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At least 1,441 records · Page 80

Detection of surface glow related to spacecraft glow phenomena

A source of low energy neutral atoms and molecules has been developed by using a biased limiter to scrape off and reflect neutralized ions from a toroidal plasma. Beams of nitrogen and nitrogen-oxygen mixtures with energies of 1 to 15 eV and fluxes greater than about 10 to the 14 per centimeter per second were directed onto target surfaces consisting of Z-302 and Z-306 paints. With the nitrogen beams, a glow due to beam-surface interactions was successfully detected. In addition, a volume glow effect due to beam-gas interactions was observed which may play a role in spacecraft glow.

Langer, W. D.↗

The Liquid Jet Endstation for Hard X-ray Scattering and Spectroscopy at the Linac Coherent Light Source

The ability to study chemical dynamics on ultrafast timescales has greatly advanced with the introduction of X-ray free electron lasers (XFELs) providing short pulses of intense X-rays tailored to probe atomic structure and electronic configuration. Fully exploiting the full potential of XFELs requires specialized experimental endstations along with the development of techniques and methods to successfully carry out experiments. The liquid jet endstation (LJE) at the Linac Coherent Light Source (LCLS) has been developed to study photochemistry and biochemistry in solution systems using a combination of X-ray solution scattering (XSS), X-ray absorption spectroscopy (XAS), and X-ray emission spectroscopy (XES). The pump–probe setup utilizes an optical laser to excite the sample, which is subsequently probed by a hard X-ray pulse to resolve structural and electronic dynamics at their intrinsic femtosecond timescales. The LJE ensures reliable sample delivery to the X-ray interaction point via various liquid jets, enabling rapid replenishment of thin samples with millimolar concentrations and low sample volumes at the 120 Hz repetition rate of the LCLS beam. This paper provides a detailed description of the LJE design and of the techniques it enables, with an emphasis on the diagnostics required for real-time monitoring of the liquid jet and on the spatiotemporal overlap methods used to optimize the signal. Additionally, various scientific examples are discussed, highlighting the versatility of the LJE.

EXAFS↗

Scientific Assessment of Stratospheric Ozone: 1989, volume 2. Appendix: AFEAS Report

The results are presented of the Alternative Fluorocarbon Environmental Acceptability Study (AFEAS), which was organized to evaluate the potential effects on the environment of alternate compounds targeted to replace fully halogenated chlorofluorocarbons (CFCs). All relevant current scientific information to determine the environmental acceptability of the alternative fluorocarbons. Special emphasis was placed on: the potential of the compounds to affect stratospheric ozone; their potential to affect tropospheric ozone; their potential to contribute to model calculated global warming; the atmospheric degradation mechanisms of the compounds, in order to identify their products; and the potential environmental effects of the decomposition products. The alternative compounds to be studied were hydrofluorocarbons (HFCs) with one or two carbon atoms and one or more each of fluorine and hydrogen.

Source record↗

The Role of Liquid Ink Transport in the Direct Placement of Quantum Dot Emitters onto Sub-Micrometer Antennas by Dip-Pen Nanolithography

Here, dip-pen nanolithography (DPN) is used to precisely position core/thick-shell (“giant”) quantum dots (gQDs; ≥10 nm in diameter) exclusively on top of silicon nanodisk antennas (≈500 nm diameter pillars with a height of ≈200 nm), resulting in periodic arrays of hybrid nanostructures and demonstrating a facile integration strategy toward next-generation quantum light sources. A three-step reading-inking-writing approach is employed, where atomic force microscopy (AFM) images of the pre-patterned substrate topography are used as maps to direct accurate placement of nanocrystals. The DPN “ink” comprises gQDs suspended in a non-aqueous carrier solvent, o-dichlorobenzene. Systematic analyses of factors influencing deposition rate for this non-conventional DPN ink are described for flat substrates and used to establish the conditions required to achieve small (sub-500 nm) feature sizes, namely: dwell time, ink-substrate contact angle and ink volume. Finally, it is shown that the rate of solvent transport controls the feature size in which gQDs are found on the substrate, but also that the number and consistency of nanocrystals deposited depends on the stability of the gQD suspension. In conclusion, the results lay the groundwork for expanded use of nanocrystal liquid inks and DPN for fabrication of multi-component nanostructures that are challenging to create using traditional lithographic techniques.

