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At least 163 records · Page 9

Processing of sintered alpha SiC

Processing methods of sintered alpha SiC for engine applications are developed in a cost effective manner, using a submicron sized powder blended with sintering aids (boron and carbon). The processes for forming a green powder compact, such as dry pressing, cold isostatic pressing and green machining, slip casting, aqueous extrusion, plastic extrusion, and injection molding, are described. Dry pressing is the simplest route to component fabrication, and is carried out at approximately 10,000 psi pressure, while in the cold isostatic method the pressure could go as high as 20,000 psi. Surfactants are added to control settling rates and casting characteristics in the slip casting. The aqueous extrusion process is accomplished by a hydraulic ram forcing the aqueous mixture through a die. The plastic forming processes of extrusion and injection molding offer the potential of greater diversity in shape capacity. The physical properties of sintered alpha SiC (hardness, Young's modulus, shear modulus, and thermal diffusivity) are extensively tested. Corrosion resistance test results of silicon carbide are included.

Storm, R. S.↗

A versatile enhanced freeze-substitution protocol for volume electron microscopy

Volume electron microscopy, a powerful approach to generate large three-dimensional cell and tissue volumes at electron microscopy resolutions, is rapidly becoming a routine tool for understanding fundamental and applied biological questions. One of the enabling factors for its adoption has been the development of conventional fixation protocols with improved heavy metal staining. However, freeze-substitution with organic solvent-based fixation and staining has not realized the same level of benefit. Here, we report a straightforward approach including osmium tetroxide, acetone and up to 3% water substitution fluid (compatible with traditional or fast freeze-substitution protocols), warm-up and transition from organic solvent to aqueous 2% osmium tetroxide. Once fully hydrated, samples were processed in aqueous based potassium ferrocyanide, thiocarbohydrazide, osmium tetroxide, uranyl acetate and lead acetate before resin infiltration and polymerization. We observed a consistent and substantial increase in heavy metal staining across diverse and difficult-to-fix test organisms and tissue types, including plant tissues ( Hordeum vulgare ), nematode ( Caenorhabditis elegans ) and yeast ( Saccharomyces cerevisiae ). Our approach opens new possibilities to combine the benefits of cryo-preservation with enhanced contrast for volume electron microscopy in diverse organisms.

59 BASIC BIOLOGICAL SCIENCES↗

Local Molecular Field Theory for Coulomb Interactions in Aqueous Solutions

Coulomb interactions play a crucial role in a wide array of processes in aqueous solutions but present conceptual and computational challenges to both theory and simulations. We review recent developments in an approach addressing these challenges–local molecular field (LMF) theory. LMF theory exploits an exact and physically suggestive separation of intermolecular Coulomb interactions into strong short-range and uniformly slowly varying long-range components. This allows us to accurately determine the averaged effects of the long-range components on the short-range structure using effective single particle fields and analytical corrections, greatly reducing the need for complex lattice summation techniques used in most standard approaches. Furthermore, the simplest use of these ideas in aqueous solutions leads to the short solvent (SS) model, where both solvent–solvent and solute–solvent Coulomb interactions have only short-range components. Here we use the SS model to give a simple description of pairing of nucleobases and biologically relevant ions in water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Local topography of Mars and its relationship to surface weathering processes

There is a growing body of evidence in favor of the importance of aqueous sedimentary processes on Mars. It is important to understand the role that surface weathering processes have played in the development of the present morphology of the Martian surface. Such an understanding is important not only for its relevance to the study of volatile sources and sinks on Mars through time, but also for its relevance to Martian geologic and tectonic history. Starting in the fall of this year, the Mars Observer Laser Altimeter will begin sending back to Earth data on the topography of Mars that is of a higher quality than most of the topography data available for the Earth. This data will be invaluable, not only for understanding global and large-scale regional processes and landforms on Mars, but also for the study of local and smaller-scale regional processes and landforms. Digital topography is an important part of geologic and geomorphic studies, useful in distinguishing between different lithologies and between different types of weathering. Digital topography data may be used to study a wide variety of local and regional-scale landforms, including valleys, sand dunes, lava flows, landslides, and slopes. Topography data are also essential to the analysis of spectral response patterns, especially in areas of high topographic relief. Geomorphic classification can be significantly improved by the addition of topographic information.

