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At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Deep anoxic aquifers could act as sinks for uranium through microbial-assisted mineral trapping

Uptake of uranium (U) by secondary minerals, such as carbonates and iron (Fe)-sulfides, that occur ubiquitously on Earth, may be substantial in deep anoxic environments compared to surficial settings due to different environment-specific conditions. Yet, knowledge of U reductive removal pathways and related fractionation between 238 U and 235 U isotopes in deep anoxic groundwater systems remain elusive. Here we show bacteria-driven degradation of organic constituents that influences formation of sulfidic species facilitating reduction of geochemically mobile U(VI) with subsequent trapping of U(IV) by calcite and Fe-sulfides. The isotopic signatures recorded for U and Ca in fracture water and calcite samples provide additional insights on U(VI) reduction behaviour and calcite growth rate. The removal efficiency of U from groundwater reaching 75% in borehole sections in fractured granite, and selective U accumulation in secondary minerals in exceedingly U-deficient groundwater shows the potential of these widespread mineralogical sinks for U in deep anoxic environments.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Directly Embedded Ni3S2/Co9S8@S-Doped Carbon Nanofiber Networks as a Free-Standing Anode for Lithium-Ion Batteries

Transition metal sulfides as electrode materials for lithium-ion batteries have attracted significant research attention due to their high theoretical capacity, excellent redox reversibility, and earth abundance. However, this material family still suffers from poor conductivity and experiences huge volume changes. Here, we demonstrate a facile and scalable electrospinning method to prepare Ni3S2 and Co9S8 nanoparticles embedded in sulfur doped carbon nanofiber networks as a free-standing anode material for lithium ion batteries. Similar to literature findings, the coupling of two different metal sulfides indeed synergistically promoted the electrochemical performance. Embedding them within individual carbon nanofibers not only enhances the intrinsic conductivity, but also provides a highly stable structure, which results in excellent battery performance. Furthermore, the individual carbon nanofibers intertwine with each other to form a free-standing 3D nanofiber network which acts as a freeway network for fast electron transfer and the pores between fibers allow easy penetration of the electrolyte, namely easy lithium ion access to active nanoparticles. When directly applied as the anode in lithium ion batteries, the free-standing nanofiber mat bypassed all slurry making steps and showed excellent cycling stability with a high specific capacity of 528 mA h g-1 after 200 cycles at a current density of 300 mA g-1. Good rate capability was also obtained. Additionally, the charge storage process analysis indicated that the pseudocapacitive behavior of the material is attributed to its good performance. This work introduces a facile strategy to simultaneously and in situ generate Co9S8 and Ni3S2 nanoparticles within a S-doped carbon fiber matrix via facile electrospinning followed by a one-step heating procedure. It is demonstrated that the free-standing transition bimetallic sulfide nanofibers prepared are very promising for light and small battery applications.

ADVANCED PROPULSION SYSTEMS,ENERGY STORAGE↗
DOE OSTI2021

Electrochemically induced metal- vs. ligand-based redox changes in mackinawite: identification of a Fe 3+ - and polysulfide-containing intermediate

Under anaerobic conditions, ferrous iron reacts with sulfide producing FeS, which can then undergo a temperature, redox potential, and pH dependent maturation process resulting in the formation of oxidized mineral phases, such as greigite or pyrite. A greater understanding of this maturation process holds promise for the development of iron-sulfide catalysts, which are known to promote diverse chemical reactions, such as H + , CO 2 and NO 3 - reduction processes. Hampering the full realization of the catalytic potential of FeS, however, is an incomplete knowledge of the molecular and redox processess ocurring between mineral and nanoparticulate phases. Here, we investigated the chemical properties of iron-sulfide by cyclic voltammetry, Raman and X-ray absorption spectroscopic techniques. Tracing oxidative maturation pathways by varying electrode potential, nanoparticulate n(Fe 2+ S 2- ) (s) was found to oxidize to a Fe 3+ containing FeS phase at -0.5 V vs. Ag/AgCl (pH = 7). In a subsequent oxidation, polysulfides are proposed to give a material that is composed of Fe 2+ , Fe 3+ , S 2- and polysulfide (S n 2- ) species, with its composition described as Fe 2+ 1-3x Fe 3+ 2x S 2- 1-y (S n 2- ) y . Thermodynamic properties of model compounds calculated by density functional theory indicate that ligand oxidation occurs in conjunction with structural rearrangements, whereas metal oxidation may occur prior to structural rearrangement. These findings together point to the existence of a metastable FeS phase located at the junction of a metal-based oxidation path between FeS and greigite (Fe 2+ Fe 3+ 2 S 2- 4 ) and a ligand-based oxidation path between FeS and pyrite (Fe 2+ (S 2 ) 2- ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Reaction processes at step edges on S-decorated Cu(111) and Ag(111) surfaces: MD analysis utilizing machine learning derived potentials