36 MATERIALS SCIENCE↗

Energetics of cobalt alloys and compounds and solute–vacancy binding in fcc cobalt: A first-principles database

Using extensive first-principles density functional calculations, we calculate thermodynamic properties of binary fcc cobalt-based alloys with 25 different solute elements. For each solute element X, we calculate its (a) nearest- and next-nearest-neighbor solute–vacancy binding energy, (b) dilute impurity mixing energy with respect to the equilibrium and hypothetical fcc-based reference states of the solute, (c) enthalpy of formation of cobalt-rich binary ordered compounds in the Co–X system, (d) solubility enthalpy, and other derived quantities. Here, we find that the solute–vacancy binding energies of all the studied solutes in fcc cobalt are positive (indicating favorable binding), in contrast to nickel, aluminum, magnesium, and copper-based alloys, where mid 3d transition metal solutes have unfavorable solute–vacancy binding. We study the physical and chemical effects influencing solute–vacancy binding energy, and find that (a) it correlates broadly with solute size—larger solute atoms possess stronger binding with vacancies—and this is understood in terms of strain relief and secondary next-nearest-neighbor interactions, and (b) it follows a parabolic trend as a function of d-occupancy across the transition metal series—falling to a minimum at the middle of the series—and this is understood in terms of a d-band filling effect. We also find this d-band filling effect in other calculated quantities such as the dilute impurity volumes and dilute impurity mixing energies. To aid in building thermodynamic databases, we tabulate all the calculated thermodynamic quantities, and compare them with experimental phase diagrams data and previous literature, and find good agreement where such data is available.

36 MATERIALS SCIENCE↗

Comparing and contrasting In-Vial and full-scale systems for sparging volatile analytes

Here, in-vial sparging was demonstrated as an effective, practical alternative to a full-scale sparging system for supporting the analysis of volatile constituents. Using elemental mercury (Hg 0 ) and toluene as representative purgeable analytes, the mass removal for various sparge configurations was measured and a reduced order model was developed and validated. In the primary experiments, Hg 0 in the sparge gas was trapped on activated carbon or gold, thermally desorbed, and quantified using atomic absorption or atomic fluorescence spectroscopy. Toluene experiments using the same in-vial sparge apparatus and sparge parameters were performed to demonstrate the applicability of the reduced order model to a broad range of compounds. Toluene removal was tracked by measuring the remaining toluene in sparged aliquots using Ultraviolet-visible (UV–Vis) spectroscopy. For the sparging, flow rates varied from 25 to 75 mL/min for periods from 0 to 30 min. Sparge performance, mass removal as a function of time, and sparge gas volume were measured for both in-vial and full-scale systems. A model based on dimensionless Henry's Law coefficient, normalized sparge gas volume, and fractional extent of equilibrium matched the experimental data for both compounds and provides a practical tool for future applications. For the conditions tested in this study, the calibrated model indicated that the sparge gas in the in-vial system reached approximately 33% of its equilibrium value before exiting the water surface, while a full-scale system reached approximately 100%. The tests validated the quality, reproducibility, and predictability of sparging performance for both full scale and in-vial sparge systems. Related factors such as waste generation, worker risk, and labor were also assessed. Full scale sparge systems provide the advantage of lower detection levels due to larger sample volume, while the in-vial sparge systems provide advantages for most other factors; including automatability, reducing secondary wastes, lessening the need to clean and check the sparge apparatus, and lowering labor and costs. The data and associated reduced order model support continued development and deployment of in-vial sparge platforms as a practical option for analysis of purgeable analytes such as volatile organic compounds and volatile metals/organometallics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and dynamics in liquid bismuth and Bi{sub n} clusters: A density functional study