Schaefer, M. W.↗

X-ray Amorphous Components of Antarctica Dry Valley Soils: Weathering Implications for Mars

The Antarctic Dry Valleys (ADV) comprise the largest ice-free region of Antarctica. Precipitation usually occurs as snow, relative humidity is frequently low, and mean annual temperatures are about -20°C [1]. Substantial work has focused on soil formation in the ADVs [2], however, little work has focused on the mineralogy of secondary alteration phases. The dominant weathering process in the ADV region is physical weathering, however, chemical weathering has been well documented [3]. The occurrence of chemical weathering processes are suggested by the presence of clay minerals and iron and titanium oxides in soil. Previously we have investigated soils from two sites in the ADV’s and have shown evidence of chemical weathering by the presence of clay minerals (vermiculite, smectite), short-range ordered (SRO) and/or X-ray amorphous materials, and Fe- and Tioxides as well as the presence of discrete calcite crystals [4, 5]. The Chemistry and Mineralogy (CheMin) instrument onboard the Mars Curiosity rover has detected abundant amounts (approx. 25-30 wt. %) of X-ray amorphous materials in a windblown deposit or “soil” (Rocknest) and in a sedimentary rocks [6,7,8]. The occurrence of large amounts of X-ray amorphous materials in Mars sediments is surprising because these materials are usually present in small quantities in terrestrial environments. The objective of this study is to further characterize the chemistry and mineralogy, specifically the secondary alteration mineralogy and the presence of X-ray amorphous material, of soils from two sites we have previously studied, a subxerous soil in Taylor Valley, and an ultraxerous soil in University Valley. While the chemical alteration processes and mineralogy of the ADV has been documented previously, there has been limited discussion on the occurrence and formation of X-ray amorphous and SRO materials in Antarctica soils. The process of aqueous alteration in the ADVs may have implications for pedogenic processes on Mars, and may lead to a better understanding to the abundance of amorphous material found in sediments in Gale crater.

Quinn, J. E.↗

Development of Magnesium Oxysulfate Formulation for SRPPF Aqueous Recovery Liquid Solidification

The liquid effluent from the Savannah River Plutonium Processing Facility (SRPPF) Aqueous Recovery Processes will be solidified into a stable form that is acceptable by Waste Isolation Pilot Plant (WIPP) for disposal. The current Aqueous Recovery flow sheet proposes to solidify the liquid effluent using a grout formula that was developed and tested for the former Waste Solidification Building process. This Portland cement based mixture results in a high pH (~13) leachate from the solidified waste form which is not acceptable to WIPP in the large quantities expected from production at SRPPF. Various cementitious materials were previously evaluated as alternative grout formulations to Portland cement and a MgO-based mix was identified as a promising alternative. A magnesium oxysulfate (MOS) cement formulation comprised of reactive magnesium oxide (MgO), anhydrous magnesium sulfate (MgSO 4 ), and sand, as a non-reactive heat sink provided good mixability, similar density to the original Portland-cement based mix, and a leachate pH of 9.4, within the assumed WIPP brine pH range. However, the MOS formulation exhibited an appreciable amount of heat generation, which resulted in premature setting of a large-scale test.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Modelling the Liquid Waste Operation at the Savannah River Site

Modeling Successes Dounreay – Site Closure Optimization and Risk Reduction Re-structuring and streamlining a complex project plan to achieve site decommissioning in reduced time and at reduced cost, through automated task prioritization. Idaho AMWTP – Multi-stream Optimization Speeding up a complex facility with many process lines, by utilizing all of the process lines more efficiently and reducing overall plant downtime, by coordinating repairs and shutdowns. AWE –Waste Repackaging and Relocation Relocating schedule for waste material from an old storage facility to a new purpose-built one, safely, and in a timely fashion that removed the need to reassure the safety of the old facility. Sellafield – Effluent, Sludge and HAW Treatment Improving a wide range of chemical engineered processes including aqueous effluent treatment, chemically-reactive sludge management and waste vitrification processing. Strategic Petroleum Reserve – Cavern Management Linking chemistry models of petroleum prediction, through engineering cavern management to financial modeling of gasoline sales to benefit US government

