SEARCH · Search NASA
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Fe( ii ) and Fe( iii ) dithiocarbamates are precursors to a range of nanoparticulate iron sulfides and in situ studies give insight into the molecular decomposition mechanism being dominated by reductive-elimination of thiuram disulfide and amide-exchange.
The nature of π–π interactions has long been debated. The term “π-stacking” is considered by some to be a misnomer, in part because overlapping π-electron densities are thought to incur steric repulsion, and the physical origins of the widely-encountered “slip-stacked” motif have variously been attributed to either sterics or electrostatics, in competition with dispersion. Here, we use quantum-mechanical energy decomposition analysis to investigate π–π interactions in supramolecular complexes of polycyclic aromatic hydrocarbons, ranging in size up to realistic models of graphene, and for comparison we perform the same analysis on stacked complexes of polycyclic saturated hydrocarbons, which are cyclohexane-based analogues of graphane. Our results help to explain the short-range structure of liquid hydrocarbons that is inferred from neutron scattering, trends in melting-point data, the interlayer separation of graphene sheets, and finally band gaps and observation of molecular plasmons in graphene nanoribbons. Analysis of intermolecular forces demonstrates that aromatic π–π interactions constitute a unique and fundamentally quantum-mechanical form of non-bonded interaction. Not only do stacked π–π architectures enhance dispersion, but quadrupolar electrostatic interactions that may be repulsive at long range are rendered attractive at the intermolecular distances that characterize π-stacking, as a result of charge penetration effects. The planar geometries of aromatic sp 2 carbon networks lead to attractive interactions that are “served up on a molecular pizza peel”, and adoption of slip-stacked geometries minimizes steric (rather than electrostatic) repulsion. The slip-stacked motif therefore emerges not as a defect induced by electrostatic repulsion but rather as a natural outcome of a conformational landscape that is dominated by van der Waals interactions (dispersion plus Pauli repulsion), and is therefore fundamentally quantum-mechanical in its origins. This reinterpretation of the forces responsible for π-stacking has important implications for the manner in which non-bonded interactions are modeled using classical force fields, and for rationalizing the prevalence of the slip-stacked π–π motif in protein crystal structures.
Here, we report the decomposition of La 2–x Sr x CuO 4 into La 2 O 3 and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150°C and is considerably expedited in the temperature range of 350°C–450°C. Two major resultant solid phases are identified as metallic Cu and La 2 O 3 by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, La 2 O 3 phases are further identified to be derivatives of a fluorite structure—fluorite, pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and LaM 4,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and La 2 O 3 phases remain unchanged after cooling to room temperature.
The 9975 surveillance program is developing a technical basis to support extending the storage period of 9975 packages in K-Area Complex beyond the currently approved 15 years. A key element of this effort is developing a better understanding of degradation of the fiberboard assembly under storage conditions. This degradation is influenced greatly by the moisture content of the fiberboard, which is not well characterized on an individual package basis. Direct measurements of humidity and fiberboard moisture content have been made on two test packages with cane fiberboard and varying internal heat levels from 0 up to 19W. With an internal heat load, a temperature gradient in the fiberboard assembly leads to varying relative humidity in the air around the fiberboard. However, the absolute humidity tends to remain approximately constant throughout the package. The moisture content of fiberboard varies under the influence of several phenomena. Changes in local fiberboard temperature (from an internal heat load) can cause fiberboard moisture changes through absorption or evaporation. Fiberboard degradation at elevated temperature will produce water as a byproduct. And the moisture level within the package is constantly seeking equilibrium with that of the surrounding room air, which varies on a daily and seasonal basis. One indicator of the moisture condition within a 9975 package might be obtained by measuring the relative humidity in the upper air space, by inserting a humidity probe through a caplug hole. However, the data indicate that for the higher internal heat loads (15 and 19 watts), a large variation in internal moisture conditions produces little or no variation in the air space relative humidity. Therefore, this approach does not appear to be sensitive to fiberboard moisture variations at the higher heat loads which are of most interest to maintaining fiberboard integrity.
This investigation was initiated to provide basic spectral data for gases of interest to the plasma core reactor concept. The attenuation of vacuum ultraviolet (VUV) radiation by helium at pressures up to 20 atm over path lengths of about 61 cm and in the approximate wavelength range between 80 and 300 nm was studied. Measurements were also conducted to provide basic VUV data with respect to UF6 and UF6/argon mixtures in the wavelength range between 80 and 120 nm. Finally, an investigation was initiated to provide basic spectral emission and absorption data for UF6 and possible thermal decomposition products of UF6 at elevated temperatures.
