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At least 217 records · Page 12

Devitrification and delayed crazing of SiO2 on single-crystal silicon and chemically vapor-deposited silicon nitride

The linear growth rate of cristobalite was measured in thin SiO2 films on silicon and chemically vapor-deposited silicon nitride. The presence of trace impurities from alumina furnace tubes greatly increased the crystal growth rate. Under clean conditions, the growth rate was still 1 order-of-magnitude greater than that for internally nucleated crystals in bulk silica. Crystallized films cracked and lifted from the surface after exposure to atmospheric water vapor. The crystallization and subsequent crazing and lifting of protective SiO2 films on silicon nitride should be considered in long-term applications.

Choi, Doo Jin↗

Phase purity of NiCo2O4, a catalyst candidate for electrolysis of water

NiCo2O4 is shown to be difficult to obtain as a pure phase, and may never have been so obtained. High resolution x-ray diffractometry is required for its precise characterization. Film XRD is not likely to show the asymmetry in the spinel diffraction lines, caused by poorly crystallized NiO, as seen in diffractometer traces. The Co3O4 which is expected to accompany NiO as an impurity in NiCo2O4 syntheses has the same diffraction pattern as the binary oxide. Firings of the co-precipitated hydroxides at 300, 350, and 400 C, including one in pure O2, failed to produce single phase cobaltate. Scanning electron microscopy showed all the sintered products to range over several orders of magnitude in agglomerate/particle size. Surface areas by BET were all in the range 40 to 110 m sq/g, equivalent to particles of 200 to 100 Angstrom diameter. The spinel diffraction line breadths were compatible with those approximate dimensions.

Singer, J.↗

Simulating vibro-acoustic damping of bubbles in fluids

Bubbles in fluids are common occurrence due to impurities, thermal or flow variations. They are sometimes considered detrimental to the flow and more importantly surrounding structural integrity. On the other hand, bubbles were used positively towards damping vibrations in fluid filled structures [1] and as barriers or curtains in the removal of plastic waste from water ways [2] and also in noise attenuation from offshore windfarms [3]. In the latter two cases, engineers hypothesized these curtains help marine life from sound pollution from surrounding machinery and ships. In this paper the authors discuss two cases to study the effect of bubble size and bubble density. In the first experiment a curtain of air bubbles was introduced in a water body and sound transmission loss (STL) through this curtain was studied. In a second experiment, a stainless-steel tank filled with liquid mercury is infused with helium bubbles and the vibration levels were monitored.

Kappagantu, Ramana↗

Manganese-cobalt spinel oxide nanowire arrays

Manganese-cobalt (Mn—Co) spinel oxide nanowire arrays are synthesized at low pressure and low temperature by a hydrothermal method. The method can include contacting a substrate with a solvent, such as water, that includes Mn04- and Co2 ions at a temperature from about 60° C. to about 120° C. The method preferably includes dissolving potassium permanganate (KMn04) in the solvent to yield the Mn04- ions. the substrate is The nanoarrays are useful for reducing a concentration of an impurity, such as a hydrocarbon, in a gas, such as an emission source. The resulting material with high surface area and high materials utilization efficiency can be directly used for environment and energy applications including emission control systems, air/water purifying systems and lithium-ion batteries.

Gao, Pu-Xian↗

Grand Challenges of Hydrologic Modeling for Food-Energy-Water Nexus Security in High Mountain Asia

Climate-influenced changes in hydrology affect water-food-energy security that may impact up to two billion people downstream of the High Mountain Asia (HMA) region. Changes in water supply affect energy, industry, transportation, and ecosystems (agriculture, fisheries) and as a result, also affect the region's social, environmental, and economic fabrics. Sustaining the highly interconnected food-energy-water nexus (FEWN) will be a fundamental and increasing challenge under a changing climate regime. High variability in topography and distribution of glaciated and snow-covered areas in the HMA region, and scarcity of high resolution (in-situ) data make it difficult to model and project climate change impacts on individual watersheds. We lack basic understanding of the spatial and temporal variations in climate, surface impurities in snow and ice such as black carbon and dust that alter surface albedo, and glacier mass balance and dynamics. These knowledge gaps create challenges in predicting where and when the impact of changes in river flow will be the most significant economically and ecologically. In response to these challenges, the United States National Aeronautics and Space Administration (NASA) established the High Mountain Asia Team (HiMAT) in 2016 to conduct research to address knowledge gaps. This paper summarizes some of the advances HiMAT made over the past 5 years, highlights the scientific challenges in improving our understanding of the hydrology of the HMA region, and introduces an integrated assessment framework to assess the impacts of climate changes on the FEWN for the HMA region. The framework, developed under a NASA HMA project, links climate models, hydrology, hydropower, fish biology, and economic analysis. The framework could be applied to develop scientific understanding of spatio-temporal variability in water availability and the resultant downstream impacts on the FEWN to support water resource management under a changing climate regime.

