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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.

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At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Cesium Ion Exchange Testing Using Crystalline Silicotitanate with Hanford Tank Waste 241-AP-107

Pacific Northwest National Laboratory has been tasked with demonstrating the unit operations for the Low Activity Waste Pretreatment System with actual Hanford tank waste. Crystalline silicotitanate (CST) ion exchange media is planned to be used to remove cesium (137Cs) from the aqueous phases of the tank wastes. Washington River Protection Solutions requested that Hanford tank waste collected from tank 241-AP-107 be processed using conceived pretreatment steps (suspended solids removal by filtration, Cs removal by ion exchange), then vitrified. Removal of Cs from these wastes is an important processing step in preparing the waste for long-term safe storage. Bench-scale ion exchange testing with approximately 9 L of filtered AP-107 supernate was conducted using CST. Column testing was performed using prototypic LAWPS operations in a lead-lag column arrangement using 10-mL CST beds. Feed was processed until the lag column effluent reached the Hanford Tank Waste Treatment and Immobilization Plant waste acceptance criteria (WAC) for receiving supernatant waste for vitrification (a function of the Na and 137Cs concentrations), at which point, a new lag column was needed to continue processing and the original lag column was moved to the lead position. Greater than 99% of the Cs processed through the ion exchange system was collected on the CST in the columns. The AP-107 feed and column processing effluent underwent extensive characterization to better define waste characteristics and assess fractionation to the CST. Selected lead column samples were analyzed to assess particular metal analyte load characteristics. Results of these analyses will be discussed.

cesium exchange, Hanford tank waste, ion exchange↗
DOE OSTI2015

The response of soil carbon storage and microbially mediated carbon turnover to simulated climatic disturbance in a northern peatland forest. Revisiting the concept of soil organic matter recalcitrance

The goal of this project was to investigate changes in the structure of dissolved and solid phase organic matter, the production of CO 2 and CH 4 , and the composition of decomposer microbial communities in response to the climatic forcing of environmental processes that determine the balance between carbon gas production versus storage and sequestration in peatlands. Cutting-edge analytical chemistry and next generation sequencing of microbial genes were been applied to habitats at the Marcell Experimental Forest (MEF), where the US DOE’s Oak Ridge National Laboratory and the USDA Forest Service are constructing a large-scale ecosystem study entitled, “Spruce and Peatland Responses Under Climatic and Environmental Change”(SPRUCE). Our study represented a comprehensive characterization of the sources, transformation, and decomposition of organic matter in the S1 bog at MEF. Multiple lines of evidence point to distinct, vertical zones of organic matter transformation: 1) the acrotelm consisting of living mosses, root material, and newly formed litter (0-30 cm), 2) the mesotelm, a mid-depth transition zone (30-75 cm) characterized by labile organic C compounds and intense decomposition, and 3) the underlying catotelm (below 75cm) characterized by refractory organic compounds as well as relatively low decomposition rates. These zones are in part defined by physical changes in hydraulic conductivity and water table depth. O-alkyl-C, which represents the carbohydrate fraction in the peat, was shown to be an excellent proxy for soil decomposition rates. The carbon cycle in deep peat was shown to be fueled by modern carbon sources further indicating that hydrology and surface vegetation play a role in belowground carbon cycling. We provide the first metagenomic study of an ombrotrophic peat bog, with novel insights into microbial specialization and functions in this unique terrestrial ecosystem. Vertical structuring of microbial communities closely paralleled the chemical evolution of peat, with large shifts in microbial populations occurring in the biogeochemical hotspot, the mesotelm, where the highest rates of decomposition were detected. Stable isotope geochemistry and potential rates of methane production paralleled vertical changes in methanogen community composition to indicate a predominance of acetoclastic methanogenesis mediated by the Methanosarcinales in the mesotelm, while hydrogen-utilizing methanogens dominated in the deeper catotelm. Evidence pointed to the availability of phosphorus as well as nitrogen limiting the microbially-mediated turnover of organic carbon at MEF. Prior to initiation of the experimental treatments, our study provided key baseline data for the SPRUCE site on the vertical stratification of peat decomposition, key enzymatic pathways, and microbial taxa containing these pathways. The sensitivity of soil carbon turnover to climate change is strongly linked to recalcitrant carbon stocks and the temperature sensitivity of decomposition is thought to increase with increasing molecular complexity of carbon substrates. This project delivered results on how climate change perturbations impact the microbially-mediated turnover of recalcitrant organic matter in peatland forest soils, both under controlled conditions in the laboratory and at the ecosystem-scale in the field. This project revisited the concept of “recalcitrance” in the regulation of soil carbon turnover using a combination of natural abundance radiocarbon and optical spectroscopic measurements on bulk DOM, and high resolution molecular characterization of DOM. The project elucidated how organic matter reactivity and decomposition will respond to climate change in a both a qualitative (organic matter lability) and quantitiative (increased rates) manner. An Aromaticity Index was developed to represent a more direct and accurate parameter for modeling of DOM reactivity in peatlands. The abundance and community composition of soil microorganisms that mediate C cycling were interrogated with depth in the peat, with season, and in manipulated climate enclosures at unprecedented resolution. Therefore this project delivered strategic new insights on the functioning of peatland ecosystems that collectively store approximately one-third of the world's soil carbon. Furthermore, results from the detailed characterization of DOM lability and microbial community structure/ function will be employed to further develop biogeochemical models to include microbial respiration pathways as well as to track carbon flow with a term that incorporates relative reactivity based on aromaticity index. As it stands now, detailed soil organic matter structure and microbial parameters are not included in Earth system models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Fiscal Year 2022. Filtration of Hanford Tank 241-AP-101 Supernatant at 16 °C