We report a variety of complexation, reconstruction, and sulfide formation processes can occur at step edges on the {111} surfaces of coinage metals (M) in the presence of adsorbed S under ultra-high vacuum conditions. Given the cooperative many-atom nature of these reaction processes, Molecular Dynamics (MD) simulation of the associated dynamics is instructive. However, only quite restricted Density Functional Theory (DFT)-level ab initio MD is viable. Thus, for M = Ag and Cu, we instead utilize the DeePMD framework to develop machine-learning derived potentials, retaining near-DFT accuracy for the M–S systems, which should have broad applicability. These potentials are validated by comparison with DFT predictions for various key quantities related to the energetics of S on M(111) surfaces. The potentials are then utilized to perform extensive MD simulations elucidating the above diverse restructuring and reaction processes at step edges. Key observations from MD simulations include the formation of small metal–sulfur complexes, especially MS 2 ; development of a local reconstruction at A-steps featuring an S-decorated {100} motif; and 3D sulfide formation. Additional analysis yields further information on the kinetics for metal–sulfur complex formation, where these complexes can strongly enhance surface mass transport, and on the propensity for sulfide formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Improved Stability of Oxysulfide Solid-State Electrolytes in Li(G3)TFSI Solvate Ionic Liquid Electrolyte

The performance of all solid-state batteries is limited by poor interfacial contact between active material and solid-state electrolyte (SSE) particles. Semi-solid batteries utilize a secondary electrolyte phase to wet the SSE/AM interface to improve cell performance. Solvate ionic liquids (SILs) are one class of liquid electrolytes under consideration for use in semi-solid batteries. This paper focuses on the Li(G3)TFSI SIL consisting of the bis(trifluoromethanesulfonyl)imide (TFSI − ) anion coupled to a [Li(G3)] + solvate cation. Sulfide SSEs are normally subject to nucleophilic attack by trigylme (G3), however, strong coordination of Li + to G3 in the [Li(G3)] + solvate cation prevents this reaction from taking place. Consequently, the stability of sulfide SSE depends on the ideal 1:1 molar ratio of G3 to TFSI, which may be difficult to maintain. We studied the chemical stability of 70Li 2 S·(30-x)P 2 S 5 ·xP 2 O 5 (x = 0, 2, 5, 10) (oxy)sulfide solid-state electrolyte in Li(G3)TFSI SIL. By physical measurement, UV–vis spectroscopy, electrochemical evaluation, X-ray photoelectron spectroscopy, and first principles calculation it is shown that increased oxygen content improves the stability of SSE in various Li(G3) x TFSI (x = 1, 2, 3, 4) liquid electrolytes. The results suggest that an oxysulfide SSE + SIL semi-solid electrolyte is a good choice for future semi-solid battery designs.