54 ENVIRONMENTAL SCIENCES↗

IVGEN Post Flight Analysis

The Intravenous Fluid Generation (IVGEN) Experiment was a technology demonstration experiment that purified ISS potable water, mixed it with salt, and transferred it through a sterilizing filter. On-orbit performance was verified as appropriate and two 1.5 l bags of normal saline solution were returned to earth for post-flight testing by a FDA certified laboratory for compliance with United States Pharmacopiea (USP) standards. Salt concentration deviated from required values and an analysis identified probable causes. Current efforts are focused on Total Organic Content (TOC) testing, and shelf life.The Intravenous Fluid Generation (IVGEN) Experiment demonstrated the purification of ISS potable water, the mixing of the purified water with sodium chloride, and sterilization of the solution via membrane filtration. On-orbit performance was monitored where feasible and two 1.5-liter bags of normal saline solution were returned to earth for post-flight testing by a FDA-registered laboratory for compliance with United States Pharmacopeia (USP)standards [1]. Current efforts have been focused on challenge testing with identified [2] impurities (total organic-carbon), and shelf life testing. The challenge testing flowed known concentrations of contaminants through the IVGEN deionizing cartridge and membrane filters to test their effectiveness. One finding was that the filters and DI-resin themselves contribute to the contaminant load during initial startup, suggesting that the first 100 ml of fluid be discarded. Shelf life testing is ongoing and involves periodic testing of stored DI cartridges and membrane filters that are capped and sealed in hermetic packages. The testing is conducted at six month intervals measuring conductivity and endotoxins in the effluent. Currently, the packaging technique has been successfully demonstrated for one year of storage testing. The USP standards specifies that the TOC be conducted at point of generation as opposed to point of consumption. Samples were generated and shipped to an FDA facility however, testing determined that the samples failed the TOC specification with most likely due to leaching from the sample container. Shelf life testing is examining packaging techniques and periodic testing of samples of DI cartridges that are capped and sealed in hermetic packages. Periodic testing of the purified water output will be conducted at six month intervals.

microgravity applications↗

Cold crucible Czochralski for solar cells

The efficiency and radiation resistance of present silicon solar cells are a function of the oxygen and carbon impurities and the boron doping used to provide the proper resistivity material. The standard Czochralski process used grow single crystal silicon contaminates the silicon stock material due to the use of a quartz crucible and graphite components. The use of a process which replaces these elements with a water cooled copper to crucible has provided a major step in providing gallium doped (100) crystal orientation, low oxygen, low carbon, silicon. A discussion of the Cold Crucible Czochralski process and recent float Zone developments is provided.

Trumble, T. M.↗

Overview of the first Wendelstein 7-X long pulse campaign with fully water-cooled plasma facing components

After a long device enhancement phase, scientific operation resumed in 2022. The main new device components are the water cooling of all plasma facing components and the new water-cooled high heat flux divertor units. Water cooling allowed for the first long-pulse operation campaign. A maximum discharge length of 8 min was achieved with a total heating energy of 1.3 GJ. Safe divertor operation was demonstrated in attached and detached mode. Stable detachment is readily achieved in some magnetic configurations but requires impurity seeding in configurations with small magnetic pitch angle within the edge islands. Progress was made in the characterization of transport mechanisms across edge magnetic islands: Measurement of the potential distribution and flow pattern reveals that the islands are associated with a strong poloidal drift, which leads to rapid convection of energy and particles from the last closed flux surface into the scrape-off layer. Using the upgraded plasma heating systems, advanced heating scenarios were developed, which provide improved energy confinement comparable to the scenario, in which the record triple product for stellarators was achieved in the previous operation campaign. However, a magnetic configuration-dependent critical heating power limit of the electron cyclotron resonance heating was observed. Exceeding the respective power limit leads to a degradation of the confinement.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Rate Coefficients for OH + NO (+N 2 ) in the Fall-off Regime and the Impact of Water Vapor