Bench-scale filtration testing of ~9 liters of supernatant from Hanford waste tank 241-AP-101, chilled to 16 °C, was conducted using a backpulse dead-end filter (BDEF) filtration system equipped with a feed vessel and a Mott inline filter Model 6610 (Media Grade 5) in the hot cells of the Radiochemical Processing Laboratory at Pacific Northwest National Laboratory. This was done to assess the performance of the anticipated third feed to the Tank Side Cesium Removal (TSCR) system. The as-received samples were diluted to the target sodium concentration and transferred to 1.5-liter polyethylene bottles and held at 16 °C for approximately 1 week prior to filtration. The feed was filtered through the BDEF system at a targeted flux of 0.065 gpm/ft 2 to match the prototypic operation of the TSCR system. During filtration, the differential pressure required to effect filtration at 0.065 gpm/ft 2 increased little over the filtration campaign and never reached 2 psid (the TSCR action limit). This indicates that the TSCR filter should perform well when processing AP-101 supernatant. After completing filtration of the AP-101 feed, the filter was cleaned. Solids concentrated from the backpulse solutions displayed sodium nitrate-type phases, aluminum and silicon phases reported as cancrinite or nitrate-cancrinite, a mixed chromium-aluminum oxide, iron oxides, and Ca-bearing phases (calcite). Scanning electron microscopy analyses showed that the average particle size was 0.5 micron.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Mass transport in a highly immiscible alloy on extended shear deformation

