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At least 1,099 records · Page 61

Synthesis of perbromates

Salts of heptavalent bromine were synthesized by a hot atom process, the beta decay of radioactive selenium-83 incorporated into a selenate. Formation of an unreactive perbromate ion led to preparation of macro amounts of perborate. A rubidium salt was isolated.

Appelman, E. H.↗

Hot-atom synthesis of organic compounds on Jupiter

Results of recent laboratory 'simulations' of photochemical processes on Jupiter are combined with available data on mixing rates and exposure times in the Jovian atmosphere to give quantitative predictions of the rate at which hot-atom reactions produce organic molecules. It is shown that abstraction reactions on methane by hot H atoms from solar UV photolysis of H2S will produce no more than 4 times 10 to the -17th power g/sq cm/sec for a steady-state mole fraction of total organics of approximately 10 to the -16th power. This is roughly 10 to the 7th power times less than the limit of detection of the most sensitive gas analysis experiments ever flown on a spacecraft. By far the most common organic molecule produced by this mechanism is CH3SH, methyl mercaptan, which is produced at a rate at least 600 times smaller than the rate of production of ethane by direct photolysis of CH4 at high altitudes.

Lewis, J. S.↗

Synthesis of ceramic powders and surface films from laser heated gases

Two new processes have been developed that are based on laser-heated gases. Both permit unusually precise levels of process control and, thereby, materials having superior properties. The power process yields Si, Si3N4 and SiC powders that are uniform in size, nonagglomerated, small diameter, spherically shaped and high purity. Manufacturing cost analyses show that submicron powders can be made with an energy cost of approximately 2 kWhr/kg and a dollar cost of 2-3.30 $/kg, exclusive of the costs of feed materials. The laser-induced chemical vapor deposition process (LICVD) causes reactant gases to be heated by absorbing IR light from a laser beam that passes parallel to the substrate surface. Laser heating permits independent control of gas and substrate temperatures while operating in a conventional, thermally activated chemical vapor deposition mode. Spin density, hydrogen content, electrical conductivity and mobility gap properties show the LICVD process capable of producing very high quality films.

Haggerty, J. S.↗

Synthesis Of Realistic Animations Of A Person Speaking

Actors computer program implements automated process that synthesizes realistic animations of person speaking. Produces "newscaster" type video sequences. Uses images of person and, therefore, not limited to cartoons and cartoonlike movies. Potential applications also include use of process for automatically producing on-the-fly animations for human/computer interfaces and for reducing bandwidth needed to transmit video telephone signals.

Scott, Kenneth C.↗

Synthesis and Purity Specifications for N,N'-Dicyclohexyl-N"-(10-nonadecyl)guanidinium Chloride for Use in Next Generation Caustic-Side Solvent Extraction

This report describes a synthesis procedure for the alkylguanidine, N,N'-dicyclohexyl-N"-(10-nonadecyl)guanidine (DCNDG), which has been identified as a promising candidate for replacing the less stable N,N',N"-tri(3,7-dimethyloctyl)guanidine (TiDG) suppressor in the Next Generation Caustic-Side Solvent Extraction (NG-CSSX) process. A verified procedure for the preparation of the amine used in this synthesis is also included. In addition, requirements for the purity of DCNDG to be utilized in the NG-CSSX process without adverse effect on the Cs + extraction and stripping are given.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessing the cumulative effects of nearshore habitat restoration actions for multiple populations of juvenile salmon in Whidbey Basin, Washington: foundation and approach for synthesis and evaluation

Ecosystem restoration is a common tool for re-establishing ecosystem processes, structures, and functions to improve biodiversity and services in coastal and estuarine ecosystems. In the Salish Sea, salmon habitats have been fragmented, reduced in size, and diminished in quality, and the ecosystem processes that form and sustain these habitats have been degraded and disrupted as well. This loss is especially prevalent in estuaries, where up to 90% of former salmon habitat has been lost or compromised. Salmon species are integral to the identities and cultures of people in the Pacific Northwest, yet salmon abundances remain at historic lows, especially in urbanized areas. Recent investments in restoration are creating rearing habitat and repairing lost ecosystem function. However, restoration efforts in this region have largely proceeded at the site scale, with less attention to big-picture thinking regarding how restoration will effectively recover degraded or lost habitats for target species. As a result, no landscape-scale evaluation program exists, and the cumulative benefits of multiple interventions are unknown. We describe innovative methods for science synthesis related to the evaluation of cumulative effects of ecosystem restoration for Pacific salmon, using years of existing, but disparate data. Building from previous work on cumulative effects evaluation and incorporating a hierarchy of hypotheses approach, we propose using causal inference across numerous hypotheses in a framework to assess the cumulative benefits to Pacific salmon from multiple estuarine restoration projects. We present the framework as a method that can be used to address many complex questions and provide examples from the Salish Sea where the approach is being implemented. The framework draws on science synthesis from numerous fields and uses a hierarchy of hypotheses, causal analysis at multiple scales, and a new hierarchy of synthesis for assessing multiple lines of evidence documenting restoration effects on Pacific salmon. We propose causal inference to synthesize dissimilar data streams, in our case, to identify various manifestations of cumulative effects of restoration and benefits to salmon, and to further inform restoration and recovery planning. A unifying framework would allow for the detection of thresholds at which restoration provides measurable improvement and would greatly advance understanding of the effects of restoration on ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗

Basic Modeling of the Solar Atmosphere and Spectrum

During the last three years we have continued the development of extensive computer programs for constructing realistic models of the solar atmosphere and for calculating detailed spectra to use in the interpretation of solar observations. This research involves two major interrelated efforts: work by Avrett and Loeser on the Pandora computer program for optically thick non-LTE modeling of the solar atmosphere including a wide range of physical processes, and work by Kurucz on the detailed high-resolution synthesis of the solar spectrum using data for over 58 million atomic and molecular lines. Our objective is to construct atmospheric models from which the calculated spectra agree as well as possible with high-and low-resolution observations over a wide wavelength range. Such modeling leads to an improved understanding of the physical processes responsible for the structure and behavior of the atmosphere.

Avrett, Eugene H.↗

Review of Solid State Consolidation Processing Techniques of ODS Steels (Hot Extrusion, Hot Isostatic Pressing, Spark Plasma Sintering, and Stir Friction Consolidation): Resulting Microstructures and Mechanical Properties

This paper reviews the solid-state consolidation processing techniques for Oxide Dispersion Strengthened steels and compares them in terms of the resulting microstructure and reported mechanical properties. Synthesis techniques include hot extrusion, hot isostatic pressing, spark plasma sintering and friction consolidation. The effects of process parameters on the resulting microstructures and performance are discussed for each technique. Average oxide size, average grain size, and porosity are compared across techniques, as well as mechanical strength and ductility. Across consolidation techniques where temperature can be controlled, a low sintering temperature with a high sintering pressure is favorable for keeping oxide sizes, grain sizes, and porosity low. The use of yttrium and titanium for oxide formation has been evidenced to reduce oxide sizes, and tungsten additions have been shown to improve strength. Current literature suggests that the more mature hot extrusion technique produces stronger steel with consistently fine oxides, while other alternative solid-state consolidation, while promising, offer margin for improvement.

36 MATERIALS SCIENCE↗

Reaching the Excitonic Limit in 2D Janus Monolayers by In Situ Deterministic Growth

Abstract Named after the two‐faced Roman god of transitions, transition metal dichalcogenide (TMD) Janus monolayers have two different chalcogen surfaces, inherently breaking the out‐of‐plane mirror symmetry. The broken mirror symmetry and the resulting potential gradient lead to the emergence of quantum properties such as the Rashba effect and the formation of dipolar excitons. Experimental access to these quantum properties, however, hinges on the ability to produce high‐quality 2D Janus monolayers. Here, these results introduce a holistic 2D Janus synthesis technique that allows real‐time monitoring of the growth process. This prototype chamber integrates in situ spectroscopy, offering fundamental insights into the structural evolution and growth kinetics, that allow the evaluation and optimization of the quality of Janus monolayers. The versatility of this method is demonstrated by synthesizing and monitoring the conversion of SWSe, SNbSe, and SMoSe Janus monolayers. Deterministic conversion and real‐time data collection further aid in conversion of exfoliated TMDs to Janus monolayers and unparalleled exciton linewidth values are reached, compared to the current best standard. The results offer an insight into the process kinetics and aid in the development of new Janus monolayers with high optical quality, which is much needed to access their exotic properties.

2D materials↗

Shifting Defect Self-Regulation via Disordered Vacancies in Hollow Tin Perovskites

