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At least 217 records · Page 12

VLTI-MATISSE L- and N-Band Aperture-Synthesis Imaging of the Unclassified B[e] star FS Canis Majoris

Context. FS Canis Majoris (FS CMa, HD 45677) is an unclassified B[e] star surrounded by an inclined dust disk. The evolutionary stage of FS CMa is still debated. Perpendicular to the circumstellar disk, a bipolar outflow was detected. Infrared aperture-synthesis imaging provides us with a unique opportunity to study the disk structure. Aims. Our aim is to study the intensity distribution of the disk of FS CMa in the mid-infrared L and N bands. Methods. We performed aperture-synthesis imaging of FS CMa with the MATISSE instrument (Multi AperTure mid-Infrared SpectroScopic Experiment) in the low spectral resolution mode to obtain images in the L and N bands. We computed radiative transfer models that reproduce the L- and N-band intensity distributions of the resolved disks. Results. We present L- and N-band aperture-synthesis images of FS CMa reconstructed in the wavelength bands of 3.4–3.8 and 8.6–9.0 μm. In the L-band image, the inner rim region of an inclined circumstellar disk and the central object can be seen with a spatial resolution of 2.7 milliarcsec (mas). An inner disk cavity with an angular diameter of ~6 × 12 mas is resolved. The L-band disk consists of a bright northwestern (NW) disk region and a much fainter southeastern (SE) region. The images suggest that we are looking at the bright inner wall of the NW disk rim, which is on the far side of the disk. In the N band, only the bright NW disk region is seen. In addition to deriving the inclination and the inner disk radius, fitting the reconstructed brightness distributions via radiative transfer modelling allows one to constrain the innermost disk structure, in particular the shape of the inner disk rim.

techniques↗

Towards Run-Time Search for Real-World Multi-Agent Systems

Multi-agent systems (MAS) may encounter uncertainties in the form of unexpected environmental conditions, sub-optimal system configurations, and unplanned interactions between autonomous agents. The number of combinations of such uncertainties may be innumerable, however run-time testing may reduce the issues impacting such a system. We posit that search heuristics can augment a run-time testing process, in-situ, for a MAS. To support our position we discuss our in-progress experimental testbed to realize this goal and highlight challenges we anticipate for this domain.

Abigail C. Diller↗

X-Ray and Near-Infrared Observations of the Middle-aged Pulsar B1055-52, Its Multiwavelength Spectrum, and Proper Motion

Previous observations of the middle-aged γ-ray, X-ray, and radio pulsar B1055–52 indicated some peculiarities, such as a suspected changing of the X-ray flux and spectral parameters, a large excess of the alleged thermal component of the UV spectrum over the Rayleigh–Jeans extension of the X-ray thermal spectrum, and a possible double break in the nonthermal spectral component between the optical and X-ray bands. We observed PSR B1055–52 with the XMM-Newton observatory in X-rays and the Hubble Space Telescope in near-infrared (NIR). The analysis of the XMM-Newton observations does not support the notion of long-term changes in the X-ray flux and broadband X-ray spectrum of the pulsar. Using an observing mode less affected by background noise than the previous XMM-Newton observations, we constrain the power-law (PL) spectral index as X 0.57 0.25 0.26 a = - - + (Fν ∝ ν α ) in the energy band 3–10 keV. From the NIR–optical data we obtain a PL slope αO = −0.24 ± 0.10 for the color index E(B − V ) = 0.03 mag. The slopes and fluxes of the NIR–optical and X-ray nonthermal spectra suggest that the NIR through X-ray emission can be described by the same PL and is generated by the same mechanism, unlike the pulsar’s γ-ray emission. The excess of the UV thermal component over the extension of the X-ray thermal component became smaller but did not disappear, indicating a nonuniformity of the bulk surface temperature. The NIR data also enable us to measure the proper motion accurately, with values μα = 47.5 ± 0.7 mas yr−1 and μδ = −8.7 ± 0.7 mas yr−1 .