The termolecular, association reaction between OH and NO is a source of nitrous acid (HONO), an important atmospheric trace gas. Rate coefficients for the title reaction as recommended by evaluation panels differ substantially at the temperatures and pressures that prevail in the Earth’s boundary layer where the reaction is in the fall-off regime between low- and high-pressure limiting rate coefficients. Using pulsed laser methods for generation and detection of OH, we have reinvestigated the kinetics of the title reaction at pressures of 22–743 Torr (1 Torr = 1.333 hPa) and temperatures (273, 298, and 333 K) in pure N 2 and in N 2 –H 2 O bath gases. In situ optical absorption measurements were used to rule out any bias due to NO 2 or HONO impurities. Our rate coefficients (k 1 ) in N 2 bath gas are parametrized in terms of low-pressure (k o ) and high-pressure (k ∞ ) rate coefficients and a fall-off parameter (F C ) with k 1,0 N 2 = 7.24 × 10 –31 (T/300 K) –2.17 cm 6 molecule –2 s –1 , k 1,∞ = 3.3 × 10 –12 (T/300 K) –3 cm 3 molecule –1 s –1 , and F C = 0.53. Used with the “Troe” expression for termolecular reactions, these parameters accurately reproduce the current data in the fall-off regime and also capture literature rate coefficients at extrapolated temperatures. The presence of water vapor was found to enhance the rate coefficients of the title reaction significantly. The low-pressure limiting rate coefficient in H 2 O bath gas is a factor 5–6 larger than in N 2 , at room temperature (k 1,o H 2 O = 4.55 × 10 –30 (T/300 K) –4.85 cm 6 molecule –2 s –1 ) indicating that H 2 O is much more efficient in quenching the association complex HONO* through collisional energy transfer. Based on measurements in N 2 –H 2 O mixtures, a parametrization of k 1 including both N 2 and H 2 O as third-body quenchers was derived. Neglecting the effect of H 2 O results, e.g., in an underestimation of k 1 by >10% in the tropical boundary layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Reduction of Flue Gas Carbon Dioxide to Commercially Viable C2-C4 Products (Final Report)

This is the final scientific/technical report for a DOE project focused on the electrochemical conversion of CO 2 in non-aqueous solvents to novel products. Electrochemical reduction of CO 2 provides an attractive route to produce valuable fuels and chemicals that can simultaneously lower greenhouse gas emissions when powered by renewable electricity. While recent technological advances have shown the feasibility of industrial CO 2 electroreduction, many challenges remain to improve this technology and expand the list of economically viable products. The vast majority of electrochemical CO 2 reduction research has been conducted in aqueous media under neutral to alkaline conditions, leading to commonly reported products including carbon monoxide, formic acid, methane, methanol, ethylene, acetic acid, and ethanol. In comparison, non-aqueous media for CO 2 reduction has been underexplored but represents a possible avenue to yield new products and improved operating conditions. The aim of the project was to convert waste CO 2 in the form of flue gas to a multicarbon C2 - C4 chemical product in a reactor designed to achieve economically competitive values of current density and selectivity. The project strived to advance the technology readiness of an electrochemical CO 2 reduction process in alcohol solvents from the proof-of-concept stage to a device capable of meeting performance metrics for commercial viability. In the initial plan, the University of Louisville researchers were to focus on investigating the electrochemical process and improving the faradaic efficiency for novel C2 – C4 species, while also working on a parallel effort to build a practical electrolysis reactor to markedly increase the CO 2 reduction current density. The reactor development effort also aimed to engineer a dual-electrolyte feed strategy with non-aqueous catholyte and aqueous anolyte to promote water oxidation as the coupling anodic half-reaction to enable a sustainable and economical overall process. At the outset, the University of North Dakota was to investigate the feasibility of operating directly from coal-derived flue gas without separate capture and purification. The research team sought to determine impurity effects and test mitigation strategies, as well as engineer the gaseous feed system for high reactor tolerance to lower CO 2 concentration. In the last half year of the project, the focus was planned to shift to integrating the advances in the catalysis, electrochemical conditions, reactor design, and flue gas compatibility into a fully functional device and improve it for maximum current density and faradaic efficiency for C2 – C4 species. Knowledge of the full system components, constraints, and maximum performance was then to be used as the basis for a thorough technoeconomic analysis (TEA) and life cycle analysis (LCA) at the end of the project.