Density functional/molecular dynamics simulations with more than 500 atoms have been performed on liquid bismuth at 573, 773, 923, and 1023 K and on neutral Bi clusters with up to 14 atoms. There are similar structural patterns (coordination numbers, bond angles, and ring patterns) in the liquid and the clusters, with significant differences from the rhombohedral crystalline form. We study the details of the structure (structure factor, pair, and cavity distribution functions) and dynamical properties (vibration frequencies, diffusion constants, power spectra), and compare with experimental results where available. While the three short covalent bonds typical to pnictogens are characteristic in both liquid and clusters, the number of large voids and the total cavity volume is much larger in the liquid at 1023 K, with larger local concentration variations. The inclusion of spin-orbit coupling results in a lowering of the cohesive energies in Bi{sub n} clusters of 0.3–0.5 eV/atom.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solar-pumped gas laser development

The direct conversion of solar radiation into an inverted population for extraction in an optical cavity holds promise as a relatively simple system design. Broad-band photoabsorption in the visible or near-UV range is required to excite large volumes of gas and to ensure good solar absorption efficiency. The state excited must be a metastable state which is not quenched by the parent gas. The emission bandwidth must be less than approximately 10 A. The system should show chemical reversibility and an insensitivity to increasing temperature. Other properties such as good quantum efficiency and kinetic efficiency are also implied. A search of electronic-vibrational transitions in diatomic molecules satisfying these conditions is now in progress. A photodissociation-pumped atomic iodine laser is now being tested under solar pumping conditions. Photodissociation studies for thallium spin-flip metastable formation will begin in the near future.

Wilson, J. W.↗

In-Lab Rapid Analytical Detection of Lunar Volatiles By Universal Gas Analyzer With Comparison to GC-MS System