Forced mixing to a single phase or supersaturated solid solution (SSS) and its prerequisite microstructure evolution in immiscible systems has been a focus of research for both fundamental science and a variety of applications. Controlling the formation of SSS by shear deformation assisted processing could enable a material design beyond conventional equilibrium microstructure in immiscible systems. Here, a highly immiscible (mixing enthalpy of ~ 20 kJ·mol -1 ) Cu-50 at. % Cr binary alloy was employed to investigate the microstructure evolution and localized tendencies of SSS during severe shear deformation. The present results demonstrate distinctive microstructure refinement process in each phase and how they lead to localized SSS as a function of shear strain. Preferential dynamic recrystallization occurs in the softer Cu phase due to strain localization, leading to substantial grain refinement. The refinement of Cr phase in the top-most layer, however, is enabled by the progressive evolution of grain lamination, splitting, and fragmentation as a function of shear strain. The eventual SSS is found to be strongly dependent on the local environments that affect the dislocation activity, including the level of microstructure refinement, the interfacial orientation relationship, hardness difference, and supposed stability of oxidation. Ab initio simulations comfirm that it is more favorable to oxidize Cr than Cu at incoherent Cu/Cr interfaces which then limits the mass transport on an incoherent boundary. Our results shed light on the underpinning mechanism for non-equilibrium mass transport in immiscible systems upon severe deformation that can be applicable to a variety of processing techniques aimed at producing immiscible alloys with superior mechanical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2014

On the radiolysis of ethylene ices by energetic electrons and implications to the extraterrestrial hydrocarbon chemistry

The chemical processing of ethylene ices (C{sub 2}H{sub 4}) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH{sub 4}), the C2 species acetylene (C{sub 2}H{sub 2}), ethane (C{sub 2}H{sub 6}), the ethyl radical (C{sub 2}H{sub 5}), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C{sub 4}H{sub 8}) and n-butane (C{sub 4}H{sub 10}). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Disordered interfaces of alkaline aluminate salt hydrates provide glimpses of Al 3+ coordination changes

Hypothesis: The precipitation and dissolution of aluminum-bearing mineral phases in aqueous systems often proceed via changes in both aluminum coordination number and connectivity, complicating molecular-scale interpretation of the transformation mechanism. Here, the thermally induced transformation of crystalline sodium aluminum salt hydrate, a phase comprised of monomeric octahedrally coordinated aluminate which is of relevance to industrial aluminum processing, has been studied. Because intermediate aluminum coordination states during melting have not previously been detected, it is hypothesized that the transition to lower coordinated aluminum ions occurs within a highly disordered quasi-two-dimensional phase at the solid-solution interface. Experiments and simulations: In this work, in situ X-ray diffraction (XRD), Raman and 27 Al nuclear magnetic resonance (NMR) spectroscopy were used to monitor the melting transition of nonasodium aluminate hydrate (NSA, Na 9 [Al(OH) 6 ] 2 ·3(OH)·6H 2 O). A mechanistic interpretation was developed based on complementary classical molecular dynamics (CMD) simulations including enhanced sampling. A reactive forcefield was developed to bridge speciation in the solution and in the solid phase. Findings: In contrast to classical dissolution, aluminum coordination change proceeds through a dynamically stabilized ensemble of intermediate states in a disordered layer at the solid-solution interface. In both melting and dissolution of NSA, octahedral, monomeric aluminum transition through an intermediate of pentahedral coordination. The intermediate dehydroxylates to form tetrahedral aluminate (Al(OH)$_4^–$) in the liquid phase. This coordination change is concomitant with a breaking of the ionic aluminate-sodium ion linkages. The solution phase Al(OH)$_4^–$ ions subsequently polymerize into polynuclear aluminate ions. However, there are some differences between bulk melting and interfacial dissolution, with the onset of the surface-controlled process occurring at a lower temperature (~30 °C) and the coordination change taking place more gradually as a function of temperature. This work to determine the local structure and dynamics of aluminum in the disordered layer provides a new basis to understand mechanisms controlling aluminum phase transformations in highly alkaline solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

An amorphous phase formation at palladium / silicon oxide (Pd/SiO{sub x}) interface through electron irradiation - electronic excitation process

A Pd-Si amorphous phase was formed at a palladium/silicon oxide (Pd/SiO{sub x}) interface at room temperature by electron irradiation at acceleration voltages ranging between 25 kV and 200 kV. Solid-state amorphization was stimulated without the electron knock-on effects. The total dose required for the solid-state amorphization decreases with decreasing acceleration voltage. This is the first report on electron irradiation induced metallic amorphous formation caused by the electronic excitation at metal/silicon oxide interface.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Extraordinary creep resistance in a non-equiatomic high-entropy alloy from the optimum solid-solution strengthening and stress-assisted precipitation process