01 COAL, LIGNITE, AND PEAT↗

Environmentally Assisted Cracking Research for Current and Advanced Nuclear Structural Materials

Understanding environmentally assisted cracking is an important aspect of nuclear materials research, as it provides information about failure mechanisms that lead to safety concerns or shutdowns. Idaho National Laboratory has ongoing research to understand how materials behave in the harsh nuclear environments for both the current fleet of light water reactors, as well as advanced reactors, where materials are exposed to more extreme environments. Corrosion and cracking of current materials, advanced materials, and materials formed through advanced manufacturing techniques are being examined, with particular interest in irradiation effects on corrosion and cracking, as well as the effects of environmental impurities. Testing, such as stress corrosion cracking, corrosion fatigue, and in-situ crack growth measurements, as well as a suite of characterization tools, including electron microscopy techniques and x-ray computed tomography, are being utilized to better understand the material response, limitations, and cracking mechanisms to ensure safe and reliable nuclear plants.

36 MATERIALS SCIENCE↗

Selective material recovery from solution

Embodiments relate to methods for generating selected materials from a natural brine, where the natural brine is sea water, saline water, fresh water, synthetic solutions, or industrial liquid wastes. A natural brine comprising at least a portion of a selected material is heated. CO 2 is added and mixes with the natural brine forming a mixture such that the CO 2 /P is a first predetermined value. The mixture is held so that impurities in the natural brine precipitate as solids leaving a second brine substantially comprising the selected material. The second brine is heated. CO 2 gas is injected into the second brine, mixing so that the CO 2 /P is a second predetermined value. The mixture is held so that the selected material precipitates out and are removed.

Nakano, Jinichiro↗

Cost Competitive Process of Battery Grade Oxides Preparation from Aged LIBS

The increasing demand for lithium-ion batteries (LIBs ) is driving development of advanced recycling and refining methods. In this project, new cathode active materials are prepared from recycled lithium battery materials and subsequently electrochemically evaluated in coin cells. In detail, scrap LIBs were mechanically processed into a metal rich black mass, then reductive acid leached into an aqueous metal solution, and finally high-purity metal hydroxide precursor materials were prepared by selective electrochemical flow precipitation. Closed-loop LIB recycling into active electrode materials will enable US manufacturers to break their reliance on foreign sources of critical materials. For example, electroextraction process used here has potential to significantly reduce chemical & water use as compared to traditional metallurgic techniques. To this end, electroextracted materials refined from used batteries were collected and processed to be tested as precursor cathode active material (pCam).During this project ,samples of high-purity recycled NMC hydroxide (~2kg each) were received from Nth Cycle. In the first received batch some impurities like cadmium, calcium, and sodium are present in quantities that would negatively impact battery performance. Nth Cycle indicated that the impurities such as cadmium are present due to poor battery separation and co-shredding of NiCd batteries with with LIB. Cadmium was not present in the two subsequent batches as Nth Cycle processed cadmium free black mass. Thus, effective recycled battery sorting is critical to closed-loop LIB recycling into active electrode materials.

99 GENERAL AND MISCELLANEOUS↗

Narrowing the band gap and suppressing electron–hole recombination in β-Fe 2 O 3 by chlorine doping

Here, the effects of halogen (F, Cl, Br, I, and At) doping in the direct-band-gap β-Fe 2 O 3 semiconductor on its band structures and electron–hole recombination have been investigated by density functional theory. Doping Br, I, and At in β-Fe 2 O 3 leads to transformation from a direct-band-gap semiconductor to an indirect-band-gap semiconductor because their atomic radii are too large; however, F- and Cl-doped β-Fe 2 O 3 remain as direct-band-gap semiconductors. Due to the deep impurity states of the F dopant, this study focuses on the effects of the Cl dopant on the band structures of β-Fe 2 O 3 . Two impurity levels are introduced when Cl is doped into β-Fe 2 O 3 , which narrows the band gap by approximately 0.3 eV. After doping Cl, the light-absorption edge of β-Fe 2 O 3 redshifts from 650 to 776 nm, indicating that its theoretical solar to hydrogen efficiency for solar water splitting increases from 20.6% to 31.4%. In addition, the effective mass of the holes in halogen-doped β-Fe 2 O 3 becomes significantly larger than that in undoped β-Fe 2 O 3 , which may suppress electron–hole recombination.