Introduction: The curation of permanently shadowed regions (PSRs) [1] on the lunar surface is centered around studies based upon the observed volatiles from the LCROSS mission [2]. The rapid detection of important volatile gases and vapors present in planetary bodies and Astromaterials by a standalone analytical device is an area of intense research interest in our group and Planetary Exploration & Astromaterials Research Laboratory (PEARL) facility and this work is relevant to the future preparation of viable lunar simulants for testing curation efforts down the road. The groundbreaking results obtained from the LCROSS Mission [2] open the requirements for the direct detection of volatiles present in regolith materials collected from the lunar surface. The mass spectrometry of volatile chemicals is a general technique that utilizes a set of instruments that creates charged ions from a gaseous chemical species and measures the intensities vs. mass-to-charge ratio (m/z) [3]. In this context, we discuss in-lab experimental results and procedures for rapid qualitative analysis of main LCROSS volatiles (water, H2S, NH3, CO2, and CH3OH) by a Universal Gas Analyzer (UGA) instrument. Additionally, the instrument performance was evaluated by measuring the isotopic abundance ratio of atmospheric Ar-40 to Ar-36 present in room air since, argon is a relevant gas in planetary studies as it can provide an insight and reference point to isotope studies [4]. Additional, cross comparisons were attempted and made between the two instruments to develop a robust analytical technique by comparing mass spectral data for H2S headspace samples with a Trace-1310/ ISQ 7000 (ThermoFisher Scientific.) GC-MS system. Background: The benchtop UGA System is equipped with an SRS UGA 300 quadrupole mass spectrometer designed and built by Stanford Research Systems [5]. This system can be configured for several types of gaseous chemical analysis. The inlet line continuously samples gases at low flow rates (several milliliters per minute) through a capillary limiting the intake pressure making the instrument ideal for online analysis of select gases and/or room atmosphere. Moreover, in our current UGA system, a change in composition at the inlet can be detected in about 200 milliseconds and a complete spectrum is acquired (for a range of 1-100 amu) in under 45 sec with masses measured at rates up to 25 msec per point [5]. This system provides a quick upstream analytical data that we can then compare to results obtained by our GC-MS system. Sample Preparation: Small volume (2-4 mL) of analyte sample was taken in a 10 mL glass vial and sealed with a crimped cap and purged with pure Ar or N2 gas to displace air from the top. The headspace sample was scanned by the UGA instrument at analog, histogram, and pressure vs. time modes. The isotopic abundance ratio for 40Ar-to-36Ar was estimated by measuring partial pressure vs. time scans and setting the mass at 40 and 36 respectively. Results and Discussions: In this work, we have investigated the applicability of the UGA system by qualitative analysis of a series of LCROSS volatiles measured individually. Fig. 1 demonstrates a set of vertically offset spectra for the partial pressures measured as a function of mass-to-charge (m/z) ratios. The average acquisition time for each spectrum was less than a minute suggesting that the UGA system is ideal for quick analysis of geochemical volatiles. For the cross-comparison, we analyzed an H2S headspace sample by a Trace-1310/ISQ-7000 system and compared mass spectral data with previously measured UGA histogram scan data (Fig. 2). In both cases, major peak positions are the same, however, the intensities of fragment ions ([1H132S]+ and [32S]+) are higher for UGA suggesting that the fragment ionization process is stronger in UGA compared to that of GC-MS. To investigate how the integrated area under each chromatogram varies with the headspace sample volume, a set of five H2S headspace samples with increasing volumes was analyzed by the GC-MS system (Fig. 3, inset). A small volume (e.g., 200 to 1000 µL) of H2S/H2O vapor was withdrawn from a 20 mL stock sample vial containing ~5 mL of 0.4% H2S in water by a gas-tight syringe and added to another 20 mL vial filled with argon and analyzed by the GC-MS system. Finally, the UGA detector sensitivity was evaluated by calculating the atmospheric 40Ar-to-36Ar isotopic abundance ratio in room air by running a partial pressure vs. time scan with setting the atomic mass at 40, and 36. Fig. 4(a) shows a ~25 min duration “P vs. time” scan for 40Ar (plot for 36Ar is not shown). The partial pressure values (~100 points) were corrected by subtracting the corresponding background pressure value for 37Ar and utilized to calculate 40Ar-to-36Ar isotopic abundance ratios as shown by Fig. 4b. The average isotopic abundance ratio is ~306 with a 2*STDEV ~13. This abundance ratio is significantly close to the previously reported value of 298.56 [6] and the ratio obtained by our GC-MS system (303 for a UHP grade Ar sample). Conclusions: Our study strongly evidenced that the benchtop UGA system is a valuable analytical tool for the detection of major LCROSS volatiles. The rapid scanning capability, the inexpensiveness of the whole system, and impressive detection sensitivity prove its worthiness as an essential device for advanced geochemical applications. Moreover, cross comparisons with the GC-MS provide important bridges into advanced curatorial efforts into the future. References: [1] Bickel, V.T., et al. (2021) Nat Commun 12, 5607. [2] Colaprete, A., et al. (2010) Science, 330, 463-468. [3] Glavin, D. P. et al. (2012) 2012 IEEE Aerospace Conference, 1-11. [4] Willett, C. D., et al. (2022) Geochimica et Cosmochimica Acta 329, 119-134. [5] Operation Manual and Programming Reference. (2018) Universal gas Analyzers, Stanford Research Systems. [6] Lee, J. Y., et al. (2006) Geochimica et Cosmochimica Acta 70, 4507–4512. Notes: (4 figures are attached with text as shown by the attached file)

Curation↗

Phase assemblage of composite cements

The phase assemblage of binary Portland cements with 45 wt% replacement by calcareous fly ash and slag has been investigated by experiment, mass balance and thermodynamic simulations. The input for these calculations was based on clinker reaction measured by XRD-Rietveld refinement, on SCM reaction measured by SEM-EDS full element mapping and on C-S-H composition by SEM-EDS point analyses. A sensitivity analysis estimates the uncertainty of determination of phase volume as at best ± 2 cm{sup 3}/100 cm{sup 3}, and thus of rather semi-quantitative character. The differences between experiment and calculations regarding AFt/AFm, C-S-H and portlandite were assessed. Gel/space ratios computed using the volumes of all hydrates showed a clear correlation to compressive strength, which was unaffected by the mix composition. This suggests that the type of hydrates formed has little or no influence on the compressive strength and that the key factor is the space filling.