Jung, Andrew W.↗

Concentration-Dependent Solvation Structure and Dynamics of Aqueous Sulfuric Acid Using Multinuclear NMR and DFT

Sulfuric acid is a ubiquitous compound for industrial processes and aqueous sulfate solutions also play a critical role in electrolytes for many prominent battery chemistries. While the thermodynamic literature for it is quite well-developed, comprehensive studies of the solvation structure, and particularly molecular-scale dynamical and transport properties, are less available. This study applies a multinuclear NMR approach to the elucidation of the solvation structure and dynamics over a wide temperature (-10 – 50?C) and concentration (0 – 18 M) range, combining 17O shift, linewidth, and T1 relaxation measurements, 33S shift and linewidth measurements, and 1H PFG-NMR measurements of the proton self-diffusivity. In conjunction, these results indicate a crossover between two regimes of solvation structure and dynamics, occurring above the concentration associated with the deep eutectic point (~ 4.5 M), with the high-concentration regime dominated by strong water-sulfate correlation. This description was borne out in detail by the activation energy trends with increasing concentration derived from the relaxation of both the H2O/H3O+ and H2SO4/HSO4-/SO42- 17O resonances and the 1H self-diffusivity. However, the 17O chemical shift difference between the H2O/H3O+ and H2SO4/HSO4-/SO42- resonances across the entire temperature range is nevertheless strikingly linear. A computational approach coupling MD simulations and DFT NMR shift calculations to reproduce this trend is presented, which will be the subject of further development. This combination of multinuclear, dynamical NMR and computational methods, and the results furnished by this study, will provide a platform for future studies on battery electrolytes where aqueous sulfate chemistry plays a central role in the solution structure.

Bazak, Jonathan D.↗

Electrochemical reduction of per- and polyfluorinated alkyl substances (PFAS): is it possible? Applying experimental and quantum mechanical insights from the reductive defluorination literature

Remediation of per- and polyfluorinated alkyl substances (PFAS) in global water systems is a critical human and environmental health challenge facing society. PFAS consumption is associated with a litany of adverse health effects, and our knowledge of these dangers is still evolving. Current techniques to remove PFAS from water include adsorption to media (e.g. granular activated carbon, ion-exchange resin), nanofiltration, and reverse osmosis. However, these processes create a concentrated PFAS residual that requires further management. Destructive techniques are therefore needed to detoxify these residuals. Oxidative techniques have garnered the most attention (e.g. supercritical water oxidation, electrochemical oxidation) but are energy intensive and potentially form toxic by-products. As an alternative, several groups have researched advanced reduction processes that form aqueous electrons, but these processes are still chemical and energy intensive (e.g. ultraviolet/SO 3 2− , electron beam). This concise review therefore focuses on whether electrochemical reduction — a chemical-free, modular process — could be technically feasible for PFAS destruction.

King, Jacob F.↗

Dynamic stability of a crude oil/brine interface: Effect of anion type

The chemical composition of the aqueous phase plays an essential role in water-based enhanced-oil recovery processes. The aqueous phase ionic profile affects the snap-off response of a crude oil-brine system by linking it to the brine-crude oil interfacial rheology. In this work, we focus on the effect of the anion on the snap-off response. To this end, a sample of crude oil from the Minnelusa Sandstone formation in Wyoming was selected, and several aqueous solutions were prepared with salts containing sodium cation and different anions (chlorides, sulfates, and phosphates) at two ionic strength values, 0.6 M and 6 mM, as cases of high- and low-salinity water. Interfacial tension, interfacial viscoelasticity and interface stability were analyzed as functions of aging time using pendant drop, dilatational rheology, and liquid bridge techniques, respectively. Here the results show that solutions with higher ionic strength led to the formation of more rigid interfaces, i.e. higher elastic modulus, and faster formation kinetics. In the low-salinity regime, solutions with polyvalent anions produce more viscoelastic interfaces at faster rates than solutions with monovalent anions. Finally, an excellent correlation (R 2 greater than 0.97) between the relative stability of the interfacial film, predicted in liquid bridge tests, and the ratio of interfacial tension and interfacial elastic modulus was found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nature of Reduced Carbon in Martian Meteorites