Tin(II)-based hybrid halide perovskites typically suffer from severe self-doping behavior as a result of facile oxidation of Sn(II) to Sn(IV), leading to high carrier densities (holes) and metallic-like conductivities that limit their applications. In this contribution, we describe how substituting the large ethylenediammonium cation for methylammonium in the intentionally defective “hollow” perovskite family, MA 1−x en x Sn 1−0.7x I 3−0.4x (MA = methylammonium, en = ethylenediammonium), where 0 ≤ x ≤ 0.38, effectively minimizes the intrinsic self-doping behavior. The use of a solvent-free, mechanochemical synthesis route further circumvents oxidative side reactions typical in solution processing, enabling more precise control and understanding of both composition and defect chemistry. Dark and time-resolved microwave conductivity measurements of these materials as a function of “x” reveal two regimes of conductivity suppression: at low x incorporation (x ≤ 0.15), the carrier density decreases by an order of magnitude via defect-mediated charge compensation, while higher substitution (0.15 < x ≤ 0.38) greatly reduces the carrier mobility. At these lower substitution levels, the observations suggest that intrinsic equilibrium tin vacancies are compensated instead by ionic defects in lieu of mobile holes. For the higher substitution levels, the less mobile carriers exhibit long recombination lifetimes, consistent with polaron-mediated transport. These findings establish a strategy for relatively low iodine chemical potential synthesis and defect-driven control of the carrier concentration in tin halide perovskites, advancing the rational discovery of dopable hybrid semiconductors.

36 MATERIALS SCIENCE↗

Lignin Formation and the Effects of Gravity: A New Approach

Two aspects of considerable importance in the enigmatic processes associated with lignification have made excellent progress. The first is that, even in a microgravity environment, compression wood formation, and hence altered lignin deposition, can be induced upon mechanically bending the stems of woody gymnosperms. It now needs to be established if an organism reorientating its woody stem tissue will generate this tissue in microgravity, in the absence of externally applied pressure. If it does not, then gravity has no effect on its formation, and instead it results from alterations in the stress gradient experienced by the organism impacted. The second area of progress involves establishing how the biochemical pathway to lignin is regulated, particularly with respect to selective monolignol biosynthesis. This is an important question since individual monomer deposition occurs in a temporally and spatially specific manner. In this regard, the elusive metabolic switch between E-p-coumaryl alcohol and E-coniferyl alcohol synthesis has been detected, the significance of which now needs to be defined at the enzyme and gene level. Switching between monolignol synthesis is important, since it is viewed to be a consequence of different perceptions by plants in the gravitational load experienced, and thus in the control of the type of lignification response. Additional experiments also revealed the rate-limiting processes involved in monolignol synthesis, and suggest that a biological system (involving metabolite concentrations, as well as enzymatic and gene (in)activation processes) is involved, rather than a single rate-limiting step.

Lewis, Norman G.↗

Hybrid Nanostructured Ni(OH) 2 /NiO for High Capacity Lithium–ion Battery Anodes

A straightforward hydrothermal process followed by a controlled calcination technique is introduced for the synthesis of a Ni(OH) 2 modified NiO nanohybrid structure. Conversion materials as Li-ion battery anodes, NiO in this case, suffer from capacity fade and structural/morphological instability during lithiation and delithiation. The novelty of this work is in utilizing this hybrid configuration to increase the specific capacity and enable reversible electrochemistry. Here, we study the lithiation/delithiation process of NiO using a suite of spectroscopy and microscopy techniques from the atomic to electrode scale. We propose a mechanism for a reversible redox couple behavior of the NiO electrode by means of a hybrid Ni(OH)2/NiO structure. The ultimate objective of this work is to guide the development of anode with rationally-designed heterogeneity to create high capacity Li-ion batteries with excellent cycling and rate performance.

25 ENERGY STORAGE↗

Conserving Land–Atmosphere Synthesis Suite (CLASS)

Accurate estimates of terrestrial water and energy cycle components are needed to better understand climate processes and improve models’ ability to simulate future change. Various observational estimates are available for the individual budget terms; however, these typically show inconsistencies when combined in a budget. In this work, a Conserving Land–Atmosphere Synthesis Suite (CLASS) of estimates of simultaneously balanced surface water and energy budget components is developed. Individual CLASS variable datasets, where possible, 1) combine a range of existing variable product estimates, and hence overcome the limitations of estimates from a single source; 2) are observationally constrained with in situ measurements; 3) have uncertainty estimates that are consistent with their agreement with in situ observations; and 4) are consistent with each other by being able to solve the water and energy budgets simultaneously. First, available datasets of a budget variable are merged by implementing a weighting method that accounts both for the ability of datasets to match in situ measurements and the error covariance between datasets. Then, the budget terms are adjusted by applying an objective variational data assimilation technique (DAT) that enforces the simultaneous closure of the surface water and energy budgets linked through the equivalence of evapotranspiration and latent heat. Comparing component estimates before and after applying the DAT against in situ measurements of energy fluxes and streamflow showed that modified estimates agree better with in situ observations across various metrics, but also revealed some inconsistencies between water budget terms in June over the higher latitudes.