Evaporated ZnS films used as a component in reflectance enhancing or decreasing multilayer coatings for mirrors, transparent optical materials, and vacuum UV reflecting optics, are investigated with reference to the reflectance loss under UV irradiation and the formation of ZnO as a result of the decomposition of ZnS in the presence of oxygen. Reflectance measurements over a broad wavelength range reveal that the UV induced reflectance losses are generally restricted to wavelengths shorter than 4000 A and are most severe in the vacuum UV region. After 134 hr of UV exposure initially polycrystalline film of 150-200 A thick is completely converted to amorphous ZnO. The results demonstrate that caution should be exercised in employing ZnS as the outer layer in an optical coating system designed for use in the UV and vacuum UV regions.
High-Test Hydrogen Peroxide (HTP) is receiving renewed interest as a monopropellant and as the oxidizer for bipropellant systems. HTP is hydrogen peroxide having concentrations ranging from 70 to 98%. In these applications the energy and oxygen released during decomposition of HTP is used for propulsion. In propulsion systems components must be fabricated and connected using available joining processes. Welding is a common joining method for metallic components. The goal of this study was to compare the HTP compatibility of welded vs. unwelded stainless steel.
Recent advances in improving efficiency of thermoelectric materials are linked to nanotechnology. Thermodynamically driven spinodal decomposition was utilized to synthesize bulk nanocomposites. TiO2/SnO2 system exhibits a large spinodal region, ranging from 15 to 85 mole % TiO2. The phase separated microstructures are stable up to 1400 C. Semiconducting TiO2/SnO2 powders were synthesized by solid state reaction between TiO2 and SnO2. High density samples were fabricated by pressureless sintering. Self assemble nanocomposites were achieved by annealing at 1000 to 1350 C. X-ray diffraction reveal phase separation of (Ti(x)Sn(1-x))O2 type phases. The TiO2/SnO2 nanocomposites exhibit n-type behavior; a power factor of 70 (mu)W/m sq K at 1000 C has been achieved with penta-valent doping. Seebeck, thermal conductivity, electrical resistivity and microstructure will be discussed in relation to composition and doping.
Recent advances in improving efficiency of thermoelectric materials are linked to nanotechnology. Thermodynamically driven spinodal decomposition was utilized to synthesize bulk nanocomposites. TiO2/SnO2 system exhibits a large spinodal region, ranging from 15 to 85 mole % TiO2. The phase separated microstructures are stable up to 1400 C. Semiconducting TiO2/SnO2 powders were synthesized by solid state reaction between TiO2 and SnO2. High density samples were fabricated by pressureless sintering. Self assemble nanocomposites were achieved by annealing at 1000 to 1350 C. X-ray diffraction reveal phase separation of (Ti(x)Sn(1-x))O2 type phases. The TiO2/SnO2 nanocomposites exhibit n-type behavior; a power factor of 70 W/mK2 at 1000 C has been achieved with penta-valent doping. Seebeck, thermal conductivity, electrical resistivity and microstructure will be discussed in relation to composition and doping.
Due to the increasing amount of polyurethane waste, chemical recycling of these materials is a topic of growing interest for many researchers. The primary purpose of polyurethane feedstock recycling is to recover the starting polyol. In this study glycerolysis using glycerine from two sources and two purity grades is proposed as a method of chemical recycling. The main effort of this paper focuses on the employment of commercial glycerine of analytical grade and waste glycerine without purification derived from the biodiesel production, as a decomposing agent for polyurethane recycling. In this study, the influence of polyurethane to glycerine mass ratio (PU/GL) and the type of decomposing agent on the chemical structure by FTIR, {sup 1}H NMR and GPC was examined. FTIR analysis of the glycerolysates showed absorption peaks similar to the virgin polyol. Those results are in compliance with GPC chromatograms, which showed for all samples, well-defined peak at ca. 13 min of retention time. The molecular weight of glycerolysates was ranging from 800 to 1300 g mol{sup −1} depending on PU/GL mass ratio. The novel decomposition agent, namely waste glycerine derived from biodiesel production was successfully used in glycerolysis process.
The uppermost portion of the peat profile, an area of active diagenetic processes, is exceedingly important for understanding peatland dynamics and the diagenesis and geochemistry of atmospherically-deposited materials. In this study, we investigated high resolution carbon (C) accrual and peat decomposition rates at two Sphagnum-rich ombrotrophic bogs and one fen in northern Minnesota, USA by analyzing 1 cm increments from 30 cm thick intact frozen blocks of peat soil. We conducted radiocarbon analysis of Sphagnum cellulose to determine peat age and net C accumulation at each depth interval. Calibrated peat ages were determined using CALIBomb and a compilation of calibration datasets for the pre-bomb period. We fit data with a negative exponential accumulation model and used model-derived parameters to estimate net primary productivity (NPP) and a peat decomposition rate constant k. FTIR spectroscopy and C:N were used to derive humification indices and to chemically characterize the peat. NPP ranged from 180 to 266 g C m -2 year -1 , k ranged from 0.015 to 0.019 year -1 . Net C accumulation rates ranged from 112 to 174 g C m -2 year -1 at 25 years and 70 to 113 g C m -2 year-1 at 50 years. Mass loss was up to 55% during the first 50 years of peat accumulation. Decomposition is greater at depth in the bogs—where 25 cm of peat correspond to 55 years of peat accumulation—than in the fen, where peat age is approximately 25 years at 25 cm depth. Lastly, information on fine-scale variations in peat mass decomposition and loss across ombrotrophic bogs and a fen help interpret other diagenetic processes in peatlands.