Electrochemistry↗
DOE OSTI2021

Time Dependence of Methane Generation Rates from Saltstone

This report documents the tests performed to address the requirements listed in the Technical Request, which resulted in a Task Technical & Quality Assurance Plan (TTQAP) and a Run Plan to obtain the required information. The research expands previous scoping work to better understand methane generation in the Saltstone Disposal Facility (SDF). That scoping work demonstrated that methane is produced when sulfide-containing material is added to methylmercury (MeHg), which is found in the SDF Tank 50 feed waste. When Tank 50 waste is combined with grout premix solids dry feed ingredients of cement, slag cement, and fly ash, sulfides are released from the slag cement component of the premix. The prior testing results showed that while the concentration of total mercury was not affected in the pH 14 waste, the MeHg likely reacted with the sulfide contained in the slag. The scoping tests were performed in sealed reactors and thus, methane generation was not measured continuously; rather, it was measured after one hour and after 24 hours. After 24 hours, a large percentage of the MeHg was converted to methane, but after 1 hour only a small percentage of methane was released. It is noteworthy that the methane generation rate (MGR) was greater at the one-hour measurement. The data compiled from the scoping work needed to be expanded to better understand the generation of methane released from grout mixed with Tank 50 waste. This expanded study developed a more extensive knowledge of how and when methane is generated to inform the Documented Safety Analysis (DSA) of the SDF. As such, employing 8 sealed reactors, the methane generation time periods were extended to 2, 4, 6, 18, 30, 48, 72, and 96 hours (4 days). Results are documented herein to determine the capacity for MeHg, contained within Tank 50 salt solution (T50SS) simulant, to produce methane when mixed with saltstone dry feed ingredients, i.e., individual components (cement, slag, and fly ash) or a combination of those components.

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

Integration of Omics into a New Comprehensive Rate Law for Competitive Terminal Electron-Accepting Processes in Reactive Transport Models: Application to N, Fe, S, and Contaminant Transformations in Stream and Wetland Sediments

Surface waters represent important sources of alternate energy and drinking water in the United States, and characterizing the biogeochemical processes that affect surface water quality is relevant to the DOE-BER mission. Sediment biogeochemical processes regulate the release of carbon (C), nutrients, and contaminants to surface waters and thus influence water quality. Sediment biogeochemical processes are dynamic and affected by the deposition and remobilization of solid material and changes in environmental conditions driven by water discharge variations. Wetlands are important natural filters of surface waters which may either trap, metabolize, or mobilize nutrients and contaminants. Despite their importance, biogeochemical processes regulating nutrient and contaminant release and C transformation in stream and wetland sediments cannot be predicted accurately by current mathematical models. These reactive transport models largely rely on detectable changes in geochemical conditions to activate metabolic processes, do not accurately account for the competition between microbial processes, and poorly constrain effects of hydrological perturbations on biogeochemical processes. In this BER-SBR exploratory project, metagenomic and geochemical signatures were combined to identify microbially-mediated redox processes in anaerobic stream and wetland sediments from the Savannah River Site (SRS, ANL SFA) and East Fork Poplar Creek (EFPC, ORNL SFA) that play important roles in C, uranium (U), and mercury (Hg) transformations. In addition, sediment incubations were conducted to examine the competition between anaerobic respiration processes Finally, new rate laws were developed for reactive transport models that rely on complementary metagenomic and geochemical signatures to identify the underlying anaerobic microbial processes in stream and wetland sediments, describe the competition between the dominant metabolic processes involved in nutrient release and U and Hg mobilization, and more accurately quantify carbon transformation and the response of microbial processes to changes in redox conditions associated with hydrological forcing. These rate laws were optimized in batch reactors with SRS wetland sediments, where iron and sulfate reduction dominate. Anaerobic carbon remineralization processes followed the expected thermodynamic sequence of microbial respiration with depth in both sediments, except that geochemical signals indicated that sulfate reduction was inactive in EFPC sediments and moderate in SRS wetland sediments. Estimates indicated that microbial iron reduction contributed to at least half of the production of reduced iron in these sediments. Incubations demonstrated that nitrate reduction, denitrification, and dissimilatory nitrate reduction to ammonium were active in the natural EFPC sediment and activated upon nitrate amendment in these nitrate-rich sediments. In turn, these processes were outcompeted by the addition of either iron oxides or sulfate as alternative terminal electron acceptors. Although geochemical products of sulfate reduction were not detected in the incubations, the abundance of sulfate reduction genes increased with depth in the sediment and was equally more pronounced in treatments amended with either iron oxides or sulfate. Simultaneously, anaerobic sulfide oxidizing bacteria coupling sulfide oxidation to DNRA (and not conventional denitrification) were apparently enriched over time, regardless of the treatments. These findings indicate that sulfate reduction is important in freshwater stream sediments and probably catalyzed by a cryptic sulfur cycle involving nitrogen species, in which the sulfur products from sulfate reduction are immediately removed by side reactions and not detectable by geochemical measurements alone. Similar experiments in SRS sediments, however, demonstrated little interaction between nitrogen and sulfur cycling microorganisms. Sulfate reduction was impacted by the addition of more thermodynamically favorable electron acceptors, suggesting either that iron-reducing microorganisms outcompeted sulfate-reducing microorganisms for organic substrate, depleting the stock of electron donor available for sulfate reduction, or that the cryptic sulfur cycle was shunted by the precipitation of FeS generated as a result of the abiotic reduction of iron oxides by dissolved sulfide. A diagnostic modeling exercise was conducted to further investigate the competition between terminal electron accepting processes. As conventional kinetic models typically do not account for cryptic cycles and used inaccurate formulations to describe competition between microbial communities, new metabolic rate laws were developed that explicitly express the electron acceptor-specific enzyme of each energetically favorable metabolic process based on gene abundance detected in the incubations. The model was tested with the sediment slurry incubation data to determine whether substrate competition could explain the decrease in sulfate reduction observed in the presence of iron oxide competitor. The model was able to reproduce geochemical concentrations really well in each treatment once the model was calibrated with the unamended control, suggesting that microbial competition was indeed driven by thermodynamic considerations. Overall, carbon remineralization processes and rates will be reproduced much more realistically with the new metabolic rate laws.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Predictive Engineering of Interfaces and Cathodes for High-Performance All Solid-State Lithium-Sulfur Batteries