B Posselt↗

Fast Single-Quantum Measurement with a Multi-Amplifier Sensing Charge-Coupled Device

A novel readout architecture that uses multiple non-destructive floating-gate amplifiers to achieve sub-electron readout noise in a thick, fully-depleted silicon detector is presented. This Multi-Amplifier Sensing Charge-Coupled Device (MAS-CCD) can perform multiple independent charge measurements with each amplifier; measurements with multiple amplifiers can then be combined to further reduce the readout noise. The readout speed of this detector scales roughly linearly with the number of amplifiers without requiring segmentation of the active area. The performance of this detector is demonstrated, emphasizing the ability to resolve individual quanta and the ability to combine measurements across amplifiers to reduce readout noise. The unprecedented low noise and fast readout of the MAS-CCD make it a unique technology for astronomical observations, quantum imaging, and low-energy interacting particles.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Estrategias de agua caliente para edificios comerciales: Una guia breve

Las calderas comerciales utilizan gas combustible o petroleo, y a veces electricidad, para producir agua caliente o vapor que se distribuye en un edificio para calefaccion de espacios y/o agua caliente sanitaria. Las calderas se encuentran en edificios de todos los tamanos, desde viviendas residenciales hasta grandes complejos comerciales y, en general, las calderas se vuelven menos eficientes y confiables con el tiempo. La vida util media de una caldera de gas es de 24 a 35 anos1 y, aunque la caldera continue funcionando, se debe planificar su reemplazo alrededor de los 15 a 20 anos de antiguedad o cuando aumentan las necesidades de mantenimiento. La lista de opciones de equipo para reemplazar calderas a gas esta creciendo, especialmente en lo que respecta a bombas de calor. Es fundamental evaluar las opciones para identificar la mejor solucion antes de su instalacion, antes de que sea necesario un reemplazo urgente. En muchos edificios existentes, el equipo se reemplaza con poca planificacion, lo que puede resultar en una operacion ineficiente, mayores costos y mantener al edificio en un ciclo de 25 anos de alto consumo energetico y emisiones. Al planificar un nuevo sistema de agua caliente, se deben considerar las emisiones de carbono, el consumo de energia, los costos y los cambios en las demandas del edificio para lograr un sistema optimo. Un enfoque colaborativo, integral e innovador puede resultar en un sistema mas limpio, energeticamente eficiente y rentable que cumpla con las necesidades de su instalacion y favorezca la disminucion de emisiones en el lugar. Este documento informativo asiste a propietarios y administradores de edificios en la planificacion del reemplazo de calderas, comprendiendo las opciones y encontrando las soluciones mas adecuadas para su situacion.

caldera↗

NMR investigation of proton transport in polybenzimidazole/polyphosphoric acid membranes prepared via novel synthesis route

Here, in this work, we present a molecular-level view of the structural changes in polybenzimidazole (PBI) membranes doped with phosphoric acid (PA) generated by a novel membrane fabrication technique. The modified PA doped membranes displayed unprecedented ionic conductivity at elevated temperatures, comparable to the starting PBI gel membranes prepared by the commonly used PPA process, while also exhibiting enhanced mechanical properties. To elucidate the cause of these effects, we used multi-nuclear ( 1 H, 13 C, 31 P) 1D PFG, MAS and CPMAS, and 2D HETCOR magnetic resonance (NMR) techniques to characterize the structure and dynamics of the modified film and the original gel PBI membranes. 1 H diffusivity measurements show significantly enhanced proton diffusivity, both in magnitude and in lower activation energy, which were consistent with its high ionic conductivity despite the lower PA content compared to the original gel membrane. CPMAS experiments further substantiated that the location of these distinct phosphate environments as being close to the polymer network. Finally, the phosphate groups in the modified membrane were revealed to be strongly bounded to each other and to the PBI polymer backbone in contrast to the combination of weakly and strongly bounded groups of the original gel membrane.