Improving creep resistance has commonly been achieved by the optimization of alloy design that results into strong solid-solution strengthening and/or coherent precipitates for dislocation blockage. High-entropy alloys (HEAs), despite their single-phase solid-solution nature, only exhibit creep properties that are comparable to precipitate-strengthened ferritic alloys. Moreover, many HEAs are found to be plagued with many incoherent second phases after long-term annealing, which reduces the lifetime and thus prohibits their usage at elevated temperatures. The present work demonstrates the extraordinary creep resistance of a non-equiatomic Al 0.3 CoCrFeNi HEA, in which the creep strain rate is found to be several orders of magnitude lower than the Cantor alloy and its subsets. Using a suite of characterization tools such as atom probe tomography (APT) and transmission electron microscopy (TEM), it was shown that a B2 precipitate phase that has been widely seen during annealing is suppressed during the early stage of the creep deformation. Currently, metastable and coherent L1 2 precipitates emerge and provide significant creep strengthening. This observation is rationalized by the coupling between the applied stress and the lattice mismatch. In the range of 973 ~ 1033 K, the stress exponent and activation energy were determined to be 3–6.53 and 390–548.2 kJ·mol –1 , respectively. The creep lifetime, on the other hand, is comparable to Cantor subset alloys because the precipitate free zone near the grain boundaries does not provide sufficient constraint for the grain boundary cavity growth. Furthermore, the present work provides a pathway to design novel HEAs with improved creep resistance.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Understanding the solidification and microstructure evolution during CSC-MIG welding of Fe–Cr–B-based alloy

The present is a study of the solidification and microstructure of Fe–28.2%Cr–3.8%B–1.5%Si–1.5%Mn (wt.%) alloy deposited onto a 1020 plain carbon steel substrate using the controlled short-circuit metal inert gas welding process. The as-solidified alloy was a metal matrix composite with a hypereutectic microstructure. Thermodynamic calculation based on the Scheil–Gulliver model showed that a primary (Cr,Fe){sub 2}B phase formed first during solidification, followed by an eutectic formation of the (Cr,Fe){sub 2}B phase and a body-centered cubic Fe-based solid solution matrix, which contained Cr, Mn and Si. Microstructure analysis confirmed the formation of these phases and showed that the shape of the (Cr,Fe){sub 2}B phase was irregular plate. As the welding heat input increased, the weld dilution increased and thus the volume fraction of the (Cr,Fe){sub 2}B plates decreased while other microstructural characteristics were similar. - Highlights: • We deposit Fe–Cr–B-based alloy onto plain carbon steel using the CSC-MIG process. • We model the solidification behavior using thermodynamic calculation. • As deposited alloy consists of (Cr,Fe){sub 2}B plates embedded in Fe-based matrix. • We study the effect of the welding heat input on the microstructure.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Pore-scale modelling of Ostwald ripening

In a saturated solution with dispersed clusters of a second phase, the mechanism by which the larger clusters grow at the expense of the smaller ones is called Ostwald ripening. Although the mechanism is well understood in situations where multiple clusters of gas exist in a liquid solution, evolution is much more complicated to predict when the two phases interact with a solid matrix, since the solid plays a significant role in determining the shape of the interface. In this paper, we study capillary dominated regimes in porous media where the driving force is inter-cluster diffusion. By decomposing the Ostwald ripening mechanism into two processes that operate on different time scales – the diffusion of solute gas in the liquid and the readjustment of the shape of the gas–liquid interface to accommodate a change in mass – we develop a sequential algorithm to solve for the evolution of systems with multiple gas ganglia. In the absence of a solid matrix, thermodynamic equilibrium is reached when all of the gas phase aggregates to form one large bubble. In porous media on the other hand, we find that ripening can lead to equilibrium situations with multiple disconnected ganglia, and that evolution is highly dependent on initial conditions and the structure of the solid matrix. The fundamental difference between the two cases is in the relationship between mass and capillary pressure.