Martian meteorites provide important information on the nature of reduced carbon components present on Mars throughout its history. The first in situ analyses for carbon on the surface of Mars by the Viking landers yielded disappointing results. With the recognition of Martian meteorites on Earth, investigations have shown carbon-bearing phases exist on Mars. Studies have yielded presence of reduced carbon, carbonates and inferred graphitic carbon phases. Samples ranging in age from the first approximately 4 Ga of Mars history [e.g. ALH84001] to nakhlites with a crystallization age of 1.3 Ga [e.g. Nakhla] with aqueous alteration processes occurring 0.5-0.7 Ga after crystallizaton. Shergottites demonstrate formation ages around 165-500 Ma with younger aqueous alterations events. Only a limited number of the Martian meteorites do not show evidence of significance terrestrial alterations. Selected areas within ALH84001, Nakhla, Yamato 000593 and possibly Tissint are suitable for study of their indigenous reduced carbon bearing phases. Nakhla possesses discrete, well-defined carbonaceous phases present within iddingsite alteration zones. Based upon both isotopic measurements and analysis of Nakhla's organic phases the presence of pre-terrestrial organics is now recognized. The reduced carbon-bearing phases appear to have been deposited during preterrestrial aqueous alteration events that produced clays. In addition, the microcrystalline layers of Nakhla's iddingsite have discrete units of salt crystals suggestive of evaporation processes. While we can only speculate on the origin of these unique carbonaceous structures, we note that the significance of such observations is that it may allow us to understand the role of Martian carbon as seen in the Martian meteorites with obvious implications for astrobiology and the pre-biotic evolution of Mars. In any case, our observations strongly suggest that reduced organic carbon exists as micrometer- size, discrete structures on Mars associated with clay and salt minerals. The Mars Science Laboratory s investigators should be aware of reduced organic carbon components within clay-bearing phases.

Gibson, Everett K., Jr.↗

Aqueous alteration on the hydrous asteroids - Results of EQ3/6 computer simulations

The two models of carbonaceous chondrite precursor material presently formulated to study the process of aqueous alteration in hydrous asteroids are based, in the first case, on the anhydrous mineralogy of CM chondrites, while the second is based on that of the CV chondrites. It is noted that the alteration mineralogy of the CM chondrites and their parent asteroids may be produced by starting with the anhydrous mineralogy of the same CM chondrites, at temperatures in the 1-25 C range, with a wide variety of rock/fluid ratios. The mineralogy of the important CI chondrites is reproducible through the alteration of either CM or CV anhydrous material, at temperatures in the 50-150 C.

Zolensky, Michael E.↗

Anions Enhance Rare Earth Adsorption at Negatively Charged Surfaces

Anions are expected to be repelled from negatively charged surfaces. At aqueous interfaces, however, ion-specific effects can dominate over direct electrostatic interactions. Using multiple in situ surface sensitive experimental techniques, we show in this study that surface affinities of SCN – anions are so strong that they can adsorb at a negatively charged floating monolayer at the air–aqueous interface. This extreme example of ion-specific effects may be very important for understanding complex processes at aqueous interfaces, such as chemical separations of rare earth metals. Adsorbed SCN – ions at the floating monolayer increase the overall negative charge density, leading to enhanced trivalent rare earth adsorption. Surface sensitive X-ray fluorescence measurements show that the surface coverage of Lu 3+ ions can be triple the apparent surface charge of the floating monolayer in the presence of SCN – . Comparison to NO 3 – samples shows that the effects are strongly dependent on the character of the anion, providing further evidence of ion-specific effects dominating over electrostatics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cost-Benefit Assessment of Krypton and Xenon Recovery from Aqueous Reprocessing

The purpose of this paper is to provide an understanding of the cost-benefit of capturing Kr and Xe from the existing process of aqueous reprocessing of UNF. The study accomplishes this with a market assessment of Xe prices and volumes today, coupled with a cost estimate of Kr and Xe capture out of cryogenic distillation within aqueous reprocessing. The market assessment shows that the average price of Xe is about $\$ $60/L while the average price of Kr is about $\$ $1/L. The assessment also shows that the market structure for Xe is one of oligopoly, in other words, very few suppliers to the Xe market. The assessment shows growing demand for Xe, particularly in medical applications like anesthesia. The cost assessment finds the unit cost of Xe to range from $\$ $71.50/L to $\$ $131.13/L. This range is only slightly above the current range of market prices today, and with growing demand for Xe, prices could reach the range it would take to support extraction of Xe from aqueous reprocessing. On the other hand, the estimated cost range for Kr is $\$ $830.15/L up to $\$ $1,522.52/L, which far exceeds the range of market prices for Kr. However, as the text notes, Kr capture is already part of aqueous reprocessing so these costs are sunk costs (already incurred) whereas the cost estimates for Xe are marginal cost (if Xe is desired, then the cost estimate would result from the Xe capture).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Zeolite Formation and Weathering Processes Within the Martian Regolith: An Antarctic Analog