74 ATOMIC AND MOLECULAR PHYSICS↗

Cassini-Huygens maneuver automation for navigation

Many times during the Cassini-Huygens mission to Saturn, propulsive maneuvers must be spaced so closely together that there isn't enough time or workforce to execute the maneuver-related software manually, one subsystem at a time. Automation is required. Automating the maneuver design process has involved close cooperation between teams. We present the contribution from the Navigation system. In scope, this includes trajectory propagation and search, generation of ephemerides, general tasks such as email notification and file transfer, and presentation materials. The software has been used to help understand maneuver optimization results, Huygens probe delivery statistics, and Saturn ring-plane crossing geometry. The Maneuver Automation Software (MAS), developed for the Cassini-Huygens program enables frequent maneuvers by handling mundane tasks such as creation of deliverable files, file delivery, generation and transmission of email announcements, generation of presentation material and other supporting documentation. By hand, these tasks took up hours, if not days, of work for each maneuver. Automated, these tasks may be completed in under an hour. During the cruise trajectory the spacing of maneuvers was such that development of a maneuver design could span about a month, involving several other processes in addition to that described, above. Often, about the last five days of this process covered the generation of a final design using an updated orbit-determination estimate. To support the tour trajectory, the orbit determination data cut-off of five days before the maneuver needed to be reduced to approximately one day and the whole maneuver development process needed to be reduced to less than a week..

propulsion maneuvers↗

Unraveling the Molecular Origin of Prey-Wrapping Spider Silk's Unique Mechanical Properties and Assembly Process Using NMR

Prey wrapping spider silk's unique mechanical properties are investigated confirming the silk's high degree of extensibility and superior toughness compared to other types of spider silk. For the first time, the pre-spinning dope phase is studied in isotope-enriched intact aciniform (AC) silk glands using solution NMR that reveals a combination of α-helical domains linked by disordered random coil chains consistent with previously proposed “beads-on-a-string” models. The model is further refined through the AlphaFold2 protein structure prediction tool. Finally, extensive magic angle spinning (MAS) solid-state (SS) NMR data for isotopically-enriched fibers is used to refine the structural model for AC silk from two species, A. aurantia and A. argentata. The SSNMR data shows that the AC silk fibers are highly α-helical, coiled-coil in structure but, also exhibit significant β-sheet components that can be traced back to the Gly-rich disordered linker regions in the pre-spinning dope phase that are converted to β-sheet structures during fiber formation. This combination of mechanical and structural characterization enhances the understanding of AC silk's liquid-to-solid transition and structure-mechanics relationship. In conclusion, these prey wrap silk results and models will provide the basis for the design of biomimetic materials inspired by the AC spider silk system.

36 MATERIALS SCIENCE↗

Defying Thermodynamics: Stabilization of Alane Within Covalent Triazine Frameworks for Reversible Hydrogen Storage

The highly unfavorable thermodynamics of direct aluminum hydrogenation can be overcome by stabilizing alane within a nanoporous bipyridine-functionalized covalent triazine framework (AlH 3 @CTF-bipyridine). This material and the counterpart AlH 3 @CTF-biphenyl rapidly desorb H 2 between 95 and 154°C, with desorption complete at 250°C. Sieverts measurements, 27 Al MAS NMR and 27 Al{ 1 H} REDOR experiments, and computational spectroscopy reveal that AlH 3 @CTF-bipyridine dehydrogenation is reversible at 60°C under 700 bar hydrogen, >10 times lower pressure than that required to hydrogenate bulk aluminum. DFT calculations and EPR measurements support an unconventional mechanism whereby strong AlH 3 binding to bipyridine results in single-electron transfer to form AlH 2 (AlH 3 ) n clusters. Here the resulting size-dependent charge redistribution alters the dehydrogenation/rehydrogenation thermochemistry, suggesting a novel strategy to enable reversibility in high-capacity metal hydrides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A New Class of Oxyhalide Solid Electrolytes NaNbCl 6‐2x O x for Solid‐state Sodium Batteries

