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At least 37 records · Page 2

Mesospheric dynamics and chemistry from SME data

A fast Curtis matrix calculation of cooling rates due to the 15 micron band of CO2 is modified to parameterize the detailed calculations by Dickinson (1984) of infrared cooling by CO2 in the mesosphere and lower thermosphere. The calculations included separate NLTE treatment of the different 15 micron bands likely to be important for cooling. The goal was to compress the detailed properties of the different bands into a modified Curtis matrix, which represents one composite band with appropriate averaged radiative properties to allow for a simple and quick calculation of cooling rates given a temperature profile. Vertical constituent transport in the mesosphere was also studied.

Strobel, Darrell F.↗

Preliminary Sizings for an Integrated SME Actuator System for the STAR system

The Star configuration consists of three legs of an aperature of total diameter of 2.5 m diameter. For the purposes of this initial study for actuator requirements, several assumptions were made. For support, we assumed that the membrane was Upilex of a thickness of 0.010 in. thick, and with a modulus of approximately YYY. Upilex was chosen as being relatively commercially available and is compatible with either TiNi or AuCd manufacture. We confined the areas in which we could apply actuators to three strips of length 2.5 meters and width of 0.1 m. This brings the problem to a solution of a strip.

Jardine, A. Peter↗

Antifoam Development for Eliminating Flammability Hazards and Decreasing Cycle Time in the Defense Waste Processing Facility

The Savannah River National Laboratory (SRNL) was requested to develop a new antifoam control method for the Defense Waste Processing Facility’s (DWPF) Chemical Process Cell (CPC). SRNL completed testing of both chemical and nonchemical foam controls. The nonchemical foam controls were either ineffective (or worse, created more foam) or impractical (a water spray can control foam, but excessive water is needed). As a result, the focus of this study was on finding a superwetter or commercial antifoam for controlling foam. Thirty potential antifoams were tested as part of this study. A series of tests were developed to help screen out ineffective alternatives including: 1. Spreading testing of superspreaders, 2. Foam column testing with physical simulants, 3. Boiling testing with physical and chemical simulants, 4. Days-only Sludge Receipt and Adjustment Tank (SRAT) process simulations with sludge (containing noble metals and mercury), Precipitate Reactor Feed Tank (PRFT), and Slurry Mix Evaporator Feed Tank (SEFT) simulants in the RC1 Reaction Calorimeter (purchased for antifoam testing), and 5. Around-the-clock SRAT and Slurry Mix Evaporator (SME) process simulations with sludge(containing noble metals and mercury), PRFT, and SEFT simulants in the RC1 Reaction Calorimeter. Evonik Surfynol® MD20, a commercially available defoamer, was relatively effective in controlling foam, while remaining chemically stable in SRAT and SME processing across the pH range of 4 to 13. No degradation products were detected in the offgas, in the condensate or in the SRAT and SME products. In nitric-glycolic acid flowsheet testing, 250 mg/kg Evonik Surfynol® MD20 was needed for foam control compared to 1,625 mg/kg for Antifoam 747, DWPF’s current antifoam. In nitric-formic acid flowsheet testing, 1,125 mg/kg of Evonik Surfynol® MD20 was needed to control foam throughout the SRAT and SME cycles. The commercially available superspreader Momentive™ Y-17112 was even more effective than Evonik Surfynol® MD20 as both a defoamer and an antifoam. Not only was the foam destroyed upon addition but also was less persistent between additions. It was the most effective antifoam in testing using both the nitric-glycolic acid flowsheet and the nitric-formic acid flowsheet. In nitric-glycolic acid flowsheet testing, only 100 mg/kg Momentive™ Y-17112 was needed to control foam throughout the SRAT and SME cycles. In nitric-formic acid flowsheet testing, 300 mg/kg Momentive™ Y-17112 was needed to control foam throughout the SRAT and SME cycles. Momentive™ Y-17112 is also resistant to hydrolysis as demonstrated by its chemical stability in SRAT and SME processing across the pH range of 4 to 13 and lack of degradation products in offgas or condensate. Both candidates were effective as potential replacements for Antifoam 747, with Y-17112 demonstrating superior foam control. During nitric-glycolic flowsheet testing 50% less antifoam was needed when using Momentive™ Y-17112 compared to MD20. During nitric-formic flowsheet testing 75% less antifoam was needed when using Momentive™ Y-17112 compared to MD20. Foam remediated with Momentive™ Y-17112 was less persistent throughout testing. In addition, no degradation products were detected in the offgas, in the condensate or in the SRAT and SME products. Based on this testing, Momentive™ Y-17112 is clearly superior to Evonik Surfynol® MD20 and Antifoam 747, especially for the nitric-formic acid flowsheet processing; it is recommended that Momentive™ Y-17112 replace Antifoam 747 in DWPF. An antifoam addition strategy is recommended for both the nitric-glycolic acid flowsheet and the nitric-formic acid flowsheet. Implementation of Momentive™ Y-17112 is expected to decrease SRAT and SME boiling times by up to 50%, eliminate the issues resulting from Antifoam 747 degradation products, and minimize foamovers. To validate the effectiveness of these defoaming agents, SRNL recommends irradiation of a SRAT or SME product simulant containing fresh antifoam. The goal of this testing is to determine whether the irradiation causes decomposition of the antifoam that would make it less effective or produce new species in the offgas or slurry. This testing began in April 2020. An evaluation should be completed to determine the thermolytic hydrogen and methane generation rate in downstream equipment, including the High-Level Waste evaporators.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