The primary goal of this project is to leverage data-driven methods and machine learning strategies to develop accurate multi-physics models for all-solid-state Li-S battery (ASLSB) materials that can capture electrochemical and transport phenomena over atomic to mesoscopic length/timescales. These models will be rigorously validated by synthesis and advanced characterization experiments. The team will leverage the predictive power of these models, alongside synthesis/characterization experiments and battery fabrication to address longstanding issues at the electrode/electrolyte interfaces in ASLSBs. The project’s proposed technology involves the following: (1) halide-doped solid sulfide electrolytes that can concurrently provide high Li + ion conductivity and suppress dendrite growth; (2) novel mesoporous cathode composed of super-P and carbon nanotubes co-infiltrated with sulfur and sulfide electrolyte, which hold potential to allow high sulfur loading and optimal ion/electron pathways; and (3) functionalization of sulfide electrolyte with ionic liquids to improve physical contact and minimize impedance at the cathode/electrolyte interface. Successful development of proposed predictive models (at multiple scales) will bridge this knowledge gap and will advance fundamental understanding of reaction chemistry, kinetics, charge transfer, and dendrite growth at electrified SSIs. This will enable predictive design of effective strategies to mitigate interfacial problems in ASSLSBs, including poor interfacial contact, interfacial impedance to Li + ion transport, and poor electron/ion conduction within cathodes. Ultimately, the fundamental knowledge gained will lead to development of high-performance ASSLSBs.

25 ENERGY STORAGE↗
DOE OSTI2020

Additive Manufacturing of Isotropic NdFeB PPS Bonded Permanent Magnets

Extrusion based additive manufacturing of polymer composite magnets can increase the solid loading volume fraction with greater mechanical force through the printing nozzle as compared to traditional injection molding process. About 63 vol% of isotropic NdFeB magnet powders were compounded with 37 vol% of polyphenylene sulfide and bonded permanent magnets were fabricated while using Big Area Additive Manufacturing without any degradation in magnetic properties. The polyphenylene sulfide bonded magnets have a tensile stress of 20 MPa, almost double than that of nylon bonded permanent magnets. Additively manufactured and surface-protective-resin coated bonded magnets meet the industrial stability criterion of up to 175 °C with a flux-loss of 2.35% over 1000 h. They also exhibit better corrosion resistance behavior when exposed to acidic (pH = 1.35) solution for 24 h and also annealed at 80 °C over 100 h (at 95% relative humidity) over without coated magnets. Thus, polyphenylene sulfide bonded, additively manufactured, protective resin coated bonded permanent magnets provide better thermal, mechanical, and magnetic properties.