bio-inspired, mechanical behavior, carbon sequestr↗
DOE OSTI2019

Investigation of Stress Field and Fracture Development During Shale Maturation Using Analog Rock Systems

The emergence of hydrocarbons within shale as a major recoverable resource has sparked interest in fluid transport through these tight mudstones. Recent studies suggest the importance to recovery of microfracture networks that connect localized zones with large organic content to the inorganic matrix. This paper presents a joint modeling and experimental study to examine the onset, formation, and evolution of microfracture networks as shale matures. Both the stress field and fractures are simulated and imaged. A novel laboratory-scale, phase-field fracture propagation model was developed to characterize the material failure mechanisms that play a significant role during the shale maturation process. The numerical model developed consists of coupled solid deformation, pore pressure, and fracture propagation mechanisms. Benchmark tests were conducted to validate model accuracy. Laboratory-grade gelatins with varying Young’s modulus were used as scaled-rock analogs in two dimensional Hele-Shaw cell apparatus. Yeast within the gelatin generates gas in a fashion analogous to hydrocarbon formation as shale matures. These setups allow study and visualization of host rock elastic-brittle fracture and fracture network propagation mechanisms. The experimental setup was fitted to utilize photoelasticity principles coupled with birefringence properties of gelatin to explore visually the stress field of the gelatin as the fracture network developed. Stress optics image analysis and Linear Elastic Fracture Mechanics (LEFM) principles for crack propagation were used to monitor fracture growth for each gelatin type. Observed and simulated responses suggest gas diffusion within and deformation of the gelatin matrix as predominant mechanisms for energy dissipation depending on gelatin strength. LEFM, an experimental estimation of principal stress development with fracture growth, at different stages was determined for each gelatin rheology. Here, the interplay of gas diffusion and material deformation determines the resulting frequency and pattern of fractures. Results correlate with Young’s modulus. Experimental and computed stress fields reveal that fractures resulting from internal gas generation are similar to, but not identical to, type 1 opening mode.

58 GEOSCIENCES↗
DOE OSTI2022

Snowmass Instrumentation Frontier IF08 Topical Group Report: Noble Element Detectors

Particle detectors making use of noble elements in gaseous, liquid, or solid phases are prevalent in neutrino and dark matter experiments and are also used to a lesser extent in collider-based particle physics experiments. These experiments take advantage of both the very large, ultra-pure target volumes achievable and the multiple observable signal pathways possible in noble-element based particle detectors. As these experiments seek to increase their sensitivity, novel and improved technologies will be needed to enhance the precision of their measurements and to broaden the reach of their physics programs. The areas of R&D in noble element instrumentation that have been identified by the HEP community in the Snowmass process are highlighted by five key messages: IF08-1) Enhance and combine existing modalities (scintillation and electron drift) to increase signal-to-noise and reconstruction fidelity; IF08-2) Develop new modalities for signal detection in noble elements, including methods based on ion drift, metastable fluids, solid-phase detectors and dissolved targets. Collaborative and blue-sky R&D should also be supported to enable advances in this area; IF08-3) Improve the understanding of detector microphysics and calibrate detector response in new signal regimes; IF08-4) Address challenges in scaling technologies, including material purification, background mitigation, large-area readout, and magnetization; and IF08-5) Train the next generation of researchers, using fast-turnaround instrumentation projects to provide the design-through-result training no longer possible in very-large-scale experiments. This topical group report identifies and documents recent developments and future needs for noble element detector technologies. In addition, we highlight the opportunity that this area of research provides for continued training of the next generation of scientists.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Influences on Subsurface Plutonium and Americium Migration