36 MATERIALS SCIENCE↗

Replacement of tritiated water from irradiated fuel storage bay

Recently, AECL developed a novel method to reduce tritium emissions (to groundwater) and personnel doses at the NRU (National Research Universal) reactor irradiated fuel storage bay (also known as rod or spent fuel bay) through a water swap process. The light water in the fuel bay had built up tritium that had been transferred from the heavy water moderator through normal fuel transfers. The major advantage of the thermal stratification method was that a very effective tritium reduction could be achieved by swapping a minimal volume of bay water and warm tritiated water would be skimmed off the bay surface. A demonstration of the method was done that involved Computational Fluid Dynamics (CFD) modeling of the swap process and a test program that showed excellent agreement with model prediction for the effective removal of almost all the tritium with a minimal water volume. Building on the successful demonstration, AECL fabricated, installed, commissioned and operated a full-scale system to perform a water swap. This full-scale water swap operation achieved a tritium removal efficiency of about 96%.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Multifunctional UV and Gas Sensors Based on Vertically Nanostructured Zinc Oxide: Volume Versus Surface Effect

This article reports that it is possible to make multifunctional sensing devices with ZnO infiltrated polymers while the sensing interactions could occur throughout the polymer. As such, we find that infiltrated devices with SU-8 polymer can result in highly sensitive UV sensors. Mesh dielectric core devices were found to make sensitive gas sensors with a better than 5 ppm sensitivity for formaldehyde and NO2. A new type of p-n junction device is further demonstrated that is sensitive to UV illumination, thus making it an enhanced UV sensor. Sensing devices relying on volume interactions, such as light absorption, can significantly benefit from the infiltrated polymer. In contrast, devices that rely on surface interactions, such as gas sensors, do not gain performance in any significant way with or without the infiltrated polymer.

47 OTHER INSTRUMENTATION↗

Superlattice-Structured Films by Magnetron Sputtering as New Era Electrodes for Advanced Lithium-ion Batteries

Sustaining sound structures in Si-based anodes is extremely challenging because of the high volumetric expansion that occurs upon cycling. To maintain high capacities over cycles, new designs rely on engineering-specific hierarchical geometries and/or optimized composite compositions such that at least one of the multiple elements serves as buffer and/or electron conductive pathways in the electrodes. In this paper, we report an innovative design in which alternating layers of periodic atomic structures involving multiple elements form a new anode material for lithium-ion batteries. In this work, a superlattice-structured amorphous film made using Si, Mo, and Cu is fabricated by a simple and scalable magnetron sputtering process for the first time. This continuous and repetitive superlattice formation along the film thickness provides a homogeneous stress-strain distribution. The Mo-Cu layer in the superlattice acts as an inactive-conductive layer and as a backbone to handle the volume expansion of active Si upon cycling. This nano-functional superlattice approach enables harnessing the high energy density of Si while maintaining its structural stability. As a result, the electrode exhibits high specific capacity and capacity retention even at high cycling rates. The possible use of the film in a full cell is also evaluated by cycling it vs. the LiMn 1.5 Ni 0.5 O 4 cathode. The full cell maintains a stable capacity of about 900 mAh g anode -1 over 150 cycles, at ~600 mA g -1 rate. The remarkable performance of this nano-functional superlattice film is found to be promising as anodes for applications that require high energy, long calendar life, and excellent abuse tolerance such as electric vehicle batteries.

25 ENERGY STORAGE↗

Understanding the Polymorphism of A 4 [(UO 2 ) 3 (PO 4 ) 2 O 2 ] (A = Alkali Metals) Uranyl Phosphate Framework Structures

In this study we combine experimental synthesis and density functional theory (DFT) calculations to gain insight into the polymorphism of A 4 [(UO 2 ) 3 (PO 4 ) 2 O 2 ] (A = Na, K, Rb, Cs) uranyl phosphate structures. Single crystals of a new 3D uranyl phosphate, Cs 4 [(UO 2 ) 3 (PO 4 ) 2 O 2 ], were grown by molten flux methods using a CsCl flux. DFT calculations, using the DFT+U method, were carried out to study the difference between this new 3D uranyl phosphate and a family of recently described layered uranyl phosphates. Variation of the computed properties with changes in Ueff values are also studied. The DFT results agree with the experimental observations, showing that the Cs-containing 3D polymorph and the K-containing layered polymorphs are more stable than their respective layered and 3D polymorph. We show an increase in the difference between the total energies of the layered and 3D polymorphs and an increase in the band gaps with increasing $U_{eff}$ value. Volume-based thermodynamics was also applied to calculate the total energies of the different polymorphs, showing consistently higher stability of the layered polymorphs compared to the 3D polymorphs. For each of the studied polymorphs, we calculated the electronic, optical, and bonding properties. We also show an anisotropy in the absorption indexes along the three crystallographic directions of the polymorphs, which is especially noticeable in the layered polymorphs. We attribute the difference in the density of states to the different coordination of the U atoms in the layered and 3D polymorphs. We attribute the preferred formation of the 3D Cs polymorph to the substantial increase in the U–A bond strength, which is more pronounced than the differences in the bond strength between structures for other atomic pairs.