36 MATERIALS SCIENCE↗
NASA NTRS1973

Oxygen and sulfur interactions with a clean iron surface and the effect of rubbing contact on these interactions

The interaction of sulfur and oxygen with an iron surface was studied with Auger spectroscopy analysis both statically and during sliding-friction experiments in a vacuum environment. Oxygen, hydrogen sulfide, methyl mercaptan, and sulfur dioxide were adsorbed to an iron surface. Results indicate that sulfide films formed on clean iron surfaces are completely displaced by oxygen. Hydrocarbons containing sulfur, such as methyl mercaptan, adsorb dissociatively. Less sulfur is adsorbed during sliding with hydrogen sulfide and methyl mercaptan than in the absence of sliding. With both oxygen and sulfur dioxide, sliding did not affect the amount of material adsorbed to iron.

Buckley, D. H.↗
NASA NTRS1976

Formation of iron sulphide in solar nebula

Noting that the iron sulfide in the Orgueil carbonaceous meteorite is an Fe-deficient monosulfide (pyrrhotite), it is suggested that such mineral chemistry is inconsistent with equilibrium condensation of the solar nebula and that the course of condensation may have been modified by kinetic effects. The effect of Ni on the reaction between Fe and S to produce FeS is examined, and possible reasons are considered for the fact that the cited meteorite differs in both crystal structure and Ni content from the predictions of equilibrium condensation. It is proposed that sulfide formation in the solar nebula may have been inhibited by sluggish diffusion, so that sulfur began to react with previously condensed troilite to form pyrrhotite. On this basis, observations of the Orgueil sulfides are shown to suggest that the course of solar-system condensation was modified by kinetic effects below about 700 K and that equilibrium may not have been achieved.

Kerridge, J. F.↗
NASA NTRS1977

Sulfur compounds in coal

The literature on the chemical structure of the organic sulfur compounds (or functional groups) in coal is reviewed. Four methods were applied in the literature to study the sulfur compounds in coal: direct spectrometric and chemical analysis, depolymerization in drastic conditions, depolymerization in mild conditions, and studies on simulated coal. The data suggest that most of the organic sulfur in coal is in the form of thiophenic structures and aromatic and aliphatic sulfides. The relative abundance of the sulfur groups in bituminous coal is estimated as 50:30:20%, respectively. The ratio changes during processing and during the chemical analysis. The main effects are the transformation during processing of sulfides to the more stable thiophenic compounds and the elimination of hydrogen sulfide.

Attar, A.↗
NASA NTRS1977

Photo sensor array technology development

The development of an improved capability photo sensor array imager for use in a Viking '75 type facsimile camera is presented. This imager consists of silicon photodiodes and lead sulfide detectors to cover a spectral range from 0.4 to 2.7 microns. An optical design specifying filter configurations and convergence angles is described. Three electronics design approaches: AC-chopped light, DC-dual detector, and DC-single detector, are investigated. Experimental and calculated results are compared whenever possible using breadboard testing and tolerance analysis techniques. Results show that any design used must be forgiving of the relative instability of lead sulfide detectors. A final design using lead sulfide detectors and associated electronics is implemented by fabrication of a hybrid prototype device. Test results of this device show a good agreement with calculated values.

Rossman, M. W.↗
NASA NTRS1977

Metallic phases in the Luna 24 soil samples

The metal and sulfide phases in the Luna 24 soil samples were studied with the optical microscope and the electron microprobe. The compositions of the metal particles fall into three groups based on their Ni and Co contents: (1) Samples of meteoritic composition which have undergone metamorphism on the lunar surface. (2) Samples of submeteoritic, low Ni and low Co contents, including most of the metal particles observed. These particles are contained in glass and agglutinate particles and were probably formed by the mixing of meteoritic metal with lunar metal produced by the reduction of silicates during shock-impact. (3) Samples of high-CO content probably formed by mixing of meteoritic material with high-Co metal from the mare basalt or by fractional crystallization from a metal silicate melt. The sulfide minerals were also studied. These are almost pure FeS, and crystallized from a late stage liquid in the mare basalt. Three high-Ni sulfides were also found in the glass phase of agglutinates.