Measurements of the oxidation rates of various forms of carbon (soot, graphite, coal char) have often shown an unexplained attenuation with increasing temperatures in the vicinity of 2000 K, even when accounting for diffusional transport limitations and gas-phase chemical effects (e.g. CO 2 dissociation). With the development of oxy-fuel combustion approaches for pulverized coal utilization with carbon capture, high particle temperatures are readily achieved in sufficiently oxygen-enriched environments. Here, in this work, a new semi-global intrinsic kinetics model for high temperature carbon oxidation is created by starting with a previously developed 5-step mechanism that was shown to reproduce all major known trends in carbon oxidation, except for its high temperature kinetic falloff, and incorporating a recently discovered surface oxide decomposition step. The predictions of this new model are benchmarked by deploying the kinetic model in a steady-state reacting particle code (SKIPPY) and comparing the simulated results against a carefully measured set of pulverized coal char combustion temperature measurements over a wide range of oxygen concentrations in N 2 and CO 2 environments. The results show that the inclusion of the spontaneous surface oxide decomposition reaction step significantly improves predictions at high particle temperatures. Furthermore, the simulations reveal that O atoms released from the oxide decomposition step enhance the radical pool in the near-surface region and within the particle interior itself. Incorporation of literature rates for O and OH reactions with the carbon surface results in a reduction in the predicted radical pool concentrations and a very minor enhancement of the overall carbon oxidation rate.
The directions of the triadic energy transfers assumed in a previous paper agree with the spectral closures, in a similarity range, if the exponent of the power-law energy spectrum is less than unity. The helical interactions showing a strong local energy transfer when the triad is nonlocal, sum up to a reverse cascade unless the spectrum falls off faster than a -7/3 power of the wave number. The energy cascades from each type of helical interaction are calculated for a -5/3 inertial range using the eddy damped quasinormal Markovian model. One type of interaction is responsible for 86 percent of the cascade. The contributions of the two classes of helical interactions to the subgrid-scale eddy viscosity are presented, together with the contributions from the forward and reverse cascading interactions. An application of the assumption on the triadic energy transfers to turbulence under rapid rotation gives a simple argument for the tendency toward nonlinear two-dimensionalization of the flow.
The decomposition selectivity of formaldehyde during steam reforming was explored using unpromoted and sodium promoted Pt/m-ZrO 2 catalysts, and the Na content was varied (0.5%Na, 1%Na, 1.8%Na, 2.5%Na, and 5%Na). In situ DRIFTS experiments during temperature programmed reaction in flowing H 2 O revealed that formaldehyde is adsorbed at reduced defect sites on zirconia, where it is converted to formate species through the addition of labile bridging OH species. Formate species achieve a maximum intensity in the range of 125–175 °C, where only slight changes in intensity are observed. Above this temperature, the formate decomposition reactivity strongly depends on the Na loading, with the optimum loadings being 1.8%Na and 2.5%Na. CO 2 temperature programmed desorption results, as well as a greater splitting observed between the formate ν asym (OCO) and ν sym (OCO) bands in infrared spectroscopy, indicate greater basicity is induced by the presence of Na. This strengthens the interaction between the formate -CO 2 functional group and the catalyst surface, weakening the formate C-H bond. A shift in the ν(CH) band of formate to lower wavenumbers was observed by addition of Na, especially at 1.8%Na and higher loadings. This results in enhanced decarboxylation and dehydrogenation of formate, as observed in in situ DRIFTS, temperature-programmed reaction/mass spectrometry experiments of the steam reforming of formaldehyde, and fixed bed reaction tests. For example, 2.5%Na addition of 2.5% increased the CO 2 selectivity from 83.5% to 99.5% and the catalysts achieved higher stable conversion at lower temperature than NiO catalysts reported in the open literature. At 5%Na loading, Pt sites were severely blocked, hindering H-transfer.