M-Star® Software Test and Verification for Impeller Mixing in a Tank

Before a sample of the Slurry Mix Evaporator (SME) can be taken, the SME product sampling procedure requires that the agitator power be stable between 20 and 30 kW for at least one hour. The SME transfer to Melter Feed Tank (MFT) procedure also requires the SME agitator power be stabilized between 20 and 30 kW prior to transfer. These requirements are specified to ensure samples are homogeneous, as discussed in the Waste Form Qualification Report. During SME Batch 804, the agitator power dropped to 19 kW and struggled to achieve and maintain 20 kW. It was later discovered that the cause of the power drop was due to one of the bottom blades of the agitator breaking off. Both the sample and the transfer occurred without the power stabilizing between 20 and 30 kW. Therefore, the quality of SME Batch 804 is indeterminate, and homogeneity was questionable.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Rapid Electron Transfer Self-Exchange in Conformationally Dynamic Copper Coordination Complexes

Here we report the electron transfer (ET) self-exchange rate constants (k 11 ) for a pair of Cu II/I complexes utilizing dpa R (dpa = dipicolylaniline, R = OMe, SMe) ligands assessed by NMR line-broadening experiments. These ligands afford copper complexes that are conformationally dynamic in one oxidation state. With R = OMe, the Cu I complex is dynamic, while with R= SMe, the Cu II complex is dynamic. Both complexes exhibit unexpectedly large k 11 of 2.48(6) x 10 5 and 2.21(9) × 10 6 M –1 s –1 for [CuCl(dpa OMe )] +/0 and [CuCl(dpa SMe )] +/0 , respectively. Among the fastest reported for molecular copper coordination complexes to date, that of [CuCl(dpa SMe )] +/0 exceeds all others by an order of magnitude and compares only to those observed in type 1 blue copper proteins. The dynamicity of these complexes establish pre-steady-state con-formational equilibria that minimize the inner sphere reorganization energies to 0.71 and 0.62 eV for R = OMe and SMe, respectively. In contrast to the emphasis on rigidity in the formulation of entatic states applied to blue copper proteins, the success of these two systems highlight the relevance of conformational dynamicity in mediating rapid ET.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Supplemental knowledge acquisition through external product interface for CLIPS

Traditionally, the acquisition of knowledge for expert systems consisted of the interview process with the domain or subject matter expert (SME), observation of domain environment, and information gathering and research which constituted a direct form of knowledge acquisition (KA). The knowledge engineer would be responsible for accumulating pertinent information and/or knowledge from the SME(s) for input into the appropriate expert system development tool. The direct KA process may (or may not) have included forms of data or documentation to incorporate from the SME's surroundings. The differentiation between direct KA and supplemental KA (indirect) would be the difference in the use of data. In acquiring supplemental knowledge, the knowledge engineer would access other types of evidence (manuals, documents, data files, spreadsheets, etc.) that would support the reasoning or premises of the SME. When an expert makes a decision in a particular task, one tool that may have been used to justify a recommendation, would have been a spreadsheet total or column figure. Locating specific decision points from that data within the SME's framework would constitute supplemental KA. Data used for a specific purpose in one system or environment would be used as supplemental knowledge for another, specifically a CLIPS project.

