is accompanied by rapid evolution in temperature, phase, structure, and strain because of its high heating and cooling rates. In this study, the evolution of grains within a thin solid plate of Ni alloy 718 during laser processing was probed with in situ high-energy x-ray diffraction experiments. The high temporal and spatial resolution available in the measurement allowed us to study the rapid evolution of the melted region beneath the surface of the sample. The characterization of the evolution of secondary phases, i.e., Laves and carbide, was captured despite the weak diffracted peaks caused by small volume fractions. Thermal history was estimated based on changes in the lattice spacing from the thermal contraction upon cooling. In conclusion, the temporal variation in 2θ with azimuthal direction revealed the evolution in anisotropy of lattice spacing and thus of the mechanical state during laser processing.

36 MATERIALS SCIENCE↗

Effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria: Soot-ceria contact and interfacial oxygen evolution

Ceria is widely used as a catalyst for soot combustion, but effects of Zr substitution on the reaction mechanism is ambiguous. The present work elucidates effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria. The nanostructured CeO 2 , Ce 0.92 Zr 0.08 O 2 , and Ce0.84Zr0.16O2 composed of 5–6 nm crystallites display Tm-CO 2 (the temperature at maximum CO 2 yield) at 383, 355, and 375°C under 10 vol.% O 2 /N 2 , respectively. Additionally, the size of agglomerate decreases from 165.5 to 51.9–57.3 nm, which is beneficial for the soot-ceria contact. Moreover, Zr increases the amount of surface oxygen vacancies, generating more active oxygen (O2- and O-) for soot oxidation. Thus, the activities of Ce 0.92 Zr 0.08 O 2 and Ce 0.84 Zr 0.16 O 2 in soot combustion are better than that of CeO2. Although oxygen vacancies promote the migration of lattice O 2- , the enriched surface Zr also inhibits the mobility of lattice O 2- . Therefore, the Tm-CO 2 of Ce 0.84 Zr 0.16 O 2 is higher than that of Ce 0.92 Zr 0.08 O 2 . Based on reaction kinetic study, soot in direct contact with ceria preferentially decomposes with low activation energy, while the oxidation of isolated soot occurs through diffusion with high activation energy. The obtained findings provide new understanding on the soot combustion over nanoceria.

54 ENVIRONMENTAL SCIENCES↗

Lattice response to ambient self-irradiation of δ-phase 239 Pu-Ga alloys exposed to cryogenic temperatures

Self-irradiation in plutonium is a continuous process that introduces radiation damage ranging from point defects to nanoscale radiation damage as well as decay daughter product impurities that require to be accommodated by the host material. These changes are affecting the structure and properties of the material by lattice swelling, mechanical strengthening, and other alterations. X-ray diffraction and dilatometry studies have shown that the room temperature self-irradiation of δ-phase Pu-Ga alloys (2 and 7 at%Ga) results in swelling of the lattice that saturates after 0.1–0.2 displacement per atom (dpa) of accumulated lattice damage. Here, for a better understanding of these self- irradiation processes, defect accumulation and damage evolution, this time-of-flight neutron diffraction study investigates the impact of ambient self-irradiation effects on the structural evolution of δ-phase 239 Pu-Ga alloys exposed to cryogenic temperatures (<120 K), associated with a varied history of storage time and thermal treatments. Two key behaviors were observed in the lattice evolution after exposure to cryogenic temperatures with respect to room-temperature accumulated self-irradiation damage. Samples with no self- irradiation damage accumulation under ambient conditions showed swelling of the lattice at the end of the measurement, while samples that accumulated significant self-irradiation damage under ambient conditions showed only a partial recovery of the lattice parameter value upon completion of the measurements (cooling followed by heating back to room temperature). Possible causes of the behavior are proposed, and their associated effects are discussed.

36 MATERIALS SCIENCE↗

Recent Progress on Topological Structures in Ferroic Thin Films and Heterostructures

Topological spin/polarization structures in ferroic materials continue to draw great attention as a result of their fascinating physical behaviors and promising applications in the field of high-density nonvolatile memories as well as future energy-efficient nanoelectronic and spintronic devices. Such developments have been made, in part, based on recent advances in theoretical calculations, the synthesis of high-quality thin films, and the characterization of their emergent phenomena and exotic phases. Herein, progress over the last decade in the study of topological structures in ferroic thin films and heterostructures is explored, including the observation of topological structures and control of their structures and emergent physical phenomena through epitaxial strain, layer thickness, electric, magnetic fields, etc. First, the evolution of topological spin structures (e.g., magnetic skyrmions) and associated functionalities (e.g., topological Hall effect) in magnetic thin films and heterostructures is discussed. Then, the exotic polar topologies (e.g., domain walls, closure domains, polar vortices, bubble domains, and polar skyrmions) and their emergent physical properties in ferroelectric oxide films and heterostructures are explored. Lastly, a brief overview and prospectus of how the field may evolve in the coming years is provided.