Abstract Sodium‐based batteries are gaining momentum due to the abundance and lower cost of sodium compared to lithium. Solid‐state sodium batteries can also provide further safety advantages. However, sodium‐based solid‐state electrolytes (SSEs) that meet all the rigorous requirements, such as high ionic conductivity, oxidative stability with the cathode, and ease of processability, are lacking. We present here a new class of sodium‐based oxyhalide electrolytes NaNbCl 6‐2x O x with a facile mechanochemical synthesis. The oxyhalide NaNbCl 4 O exhibits close to two orders of magnitude higher ambient‐temperature sodium‐ion conductivity (1.03×10 −4 S cm −1 ) compared to the halide counterpart NaNbCl 6 (3×10 −6 S cm −1 ). Structural motifs unique to the oxygen content in NaNbCl 6‐2x O x are identified with 23 Na and 93 Nb magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and x‐ray diffraction (XRD). Solid‐state sodium batteries assembled with NaNbCl 4 O electrolyte and the cobalt‐ and nickel‐free layered Na 0.70 Fe 0.3 Mn 0.65 Al 0.05 O 2 cathode exhibit a maximum discharge capacity of 155 mAh g −1 with good cycle life at ambient temperature.

Kmiec, Steven↗

Defying Thermodynamics: Stabilization of Alane Within Covalent Triazine Frameworks for Reversible Hydrogen Storage

Metastable metal hydrides such as AlH 3 have many attractive features as hydrogen storage media, but generally require complex reaction schemes for regeneration following H 2 release. Here in this paper, we demonstrate that the highly unfavorable thermodynamics of direct aluminum hydrogenation can be overcome by stabilizing alane within a nanoporous bipyridine-functionalized Covalent Triazine Framework (AlH 3 @CTF-bipyridine). This material and the counterpart AlH 3 @CTF-biphenyl rapidly desorb H 2 between 95 and 154 °C, with desorption complete at 250 °C. Sieverts measurements, 27 Al MAS NMR and 27 Al{ 1 H} REDOR experiments, and computational spectroscopy reveal that AlH 3 @CTF-bipyridine dehydrogenation is reversible at 60 °C under 700 bar hydrogen, >10 times lower pressure than that required to hydrogenate bulk aluminum. DFT calculations and EPR measurements support an unconventional mechanism whereby strong AlH 3 binding to bipyridine results in single-electron transfer to form AlH 2 (AlH 3 ) n clusters. The resulting size-dependent charge redistribution alters the dehydrogenation/rehydrogenation thermochemistry, suggesting a novel strategy to enable reversibility in high-capacity metal hydrides.

Coordination Chemistry↗

A New Class of Oxyhalide Solid Electrolytes NaNbCl 6‐2x O x for Solid‐state Sodium Batteries

Abstract Sodium‐based batteries are gaining momentum due to the abundance and lower cost of sodium compared to lithium. Solid‐state sodium batteries can also provide further safety advantages. However, sodium‐based solid‐state electrolytes (SSEs) that meet all the rigorous requirements, such as high ionic conductivity, oxidative stability with the cathode, and ease of processability, are lacking. We present here a new class of sodium‐based oxyhalide electrolytes NaNbCl 6‐2x O x with a facile mechanochemical synthesis. The oxyhalide NaNbCl 4 O exhibits close to two orders of magnitude higher ambient‐temperature sodium‐ion conductivity (1.03×10 −4 S cm −1 ) compared to the halide counterpart NaNbCl 6 (3×10 −6 S cm −1 ). Structural motifs unique to the oxygen content in NaNbCl 6‐2x O x are identified with 23 Na and 93 Nb magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and x‐ray diffraction (XRD). Solid‐state sodium batteries assembled with NaNbCl 4 O electrolyte and the cobalt‐ and nickel‐free layered Na 0.70 Fe 0.3 Mn 0.65 Al 0.05 O 2 cathode exhibit a maximum discharge capacity of 155 mAh g −1 with good cycle life at ambient temperature.

Kmiec, Steven↗

Mechanistic Insights into Adsorptive and Catalytic Reactions from Controllable Distributions of Metal Cations (Pd, Pt, Ni, Cr, Cu) as [M‐OH] +1 /1Al or M +2 /2Al in Zeolites