Plutonium (Pu) has been released to the environment worldwide, including approximately 1.85 × 1015 Bq (200 kg) of Pu from process waste solutions to unconfined soil structures at the Hanford Site in Washington State. The subsurface mobility of Pu is influenced by complex interactions with sediments, groundwater, and any co-contaminants within the waste stream. Previous investigations at Hanford have shown that Pu exists as discrete PuO 2 particles forming before or after disposal, as secondary solid phases formed from waste interactions with sediments as adsorbed/incorporated species, and/or as dissolved species. In this research, new evidence is presented for the existence of PuO 2 , PuO 2 -Bi 2 O 3 composites, and particles from burnt Pu metal in near-surface sediments where Pu-laden acidic process waste was disposed to sediments. Pu and americium (Am) L3 X-ray absorption spectroscopy and density functional theory suggest that, in larger, more crystalline PuO 2 particles, Am formed from radioactive decay is retained in the Pu IV O 2 structure as Am IV . The Pu and Am that were disposed of in an acidic waste stream have since migrated deeper into the subsurface with detection to at least 37 meters below ground surface. In contrast, Pu deposited near the ground surface from neutral pH waste is found to be homogeneously distributed and relatively immobile. Groundwater extractions performed on contaminated sediments indicate that both Pu and Am are recalcitrant, with Am being fractionally less extractable than Pu on a molar basis. These results suggest that the more mobile fraction of Am has migrated from the near-surface and may be present in the deeper sediments as a different phase than Pu. From these results, it is suggested that Pu and Am deposited from acidic wastes were initially mobile and became significantly less mobile as wastes were neutralized within the soil profile.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2017

Iron Behavior in Microcosms Simulating Bioreduction in Savannah River Site Sediments - 17389

An estimated 1.8 billion gallons of acidic low-activity waste solutions originating from the processing of uranium slugs and irradiated fuel at separation facilities at the Savannah River Site (SRS) were discharged to the unlined seepage basins located in the F/H-area. The acidic solutions of the basin influent (pH from 3.2 to 5.5) contaminated with a variety of radionuclides and dissolved metals caused groundwater contamination. In 2010, DOE funded a demonstration of the Enhanced Anaerobic Reductive Precipitation (EARP) process at the SRS F-Area that consisted of in-situ injections of a carbohydrate substrate to establish anaerobic reactive zones for metal and radionuclide remediation. The addition of the molasses substrate solution to groundwater was done to produce anaerobic conditions conducive to uranium reduction and then precipitation as uranium (IV). The SRS soil is highly weathered and features very low natural alkalinity. A microcosm study, prepared with sieved SRS sediments and augmented with a solution mixture containing molasses and sulfate, was designed to provide evidence of the capabilities of this remediation technology under SRS environmental conditions. The objective of these microcosm experiments was to replicate the anaerobic conditions created as a result of injections of molasses combined with sulfate ions, similar to the EARP process that was performed at SRS, and investigate if any mineralogical changes could occur in the soil due to the addition of molasses. Specifically, the study aimed to determine if solid phases of reduced iron such as siderite and pyrite would be formed, as this would indicate the potential to form a long-lasting bioreductive zone. An understanding of this technology will be useful in determining if it is a viable option for remediation. In the experiments, the media solution was amended with molasses and sulfate to stimulate sulfate-reducing bacteria. Sulfate reduction occurs extensively under the redox conditions occurring after iron reduction and before methanogenic conditions. These conditions are considered the second most reducing condition in natural groundwater systems. Microcosm tubes prepared in triplicate were kept inside an anaerobic glove box, which was continuously monitored to ensure that conditions remained anaerobic. The initial X-ray diffraction (XRD) analyses on the background sediment samples indicated the presence of quartz, kaolinite, montmorillonite, and goethite. In the molasses-treated samples there were no visible peaks for reduced forms of iron such as siderite and pyrite. The pH measurements suggest that all samples in either batch, including those that were brought to a neutral pH before the addition of the sediments, have followed a similar trend with a decline in the pH value to between 4 and 4.7. This can be attributed to the fermentation of molasses and the natural acidity of the SRS sediments used for the microcosm study. In the acidic iron-rich sediment, the microbial reduction of Fe (III) was the predominant electron-accepting process for oxidation of the organic substrate. The maximum iron concentration detected during the experiments was 13 mg/L. Analytical results showed that there was no sulfate reduction in any of the samples augmented with sulfate and the concentration remained level at 500 ppm as originally added to the initial solutions (518 - 542 mg/L). This is consistent with the absence of any indication of iron sulfide formation. Under the experimental conditions in these microcosms, the abundance of biologically available Fe (III) allows Fe (III)-reducers to out-compete sulfate-reducing bacteria using molasses as an electron donor. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Mean Inner Potential of Liquid Water