Friel, J. J.↗
NASA NTRS1979

Sulfur Isotropic Studies of Archean Slate and Graywacke from Northern Minnesota: Evidence for the Existence of Sulfate Reducing Bacteria

Sulfur isotopic studies of pyrite from metasediments in the 2.6 b.y. old Deer Lake greenstone sequence, Minnesota, were conducted in order to evaluate the possible importance of sulfate reducing bacteria in sulfide formation. Pyrite occurs as ovules up to 2 cm in diameter within graphitic slates, and as fine disseminations in metagraywacke units. SEM studies indicate the pyrite is framboidal in morphology. Delta notation values of pyrite from the Deer Lake sediments range from -2.3 to 11.1 0/00, with a peak at approximately +2 o/oo. Isotopic data is consistent with either high temperature inorganic reduction of circulating seawater sulfate, or low temperature bacterial reduction. However, the lack of sulfide bands or massive occurrences in the sediments, the restriction of pyrite mineralization to the sediments, and the absence of evidence for hot spring activity suggest that a diagenetic origin of pyrite is more feasible. Sulfide in such an environment would be produced principally by the action of sulfate reducing bacteria.

Ripley, E. M.↗
NASA NTRS1979

Investigations of submicron sized metal particles in glass coatings of lunar breccia 15286

Almost all the submicron metal particles in the glass coating of breccia 15286 are rounded and contain two phases, metal and sulfide (FeS). The Ni content of the metal phase as determined by scanning transmission electron microscope X-ray analysis ranged from 9.4 to 15.5 wt %. The sulfide was nearly stoichiometric troilite containing up to 1.3 wt % Ni. The close chemical and microstructural similarities between the coarse (greater than 1-micron) and the submicron sized metal indicate a common origin probably as meteoritic debris. Metal-silicate melt experiments under controlled oxygen partial pressured indicate that the metal particles may have formed from a fine dispersion of immiscible metal-sulfide droplets into an impact-generated silicate melt.

Mehta, S.↗
NASA NTRS1982

Venus: Halide cloud condensation and volatile element inventories

Several Venus cloud condensates, including A12C16 as well as halides, oxides and sulfides of arsenic and antimony, are assessed for their thermodynamic and geochemical plausibility. Aluminum chloride can confidently be ruled out, and condensation of arsenic sulfides on the surface will cause arsenic compounds to be too rare to produce the observed clouds. Antimony may conceivably be sufficiently volatile, but the expected molecular form is gaseous SbS, not the chloride. Arsenic and antimony compounds in the atmosphere will be regulated at very low levels by sulfide precipitation, irrespective of the planetary inventory of As and Sb. Thus the arguments for a volatile-deficient origin for Venus based on the depletion of water and mercury (relative to Earth) cannot be tested by a search for atmospheric arsenic or antimony.

Lewis, J. S.↗
NASA NTRS1982

Vaporization thermodynamics of K2S and K2SO3

The vaporization reactions, vapor pressures, and thermodynamics of potassium sulfide and potassium sulfite were studied for purposes of providing fundamental data for the seed cycle in magnetohydrodynamic electric power generation. Rate of effusion studies, supported by tube furnace experiments, X-ray powder diffraction, mass spectrometry and appropriate chemical analyses and tests, revealed that potassium sulfite disproportionates at high temperatures to form potassium sulfide and potassium sulfate. Potassium sulfide was observed to vaporize incongruently, the initial vapors beng predominantly potassium atoms, with minor species being S2 and various K-S molecules. The ratio of K/S2 in the vapor is very large initially and decreases steadily with prolonged heating. Several materials were evaluated for purposes of containing K2S/K2SO3 at temperatures or = 800 C: Pt, Mo, W, quartz, machinable glass, BN, high density graphite, pyrolytic coated graphite, and alumina. Of these, only alumina was observed to be chemically inert to both K2S but reacted with K2SO3. The other materials were not suitable for either substance. Thermodynamic calculations based on measured vapor pressures and approximate free energy functions are described. Results from isothermal total mass loss experiments and from thermogravimetric experiments are also included.

Bennet, J. E.↗