36 MATERIALS SCIENCE↗

Ion-specific clustering of metal-amphiphile complexes in rare earth separations

The nanoscale structure of a complex fluid can play a major role in the selective adsorption of ions at the nanometric interfaces, which is crucial in industrial and technological applications. Here we study the effect of anions and lanthanide ions on the nanoscale structure of a complex fluid formed by metal-amphiphile complexes, using small angle X-ray scattering. The nano- and mesoscale structures we observed can be directly connected to the preferential transfer of light (La and Nd) or heavy (Er and Lu) lanthanides into the complex fluid from an aqueous solution. While toluene-based complex fluids containing trioctylmethylammonium-nitrate (TOMA-nitrate) always show the same mesoscale hierarchical structure regardless of lanthanide loading and prefer light lanthanides, those containing TOMA-thiocyanate show an evolution of the mesoscale structure as a function of the lanthanide loading and prefer heavy lanthanides. The hierarchical structure indicates the presence of attractive interactions between ion-amphiphile aggregates, causing them to form clusters. A clustering model that accounts for the hard sphere repulsions and short-range attractions between the aggregates has been adapted to model the X-ray scattering results. The new model successfully describes the nanoscale structure and helps in understanding the mechanisms responsible for amphiphile assisted ion transport between immiscible liquids. Accordingly, our results imply different mechanisms of lanthanide transport depending on the anion present in the complex fluid and correspond with anion-dependent trends in rare earth separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural insights into the formation of repulsive netrin guidance complexes

Netrins dictate attractive and repulsive responses during axon growth and cell migration, where the presence of the receptor Uncoordinated-5 (UNC-5) on target cells results in repulsion. Here, we showed that UNC-5 is a heparin-binding protein, determined its structure bound to a heparin fragment, and could modulate UNC-5–heparin affinity using a directed evolution platform or structure-based rational design. We demonstrated that UNC-5 and UNC-6/netrin form a large, stable, and rigid complex in the presence of heparin, and heparin and UNC-5 exclude the attractive UNC-40/DCC receptor from binding to UNC-6/netrin to a large extent. Caenorhabditis elegans with a heparin-binding–deficient UNC-5 fail to establish proper gonad morphology due to abrogated cell migration, which relies on repulsive UNC-5 signaling in response to UNC-6. Combining UNC-5 mutations targeting heparin and UNC-6/netrin contacts results in complete cell migration and axon guidance defects. Our findings establish repulsive netrin responses to be mediated through a glycosaminoglycan-regulated macromolecular complex.

59 BASIC BIOLOGICAL SCIENCES↗

Monte-Carlo Simulation of Heavy Ion Track Structure Calculation of Local Dose and 3D Time Evolution of Radiolytic Species

Heavy ions have gained considerable importance in radiotherapy due to their advantageous dose distribution profile and high Relative Biological Effectiveness (RBE). Heavy ions are difficult to produce on Earth, but they are present in space and it is impossible at this moment to completely shield astronauts from them. The risk of these radiations is poorly understood, which is a concern for a 3-years Mars mission. The effects of radiation are mainly due to DNA damage such as DNA double-strand breaks (DSBs), although non-targeted effects are also very important. DNA can be damaged by the direct interaction of radiation and by reactions with chemical species produced by the radiolysis of water. The energy deposition is of crucial importance to understand biological effects of radiation. Therefore, much effort has been done recently to improve models of radiation tracks.

Plante, Ianik↗

Pulsed Flows Along a Cusp Structure Observed with SOO/AIA

We present observations of a cusp-shaped structure that formed after a flare and coronal mass ejection on 14 February 2011. Throughout the evolution of the cusp structure, blob features up to a few Mm in size were observed flowing along the legs and stalk of the cusp at projected speeds ranging from 50 to 150 km/sec. Around two dozen blob features, on order of 1 - 3 minutes apart, were tracked in multiple AlA EUV wavelengths. The blobs flowed outward (away from the Sun) along the cusp stalk, and most of the observed speeds were either constant or decelerating. We attempt to reconstruct the 3-D magnetic field of the evolving structure, discuss the possible drivers of the flows (including pulsed reconnect ion and tearing mode instability), and compare the observations to studies of pulsed reconnect ion and blob flows in the solar wind and the Earth's magnetosphere.

Thompson, Barbara↗

Introduction: "Let there be (some) life"

The author introduces a meeting session about the origins of life by briefly reviewing theories of chemical and molecular evolution. The discussion focuses on structures of early life, sequences of chemical synthesis, and evolution of biomolecules.