Improving our experimental and theoretical knowledge of electric potentials at liquid-solid boundaries is essential to achieve a deeper understanding of the driving forces behind interfacial processes. Electron holography has proved successful in probing solid-solid interfaces but requires knowledge of the materials’ mean inner potential (MIP, V0), which is a fundamental bulk material property. Combining off-axis electron holography with liquid phase transmission electron microscopy (LPTEM), we provide the first quantitative MIP determination of liquid water V0=+4.48±0.19 V. This value is larger than most theoretical predictions, and to explain the disagreement we assess the dominant factors needed in quantum simulations of liquid water. A precise MIP lays the foundations for nanoscale holographic potential measurements in liquids and provides a benchmark to improve quantum mechanical descriptions of aqueous systems and their interfaces in e.g. electrochemistry, solvation processes and spectroscopy.

Yesibolati, Murat N.↗
DOE OSTI2021

Diffusion-to-Imbibition Transition in Water Sorption in Nanoporous Media: Theoretical Studies

The ability to predict multiphase fluid transport in nanoporous rocks such as shales is critical for many geoscience applications, for example unconventional hydrocarbon production, geologic carbon sequestration, and nuclear waste disposal. When the pore sizes approach nanoscales, the impact of the molecular interaction forces between fluids and solids becomes increasingly important. These forces can alter macroscopic fluid phase behavior and control transport. Recent experimental studies have shown that capillary condensation and subsequent imbibition of liquid water can occur in hydrophilic nanoporous media even if the vapor phase is at a critical relative humidity (rhcrit) well below vapor saturation. This study presents a theoretical investigation of the processes controlling adsorption, capillary condensation and imbibition in nanoporous media, using the square-gradient classical density functional theory. The proposed theoretical model explicitly includes the relevant interaction forces among fluids and solids in macroscopic porous media. Application of the model to a relative-humidity-controlled water adsorption experiment is presented to demonstrate the impact of water-pore wall attractive forces on multiphase water behavior in a hydrophilic silicon nanoporous medium. Here, the model represents well the measured time-dependent evolution of the water imbibition front inside the nanoporous medium and also explains the diffusion-like water transport regimes observed at rh < rh crit and the imbibition-like flow regimes observed at rh > rh crit . The study furthermore gives an insight on hysteresis phenomenon in adsorption and desorption isotherms.

58 GEOSCIENCES↗
DOE OSTI2015

Formation of titanium carbonitride film by laser treatment: Structural and transport properties

In-plane and Out-of-plane Grazing incidence X-ray diffraction is used to characterize the preferred orientation present in the titanium carbonitride films using ADXRD beamline at INDUS 2 synchrotron radiation source. GIXRD shows the formation of mixture of FCCTiC{sub x}N{sub (1-x)} films for different values of x along with the solid solution. From the in-plane and out-of-plane XRD measurements, we have observed that a specific texture along the c-axis of Ti has been formed during the laser treatment process. Due to the diffusion of C and N into Ti, the resistance of the specimen has been decreases with respect to the resistance of pure Ti sheet. The formed phases are stable and there is no structural relaxation has been observed during annealing process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