Saito, Tim↗

Satellite Metallicity Enhancement I: Suppressed Star Formation, Stellar Mass Loss, and Enriched Inflow of DESI and EAGLE Galaxies around Massive Clusters

Environmental effects are a primary driver of elevated gas-phase metallicities in galaxies around massive clusters, but the underlying physical mechanisms for this satellite metallicity enhancement (SME) are still unclear. Using the Dark Energy Spectroscopic Instrument (DESI) Data Release 1, we present the first measurement of the average SME as a function of projected cluster-centric distance. The resulting profile reveals three distinct regimes: a steep decline from the cluster center, a plateau near the cluster boundary, and an extended downturn across several cluster radii. Remarkably, the complex shape and amplitude of this observed SME profile are successfully reproduced in the EAGLE cosmological simulation. Drawing insights from EAGLE, we develop a novel satellite chemical evolution model to decompose the observed SME into physical contributions from suppressed star formation, stellar mass loss, and enriched gas inflow. Our analysis shows that continuous accretion of enriched intracluster medium dominates the SME plateau within the cluster virial radius, while mass loss and quenching jointly drive the rapid metallicity decline in the cluster core. Our method disentangles the impacts of three environmental processes on galactic chemical enrichment in the cosmic web, providing a powerful framework for understanding cluster galaxy evolution with current and future spectroscopic surveys.

Lin, Yuanye [Shanghai Jiao Tong U.; Shanghai Jiaot↗

Insensitivity of Magnetic Coupling to Ligand Substitution in a Series of Tetraoxolene Radical-Bridged Fe 2 Complexes

The elucidation of magnetostructural correlations between bridging ligand substitution and strength of magnetic coupling is essential to the development of high-temperature molecule-based magnetic materials. Toward this end, we report the series of tetraoxolene-bridged Fe II 2 complexes [(Me 3 TPyA) 2 Fe 2 ( R L)] n + (Me 3 TPyA = tris(6-methyl-2-pyridylmethyl)amine; n = 2: OMe LH 2 = 3,6-dimethoxy-2,5-dihydroxo-1,4-benzoquinone, Cl LH 2 = 3,6-dichloro-2,5-dihydroxo-1,4-benzoquinone, Na 2 [ NO 2 L] = sodium 3,6-dinitro-2,5-dihydroxo-1,4-benzoquinone; n = 4: SMe 2 L = 3,6-bis(dimethylsulfonium)-2,5-dihydroxo-1,4-benzoquinone diylide) and their one-electron-reduced analogues. Furthermore, variable-temperature dc magnetic susceptibility data reveal the presence of weak ferromagnetic superexchange between Fe II centers in the oxidized species, with exchange constants of J = +1.2(2) (R = OMe, Cl) and +0.3(1) (R = NO 2 , SMe 2 ) cm –1 . In contrast, X-ray diffraction, cyclic voltammetry, and Mössbauer spectroscopy establish a ligand-centered radical in the reduced complexes. Magnetic measurements for the radical-bridged species reveal the presence of strong antiferromagnetic metal–radical coupling, with J = -57(10), -60(7), -58(6), and -65(8) cm –1 for R = OMe, Cl, NO 2 , and SMe 2 , respectively. The minimal effects of substituents in the 3- and 6-positions of R L x –• on the magnetic coupling strength is understood through electronic structure calculations, which show negligible spin density on the substituents and associated C atoms of the ring. Finally, the radical-bridged complexes are single-molecule magnets, with relaxation barriers of U eff = 50(1), 41(1), 38(1), and 33(1) cm –1 for R = OMe, Cl, NO 2 , and SMe 2 , respectively. Taken together, these results provide the first examination of how bridging ligand substitution influences magnetic coupling in semiquinoid-bridged compounds, and they establish design criteria for the synthesis of semiquinoid-based molecules and materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An analysis of Solar Mesospheric Explorer temperatures for the upper stratosphere and mesosphere