30 DIRECT ENERGY CONVERSION↗

Cost Competitive Process of Battery Grade Oxides Preparation from Aged LIBS

The increasing demand for lithium-ion batteries (LIBs) is driving development of advanced recycling and refining methods. In this project, new cathode active materials are prepared from recycled lithium battery materials and subsequently electrochemically evaluated in coin cells. In detail, scrap LIBs were mechanically processed into a metal rich black mass, then reductive acid leached into an aqueous metal solution, and finally high-purity metal hydroxide precursor materials were prepared by selective electrochemical flow precipitation. Closed-loop LIB recycling into active electrode materials will enable US manufacturers to break their reliance on foreign sources of critical materials. For example, electroextraction process used here has potential to significantly reduce chemical & water use as compared to traditional metallurgic techniques. To this end, electroextracted materials refined from used batteries were collected and processed to be tested as precursor cathode active material (pCam). During this project , samples of high-purity recycled NMC hydroxide (~2 kg each) were received from Nth Cycle. In the first received batch some impurities like cadmium, calcium, and sodium are present in quantities that would negatively impact battery performance. Nth Cycle indicated that the impurities such as cadmium are present due to poor battery separation and co-shredding of NiCd batteries with with LIB. Cadmium was not present in the two subsequent batches as Nth Cycle processed cadmium free black mass. Thus, effective recycled battery sorting is critical to closed-loop LIB recycling into active electrode materials.

25 ENERGY STORAGE↗

The effects of surface pretreatment and nitrogen tetroxide purification on the corrosion rate of Type 304L stainless steel

Corrosion rates of 304L stainless steel coupons in MON-1 oxidizer have been measured as a function of cleaning procedures employed, surface layer positions, propellant impurity levels, and short-term exposure durations (14 to 90 days). Of special interest was propellant contamination by buildup of soluble iron, which may cause flow decay. Surface treatments employed were combinations of cleaning, pickling, and passivation procedures. Propellants used were MIL-SPEC MON-1 and several types of purified NTO (i.e., low water, low chloride) which may, at a later time, be specified as spacecraft grade. Pretest coupon surface analysis by X-ray photoelectron spectroscopy (XPS-ESCA) has revealed important differences, for the different cleaning procedures, in the make-up of the surface layer, both in composition and state of chemical combination of the elements involved. Comparisons will be made of XPS/ESCA data, for different cleaning procedures, for specimens before and after propellant exposure.

Blue, G. D.↗

Hydroxylation and Cation Segregation in (La 0.5 Sr 0.5 )FeO 3-$δ$ Electrodes

Simultaneously achieving high activity and stability is the primary challenge when engineering (electro)catalysts. Transition metal perovskite oxides are employed as air electrodes for solid-oxide fuel cells and electrolyzers. However, degradation of oxygen exchange kinetics at the solid–gas interface, often linked to alkaline-earth cation segregation and precipitation, limits widespread commercialization. Here, we systematically investigated the surface degradation mechanism induced by gas-phase impurities in La 0.5 Sr 0.5 )FeO 3-$δ$ (LSF55) thin-film electrodes by varying the concentration of H 2 O, SO 2 , and CO 2 . Degradation of the area-specific resistance in ambient and humidified synthetic air is significantly greater than in dry ambient and dry synthetic air, pointing to the importance of water vapor. Time-resolved, in situ ambient pressure X-ray photoelectron spectroscopy performed in O 2 showed that nonbulk Sr is present on the surface before the exposure to water vapor. Upon introduction of water vapor, neither additional Sr segregation nor precipitation driven by water vapor is a necessary condition for degradation. Rather, hydroxylation of the surface induces irreversible and significant degradation. At the same time, we show that Sr migration driven by water vapor is partially reversible. These fundamental insights can be used for the rational design of electrodes with improved catalytic stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