As more information is obtained about the nature of the surface compositions and processes operating on Mars, it is clear that significant erosional and depositional features are present on the surface. Apparent aqueous or other fluid activity on Mars has produced many of the erosional and outflow features observed. Evidence of aqueous activity on Mars has been reported by earlier studies. Gooding and colleagues championed the cause of pre-terrestrial aqueous alteration processes recorded in Martian meteorites. Oxygen isotope studies on Martian meteorites by Karlsson et al. and Romenek et al. gave evidence for two separate water reservoirs on Mars. The oxygen isotopic compositions of the host silicate minerals was different from the oxygen isotopic composition of the secondary alteration products within the SNC meteorites. This implied that the oxygen associated with fluids which produced the secondary alteration was from volatiles which were possibly added to the planetary inventory after formation of the primary silicates from which the SNC s were formed. The source of the oxygen may have been from a cometary or volatile-rich veneer added to the planet in its first 600 million years.

Gibson, E. K.↗

Insights into the Martian Regolith from Martian Meteorite Northwest Africa 7034

Everything we know about sedimentary processes on Mars is gleaned from remote sensing observations. Here we report insights from meteorite Northwest Africa (NWA) 7034, which is a water-rich martian regolith breccia that hosts both igneous and sedimentary clasts. The sedimentary clasts in NWA 7034 are poorly-sorted clastic siltstones that we refer to as protobreccia clasts. These protobreccia clasts record aqueous alteration process that occurred prior to breccia formation. The aqueous alteration appears to have occurred at relatively low Eh, high pH conditions based on the co-precipitation of pyrite and magnetite, and the concomitant loss of SiO2 from the system. To determine the origin of the NWA 7034 breccia, we examined the textures and grain-shape characteristics of NWA 7034 clasts. The shapes of the clasts are consistent with rock fragmentation in the absence of transport. Coupled with the clast size distribution, we interpret the protolith of NWA 7034 to have been deposited by atmospheric rainout resulting from pyroclastic eruptions and/or asteroid impacts. Cross-cutting and inclusion relationships and U-Pb data from zircon, baddelleyite, and apatite indicate NWA 7034 lithification occurred at 1.4-1.5 Ga, during a short-lived hydrothermal event at 600-700 C that was texturally imprinted upon the submicron groundmass. The hydrothermal event caused Pb-loss from apatite and U-rich metamict zircons, and it caused partial transformation of pyrite to submicron mixtures of magnetite and maghemite, indicating the fluid had higher Eh than the fluid that caused pyrite-magnetite precipitation in the protobreccia clasts. NWA 7034 also hosts ancient 4.4 Ga crustal materials in the form of baddelleyites and zircons, providing up to a 2.9 Ga record of martian geologic history. This work demonstrates the incredible value of sedimentary basins as scientific targets for Mars sample return missions, but it also highlights the importance of targeting samples that have not been overprinted by metamorphic processes, which is the case for NWA 7034.

McCubbin, Francis M.↗

Phyllosilicate absorption features in main-belt and outer-belt asteroid reflectance spectra

Absorption features having depths up to 5 percent are identified in high-quality, high-resolution reflectance spectra of 16 dark asteroids in the main belt and in the Cybele and Hilda groups. Analogs among the CM2 carbonaceous chondrite meteorites exist for some of these asteroids, suggesting that these absorptions are due to iron oxides in phyllosilicates formed on the asteroidal surfaces by aqueous alteration processes. Spectra of ten additional asteroids, located beyond the outer edge of the main belt, show no discernible absorption features, suggesting that aqueous alteration did not always operate at these heliocentric distances.

Vilas, Faith↗