Anchoring divalent metal ions in the same zeolite framework with similar Si/Al ratio selectively as zeolite-bound M +2 or [M +2 -OH] +1 cationic species enables critical comparison of the species’ intrinsic reactivity for industrially and fundamentally relevant reactions. H-BEA zeolites with similar Si/Al ratios but differing framework Al siting were used to anchored multiple divalent metal cations (Ni, Pd, Pt, Cr, Cu) in the zeolite micropores. State-of-the-art infrared (IR) spectroscopy, electron paramagnetic resonance (EPR) measurements, including two-dimensional pulsed HYSCORE EPR, extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT) calculations together provide unambiguous evidence for the selective formation of divalent metal cations as M +2 /2Al species (for H-BEA prepared in the conventional hydroxide media), and [M +2 OH] +1 /1Al species for H-BEA prepared in HF. Solid-state proton-decoupled triple-quantum magic-angle spinning (3Q MAS) NMR measurements confirmed contrasting Al distributions in the two H-BEA zeolites, which led to a contrasting divalent cation speciation. The reactivities of the two cationic species were explored for catalytic and adsorptive applications in both organometallic homogeneous and heterogeneous catalysis. This work demonstrates their divergent reactivity in ethylene dimerization, ethylene oxidation (Wacker process), selective catalytic reduction (SCR) of NO, NO adsorption, and methane oxidation. Both M +2 /2Al and [M +2 OH] +1 /1Al cations are both active for ethylene dimerization, but [M +2 OH] +1 /1Al species show higher reaction rates for each Pd, Ni, Pt. [M +2 OH] +1 /1Al is active for acetaldehyde formation in Wacker ethylene oxidation. A new active site for ethylene oligomerization is proposed that possesses a terminal OH group (Cr-OH) in Phillips catalysts evident by a nearly inactive isolated Cr +2 /2Al species that contrast an active Cr─OH motif.

Divalent metal cations in a zeolite↗

Dual Chemical Looping/Catalytic Process for Alkylation of Benzene With Ethane and Propane Yielding Ethylbenzene and Cumene Over Copper‐Containing Mordenite

Given the sustained demand for alkylated aromatics and the strained olefin market, there is an urgent need to develop efficient one‐step processes for the direct alkylation of aromatics using alkanes instead of olefins. Such technologies offer greater energy efficiency and sustainability by eliminating the need for separate, energy‐intensive alkane dehydrogenation steps. In this work, we report a dual chemical looping / catalytic process that couples alkane dehydrogenation with aromatic alkylation over a copper‐containing mordenite yielding up to 25% of alkylated aromatics with >97% selectivity per cycle. In situ MAS NMR and FTIR spectroscopies combined with DFT calculations showed that the alkylation of benzene with alkanes proceeds via a π‐bounded Cu(I)‐olefin intermediate, which subsequently interacts with benzene, catalyzed by Brønsted acid sites, leading to alkylated products that readily desorb from the active material into the gas phase. DFT calculations show that alkylation mediated solely by Cu(I) has prohibitively high barriers (>1.8 eV), whereas a bi‐functional pathway involving both Cu(I) and Brønsted acid sites can proceed with significantly lower barrier (0.8 eV) through a concerted C–C bond formation and proton transfer step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elucidating the Reaction Pathways of Veratrylglycero-β-Guaiacyl Ether Degradation over Metal-Free Solid Acid Catalyst with Hydrogen

Efficient cleavage of β-O-4 bonds in lignin to high-yield aromatic compounds for the potential production of fuels and chemicals is vital for the economics of the modern biorefinery industry. This work is distinct in that a detailed mechanistic analysis of the reaction pathways of veratrylglycero-β-guaiacyl ether (VGE) catalyzed by transition-metal-free solid acid zeolite in aqueous conditions at high hydrogen pressure has been performed. VGE degradation produced high monomers yields (≈87 %), including guaiacol (48.2 %), 1-(3,4-dimethoxyphenyl)ethanol (10.3 %), 1-(3,4-dimethoxyphenyl)-2-propanol (6.1 %), 3,4-dimethoxyphenylpropanol (4.7 %), 3,4-dimethoxycinnamyl alcohol (4.1 %), and 1,2-dimethoxy-4-propylbenzene (2 %). The products were identified and confirmed by the in situ solid-state magic angle spinning (MAS) 13 C NMR spectroscopy in real-time conditions and the two-dimensional gas chromatography (GC×GC). A variety of products reveal the crucial role of hydrogen, water, and acid sites for heterolytic cleavage of the β-O-4 bond in VGE. Decarbonylation, hydrogenolysis, hydrogenation, and dehydration reaction pathways are proposed and further validated using first-principles calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Incorporation of rare earth elements $\text{Sc}$, $\text{Y}$ and $\text{La}$ into gibbsite