Bias correction is a crucial step in using Earth system model outputs for assessments, as it adjusts systematic errors by comparing the model to observations. However, standard methods – ranging from mean-based linear scaling to distribution-based quantile mapping typically treat bias correction as a single-scale process, overlooking the fact that biases can manifest differently across daily, seasonal, and annual timescales. In this study, we propose a novel, timescale-aware bias-correction approach built on Empirical Mode Decomposition. By decomposing the meteorological signal into multiple oscillatory components and aggregating them to represent distinct timescales, we apply targeted corrections to each component, thereby preserving both short- and long-term structure in the data. Experimental illustrations show that the timescale-aware EMDBC framework matches the performance of conventional quantile-delta mapping (QDM) at the native daily scale and achieves progressively larger bias reductions at bi-weekly, seasonal, and annual scales. As a result, the proposed approach offers a more robust path to accurate and reliable Earth system projections, strengthening their utility for resilience and adaptation planning.
Fungi generate a wide range of extracellular hydrolytic and oxidative enzymes and reactive metabolites, collectively known as the secretome, that synergistically drive plant litter decomposition in the environment. While secretome studies of model organisms have greatly expanded our knowledge of these enzymes, few have extended secretome characterization to environmental isolates or directly compared temporal patterns of enzyme utilization among diverse species. Thus, the mechanisms of carbon (C) degradation by many ubiquitous soil fungi remain poorly understood. Here we use a combination of iTRAQ proteomics and custom bioinformatic analyses to compare the protein composition of the secretomes of four manganese(II)-oxidizing Ascomycete fungi over a three-week time course. We demonstrate that although the fungi produce a similar suite of extracellular enzymes, they exhibit striking differences in the regulation of these enzymes among species and over time, revealing species-specific and temporal shifts in C utilization strategies as they degrade the same substrate. Specifically, our findings suggest that Paraconiothyrium sporulosum AP3s5-JAC2a and Alternaria alternata SRC1lrK2f employ sequential enzyme secretion patterns concomitant with decreasing resource availability, Stagonospora sp. SRC1lsM3a preferentially degrades proteinaceous substrate before switching to carbohydrates, and Pyrenochaeta sp. DS3sAY3a utilizes primarily peptidases to aggressively attack carbon sources in a concentrated burst. This work highlights the diversity of operative metabolic strategies among cellulose-degrading Ascomycetes and enhances our understanding of their role in C turnover in the environment.
Here, this study explores the nature, dynamics, and reactivity of the photo-induced charge separated excited state in a Fe 3+ -doped titanium-based metal organic framework (MOF), xFeMIL125-NH 2 , as a function of iron concentration. The MOF is synthesized with doping levels x = 0.5, 1 and 2 Fe node sites per octameric Ti-oxo cluster and characterized by powder x-ray diffraction, UV-vis diffuse reflectance, atomic absorption, and steady state Fe K-edge X-ray absorption spectroscopy. For each doping level, time-resolved X-ray transient absorption spectroscopy studies confirm the electron trap site role of the Fe sites in the excited state. Time scan data reveal multiexponential decay kinetics for the charge recombination processes which extend into the microsecond range for all three concentrations. A series of dye photodegradation studies, based on the oxidative decomposition of Rhodamine B, demonstrates the reactivity of the charge separated excited state and the photocatalytic capacity of these MOF materials compared to traditional heterometal-doped semiconductor photocatalysts.
Lithium-ion batteries (LIBs) are a widely used energy storage device. For decades, researchers have been studying aqueous electrolytes due to their non-flammability and environmental friendless. However, the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) of water greatly limit the voltage window of the aqueous electrolyte. The recent concept of ‘solvent-in-salt’ electrolytes, namely ‘water-in-salt’ electrolytes (WISE) for aqueous batteries and ‘super-concentrated’ electrolytes for non-aqueous batteries, greatly expands the electrochemical window of these battery systems and consequently their energy density. This expansion occurs because the large number of salt aggregates in ‘solvent-in-salt’ electrolytes enables preferential salt decomposition over solvent decomposition to form robust interphase layers on electrodes, thus enhancing their stability in a wide range of operating voltages. However, even when the salt concentration reached 63m, regardless of cost, the cathodic potential of the WISE expanded only to 1.75V with an overall electrochemical stability window of <3.25V. To design the next generation of high energy aqueous LIBs, electrolytes that possess a wider electrochemical stability window and lower cost but still maintain the merit of non-flammability are much needed. In this project, we designed the aqueous LIBs with widened voltage window. We reported a cheap and non-flammable ternary eutectic electrolyte that can form a robust solid electrolyte interface (SEI)so that the cathodic limiting potential can be decreased to <1.5 V for Li 4 Ti 5 O 12 anodes, while maintaining both a high ionic conductivity of >10 -3 S cm –1 and a low viscosity. We demonstrated the super-stable2.5V LiMn 2 O 4 ||Li 4 Ti 5 O 12 pouch cell with mass loading of 2.5 mAh/cm. Further, LiCl-LiBr-Graphite/Li full cells were designed with high energy density. Finally, we use a bi-layer design to enlarge the voltage window of aqueous electrolyte, which can endow the stable cycling of aqueous Lithium metal batteries.