36 MATERIALS SCIENCE↗

A global model of the self-pulsing regime of micro-hollow cathode discharges

A global (volume-averaged) model of the self-pulsing regime of micro-hollow cathode discharges working in argon gas is proposed. The power balance is done using an equivalent circuit model of the discharge that allows the current and voltage dynamics to be calculated. The fraction of the total power dissipated in the discharge that contributes to electron heating is deduced from a sheath model previously described. The particle balance is first done in a very simplified reaction scheme involving only electrons, argon atomic ions, and argon molecular ions. In a second step, the excited states (the metastable state Ar*({sup 3}P{sub 2}) and the resonant state Ar*({sup 3}P{sub 1})) are included in the particle balance equations. The models are compared to experiments and several conclusions are drawn. The model without excited states underestimates the electron density and does not capture well the trends in pressure. The model with the excited states is in better agreement which shows that multi-step ionization plays a significant role. The time-evolution of the electron density follows closely that of the discharge current but the excited states density presents two peaks: (i) the first at the early stage of the current peak due to direct excitation with high electron temperature, (ii) the second at the end of the current (and electron density) peak due to large production of excited states by electron-ion recombination at very low electron temperature.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Calibration of Traceable Solid Mock 131 I Phantoms Used in an International SPECT Image Quantification Comparison

The International Atomic Energy Agency (IAEA) has organized an international comparison to assess Single Photon Emission Computed Tomography (SPECT) image quantification capabilities in 12 countries. Iodine-131 was chosen as the radionuclide for the comparison because of its wide use around the world, but for logistical reasons solid 133 Ba sources were used as a long-lived surrogate for 131 I. For this study, we designed a set of solid cylindrical sources so that each site could have a set of phantoms (having nominal volumes of 2 mL, 4 mL, 6 mL, and 23 mL) with traceable activity calibrations so that the results could be properly compared. We also developed a technique using two different detection methods for individually calibrating the sources for 133 Ba activity based on a National standard. This methodology allows for the activity calibration of each 133 Ba source with a standard uncertainty on the activity of 1.4 % for the high-level 2-, 4-, and 6-mL sources and 1.7 % for the lower-level 23 mL cylinders. This level of uncertainty allows for these sources to be used for the intended comparison exercise, as well as in other SPECT image quantification studies.

47 OTHER INSTRUMENTATION↗

Probing long-range ordering in nickel-base alloys with proton irradiation

In this paper, twelve commercial-grade austenitic alloys based on the Ni-Cr-Mo-Fe quaternary system were irradiated using 2 MeV protons at 360 °C to a damage level of 2.5 displacements per atom (dpa). Long-range ordered (Pt 2 Mo-type) precipitation under proton irradiation was observed, for the first time, in alloys C22, 625, 625P, 625D, 725, and 690. No relevant short-range ordering was observed. These irradiation-enhanced long-range ordered precipitates are coherent with the matrix despite their irregular shape. Of the potential influences on long-range ordering (Ni:Cr, and Ni:(Cr + Mo) ratios, Mo, and iron concentration), Fe content was the strongest by far. The volume fraction of LRO decreases with increasing Fe content by virtue of its role as a stabilizer of the disordered FCC phase, thus reducing the energy savings from ordering. The observed effects of Fe on long-range ordering show qualitative agreement with predictions from thermodynamic modeling. Although solid state diffusion kinetics dominate long-range ordering under purely thermal conditions, ordering under irradiation here (~ 2.5dpa) is controlled by the thermodynamic driving force. Finally, proton irradiation thus offers a unique approach for studying the low temperature phase transformation in a thermodynamically favored, but kinetically constrained condition.

36 MATERIALS SCIENCE↗