Non-NASA Center↗

Cathodic Protection Deployment on Space Shuttle Solid Rocket Boosters

Corrosion protection of the space shuttle solid rocket boosters incorporates the use of cathodic protection(anodes) in concert with several coatings systems. The SRB design has large carbon/carbon composites(motor nozzle) electrically connected to an aluminum alloy structure. Early in the STS program, the aluminum structures incurred tremendous corrosive attack due primarily to the galvanic couple to the carbon/carbon nozzle at coating damage locations. Also contributing to the galvanic corrosion problem were stainless steel and titanium alloy components housed within the aluminum structures and electrically connected to the aluminum structures. This paper will highlight the evolution in the protection of the aluminum structures, providing historical information and summary data from the operation of the corrosion protection systems. Also, data and information will be included regarding the evaluation and deployment of inorganic zinc rich primers as anode area on the aluminum structures.

Zook, Lee M.↗

Evolution of solid electrolyte interphase and active material in the silicon wafer model system

Alloying anode materials for lithium-ion batteries, such as silicon (Si), are an important focus of materials research due to the demand for increased energy density for electric vehicles and stationary grid storage. However, progress towards next generation anode materials has been hindered by poor capacity retention due to the instability of the Si active material and the solid electrolyte interphase (SEI). Herein, the evolution of the active Si material and the SEI are simultaneously investigated from the perspective of chemical, structural, morphological, and electronic evolution in the Si wafer model system through its cycling life, using time-of-flight secondary ion mass spectrometry (TOF-SIMS), scanning transmission electron microscopy (STEM), atomic force microscopy (AFM), and scanning spreading resistance microscopy (SSRM). The results illustrate a dynamic evolution of the SEI and active Si material through cycling. Through an improved understanding of evolution of SEI and Si active material within the Si wafer model system, mitigation strategies may be designed to extend the lifetime of Si anodes.

25 ENERGY STORAGE↗

Interplanetary Mesoscale Observatory (InterMeso): A Mission to Untangle Dynamic Mesoscale Structures Throughout the Heliosphere

Mesoscale dynamics are a fundamental process in space physics, but fall within an observational gap of current and planned missions. Particularly in the solar wind, measurements at the mesoscales (100s RE to a few degrees heliographic longitude at 1 au) are crucial for understanding the connection between the corona and an observer anywhere within the heliosphere. Mesoscale dynamics may also be key to revealing the currently unresolved physics regulating particle acceleration and transport, magnetic field topology, and the causes of variability in the composition and acceleration of solar wind plasma. Studies using single-point observations do not allow for investigations into mesoscale solar wind dynamics and plasma variability, nor do they allow for the exploration of the sub-structuring of large-scale solar wind structures like coronal mass ejections (CMEs), co-rotating/stream interaction regions (CIR/SIRs), and the heliospheric plasma sheet. To address this fundamental gap in our knowledge of the heliosphere at these scales, the Interplanetary Mesoscale Observatory (InterMeso) concept employs a multi-point approach using four identical spacecraft in Earth-trailing orbits near 1 au. Varying drift speeds of the InterMeso spacecraft enable the mission to span a range of mesoscale separations in the solar wind, achieving significant and innovative science return. Simultaneous, longitudinally-separated measurements of structures co-rotating over the spacecraft also allow for disambiguation of spatiotemporal variability, tracking of the evolution of solar wind structures, and determination of how the transport of energetic particles is impacted by these variabilities.

solar wind↗

Interplanetary Mesoscale Observatory (InterMeso): A mission to untangle dynamic mesoscale structures throughout the heliosphere

Mesoscale dynamics are a fundamental process in space physics, but fall within an observational gap of current and planned missions. Particularly in the solar wind, measurements at the mesoscales (100s RE to a few degrees heliographic longitude at 1 au) are crucial for understanding the connection between the corona and an observer anywhere within the heliosphere. Mesoscale dynamics may also be key to revealing the currently unresolved physics regulating particle acceleration and transport, magnetic field topology, and the causes of variability in the composition and acceleration of solar wind plasma. Studies using single-point observations do not allow for investigations into mesoscale solar wind dynamics and plasma variability, nor do they allow for the exploration of the sub-structuring of large-scale solar wind structures like coronal mass ejections (CMEs), co-rotating/stream interaction regions (CIR/SIRs), and the heliospheric plasma sheet. To address this fundamental gap in our knowledge of the heliosphere at these scales, the Interplanetary Mesoscale Observatory (InterMeso) concept employs a multi-point approach using four identical spacecraft in Earth-trailing orbits near 1 au. Varying drift speeds of the InterMeso spacecraft enable the mission to span a range of mesoscale separations in the solar wind, achieving significant and innovative science return. Simultaneous, longitudinally-separated measurements of structures co-rotating over the spacecraft also allow for disambiguation of spatiotemporal variability, tracking of the evolution of solar wind structures, and determination of how the transport of energetic particles is impacted by these variabilities.

solar wind↗