54 ENVIRONMENTAL SCIENCES↗

Machine Learning Guided Synthesis of Flash Graphene

Advances in nanoscience have enabled the synthesis of nanomaterials, such as graphene, from low-value or waste materials through flash Joule heating. Though this capability is promising, the complex and entangled variables that govern nanocrystal formation in the Joule heating process remain poorly understood. In this work, machine learning (ML) models are constructed to explore the factors that drive the transformation of amorphous carbon into graphene nanocrystals during flash Joule heating. An XGBoost regression model of crystallinity achieves an r 2 score of 0.8051 ± 0.054. Feature importance assays and decision trees extracted from these models reveal key considerations in the selection of starting materials and the role of stochastic current fluctuations in flash Joule heating synthesis. Furthermore, partial dependence analyses demonstrate the importance of charge and current density as predictors of crystallinity, implying a progression from reaction-limited to diffusion-limited kinetics as flash Joule heating parameters change. Finally, a practical application of the ML models is shown by using Bayesian meta-learning algorithms to automatically improve bulk crystallinity over many Joule heating reactions. Furthermore, these results illustrate the power of ML as a tool to analyze complex nanomanufacturing processes and enable the synthesis of 2D crystals with desirable properties by flash Joule heating.

01 COAL, LIGNITE, AND PEAT↗

Carbon fiber synthesis from pitch: Insights from ReaxFF based molecular dynamics simulations

Despite the potential to lowering fabrication costs of pitch-based carbon fiber (CF) compared to polyacrylonitrile-based CF, large scale utilization is currently limited by the complexity in manufacturing. This is mainly due to the lack of consistency between the pitch structure/chemistry and CF properties under different processing conditions. Here, we employed full atomistic simulations based on reactive force fields to investigate the conversion of pitch precursors to CFs. Additionally, it was found that at the carbonization stage, the consumption rates of precursors, gas formations, and solid yields (carbonized CFs) are all dependent on the composition and arrangement of molecular moieties in the precursor. Specifically, precursors with sp 3 carbons in the cata-condensed core area have limited decomposition pathways (i.e., limited reaction sites), which leads to the formation of carbonized CFs with similar compositions. Furthermore, carbonized CFs possess distinct structural characteristics, and finally lead to the formation of CFs with different moduli. By analyzing CF crystallinity and elemental composition, general rationales are proposed for the selection of optimal precursors and processing conditions, and thus shed lights on parameter screening during industrial CF synthesis. For instance, inclusion of sp 3 carbons in cata- condensed rings can be preferred over the presence of sp 3 carbons on side chains.

01 COAL, LIGNITE, AND PEAT↗

Unconventional Catalytic Approaches to Ammonia Synthesis

Ammonia is a critically important industrial chemical and is largely responsible for sustaining the growing global population. To provide ammonia to underdeveloped regions and/or regions far from industrial production hubs, modular systems have been targeted and often involve unconventional production methodologies. These novel approaches for ammonia production can tap renewable resources at smaller scales located at the point of use, while decreasing the CO 2 footprint. Plasma-assisted catalysis and electrochemical ammonia synthesis have promise owing to their atmospheric pressure and low-temperature operation conditions and the ability to construct units at scales desired for modularization. Fundamental and applied studies are underway to assess these processes, although many unknowns remain. In this review, we discuss recent developments and opportunities for unconventional ammonia synthesis with a focus on plasma-stimulated systems.

42 ENGINEERING↗

Preservation of high-pressure volatiles in nanostructured diamond capsules

High pressure induces dramatic changes and novel phenomena in condensed volatiles(1,2) that are usually not preserved after recovery from pressure vessels. In this study we report a process that pressurizes volatiles into nanopores of type 1 glassy carbon precursors, converts glassy carbon into nanocrystalline diamond by heating and synthesizes free-standing nanostructured diamond capsules (NDCs) capable of permanently preserving volatiles at high pressures, even after release back to ambient conditions for various vacuum-based diagnostic probes including electron microscopy. As a demonstration, we perform a comprehensive study of a high-pressure argon sample preserved in NDCs. Synchrotron X-ray diffraction and high-resolution transmission electron microscopy show nanometre-sized argon crystals at around 22.0 gigapascals embedded in nanocrystalline diamond, energy-dispersive X-ray spectroscopy provides quantitative compositional analysis and electron energy-loss spectroscopy details the chemical bonding nature of high-pressure argon. The preserved pressure of the argon sample inside NDCs can be tuned by controlling NDC synthesis pressure. To test the general applicability of the NDC process, we show that high-pressure neon can also be trapped in NDCs and that type 2 glassy carbon can be used as the precursor container material. Additional experiments on other volatiles and carbon allotropes open the possibility of bringing high-pressure explorations on a par with mainstream condensed-matter investigations and applications.

36 MATERIALS SCIENCE↗