We proposed to analyze Solar Mesosphere Explorer (SME) limb profiles of Rayleigh scattered solar flux at wavelengths of 304, 313, and 443 nm to retrieve atmospheric temperature profiles over the 40-65 km altitude region. These temperatures can be combined with the previous analysis of SME 296 nm limb radiances to construct a monthly average climatology of atmospheric temperatures over the 40-90 km, upper stratosphere-mesosphere region, with approximately 4 km vertical resolution. We proposed to investigate the detailed nature of the global temperature structure of this poorly measured region, based on these 1982-1986 SME temperatures. The average vertical structure of temperatures between the stratopause and mesopause has never been determined globally with vertical resolution sufficient to retrieve even scale-height structures. Hence, the SME temperatures provided a unique opportunity to study the detailed thermal structure of the mesosphere, in advance of Upper Atmosphere Research Satellite (UARS) measurements and the Thermosphere Ionosphere Mesosphere Energy and Dynamics (TIMED) mission.

Clancy, R. Todd↗

Shape memory effect in metallic glasses

Shape memory effect (SME), mainly present in crystalline Ti-Ni alloys, is basically missing in metallic glasses (MGs) that lack the long-range periodic order of crystals. In this work, we report experimental results of SME in annealed MGs, in which the low-energy configuration state recovery is observed by both differential scanning calorimetry and X-ray photon correlation spectroscopy. We elucidate the origin of SME in MGs under the potential energy landscape framework, i.e., after annealing, the energy of MGs enters into a deep basin and atoms are located in the low-energy configuration state. Albeit deviating from their relative stable configurations by temperature changes, atoms in the annealed MGs tend to return to the low-energy atomic configurations along certain trajectories as pre-annealing temperature is approached, These results could extend the application of MGs as functional materials by directionally manipulating their energy states via annealing and rejuvenation.

36 MATERIALS SCIENCE↗

Assessment of simplified composite micromechanics using three-dimensional finite-element analysis

Three-dimensional finite-element analyses are used to assess the accuracy of simplified composite micromechanics equations (SME) for hygral, thermal, and mechanical properties of unidirectional composites with orthotropic fibers. The properties predicted by the SME are in reasonably good agreement with those predicted by the three-dimensional finite-element analyses. This correlation demonstrates that the SME can be used with confidence in predicting the hygral, thermal, and mechanical behavior of unidirectional fiber composites.

Caruso, J. J.↗

Flight experience of solar mesosphere explorer's power system over high temperatures ranges

The performance of the power system on the Solar Mesosphere Explorer (SME) satellite for the life of the mission and the techniques used to ensure power system health are summarized. Early in the mission high cell imbalances in one of the batteries resulted in a loading scheme which attempted to minimize the cell imbalances without causing an undervoltage condition. A short term model of the power system allowed planners to predict depth of discharge using the latest available data. Due to expected orbital shifts the solar arrays experience extended periods of no eclipse. This has required special conditioning schemes to keep the batteries healthy when the eclipses return. Analysis of the SME data indicates long term health of the SME power system as long as the conditioning scheme is continued.

Faber, Jack↗

Solar Mesosphere Explorer observations of stratospheric and mesospheric water vapor

It is noted that while the SME (Solar Mesosphere Explorer) data is consistent with the earlier LIMS (Limb Infrared Monitor of the Stratosphere) results, its interpretation is complicated by aerosol contamination, particularly at altitudes below 35 km. This contamination arose from several volcanic eruptions, including that of El Chichon. Analyses are reported of a subset of data from the SME satellite, concentrating primarily on the period January through March 1982 so as to avoid contamination from the El Chichon volcanic aerosol. The SME observations of water vapor between 20 and 60 km were inverted for the first three months of 1982 as well as for selected additional periods. Reasonable results are obtained at locations where no contamination by aerosol is suspected.

Jakosky, Bruce M.↗