Rare earth elements (REE) are increasingly critical resources in technological applications, but the current understanding of their separation by uptake into minerals remains limited. We examined the adsorption and solubilization of scandium (Sc), yttrium (Y), and lanthanum (La) into aluminum hydroxide (gibbsite, Al(OH) 3 ). Based on spectroscopic investigations such as inductively coupled plasma-optical emission spectroscopy (ICP-OES) and time of flight-secondary ion mass spectrometry (ToF-SIMS), only Sc exhibited favorable incorporation and adsorption (0.66 and 0.06 atom%, respectively). Analysis of solid state 45 Sc magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR) indicated that Sc exhibits an octahedral coordination consistent with isolated substitutions for Al in the gibbsite structure, leading to a increase in lattice constants detectable by X-ray diffraction. Density functional theory (DFT) calculations reinforced this interpretation by reproducing the detected structural distortion as well as demonstrating the relatively favorable energetic basis for Sc incorporation into gibbsite by substitution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mineralogical and microstructural alterations in a portland cement paste after an accelerated decalcification process

Cement paste leaching and concomitant decalcification is a common cause of concrete structure deterioration. Such alterations entail microstructural changes that condition concrete durability. This study analysed those changes in cement pastes exposed to accelerated decalcification, layer-by-layer, from the surface in contact with the leaching agent, 6 M NH{sub 4}NO{sub 3,} to the unaltered area. The microstructural changes were analysed with BSEM, MIP and BET whilst the mineralogical and nanostructural alterations in each layer were assessed with XRD, FTIR, {sup 29}Si and {sup 27}Al MAS NMR and BSD. Decalcification affected not only portlandite and CSH gel, but also the anhydrous clinker and ettringite, inducing major micro- and nano-structural changes, particularly in the two layers closest to the leaching agent. CSH gel decalcification was more intense in the outer layers where long chain gels co-existed with silicon rich gels. BDS, in turn, revealed differences between the amount of bound water in the surface interfacing with the leaching agent and in the leaching front. More specifically, larger numbers of water molecules were tightly bound to silanol groups in the outer, whereas hydroxyl group distribution was more orderly in the inner layers.

36 MATERIALS SCIENCE↗

Temperature transformation of blended magnesium potassium phosphate cement binders

In this study, a multi-technique approach was utilised to determine the high temperature performance of magnesium potassium phosphate cement (MKPC) blended with fly ash (FA) or ground granulated blast furnace slag (GBFS) with respect to nuclear waste immobilisation applications. Conceptual fire conditions were employed (up to 1200 °C, 30 min) to simulate scenarios that could occur during interim storage, transportation or within a final geological disposal facility. After exposure up to 400 °C, the main crystalline phase, struvite-K (MgKPO{sub 4}·6H{sub 2}O), was dehydrated to poorly crystalline MgKPO{sub 4} (with corresponding volumetric and mass changes), with MgKPO{sub 4} recrystallisation achieved by 800 °C. XRD and SEM/EDX analysis revealed reaction occurred between the MgKPO{sub 4} and FA/GBFS components after exposure to 1000–1200 °C, with the formation of potassium aluminosilicate phases, leucite and kalsilite (KAlSi{sub 2}O{sub 6} and KAlSiO{sub 4}), commensurate with a reduced relative intensity (or complete elimination) of the dehydrated struvite-K phase, MgKPO{sub 4.} This was further supported by solid-state NMR ({sup 27}Al and {sup 29}Si MAS), where only residual features associated with the raw FA/GBFS components were observable at 1200 °C. The high temperature phase transformation of blended MKPC binders resulted in the development of a glass/ceramic matrix with all existing porosity infilled via sintering and the formation of a vitreous phase, whilst the physical integrity was retained (no cracking or spalling). This study demonstrates that, based on small-scaled specimens, blended MKPC binders should perform satisfactorily under fire performance parameters relevant to the operation of a geological disposal facility, up to at least 1200 °C.

36 MATERIALS SCIENCE↗