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At least 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Instabilities and finger formation in replacement fronts driven by an oversaturated solution: FINGER FORMATION IN MINERAL REPLACEMENT

We consider a simple model of infiltration-driven mineral replacement, in which the chemical coupling between precipitation and dissolution leads to the appearance of a reaction front advancing into the system. Such fronts are usually accompanied by a local increase of porosity. We analyze the linear stability of the replacement front to establish whether such a localized porosity increase can lead to global instability and pattern formation in these systems. We find that for a wide range of control parameters such fronts are unstable. However, both short- and long-wavelength perturbations are stabilized, whereas in a purely dissolutional instability only short wavelengths are stable. We analyze the morphologies of the dissolution patterns emerging in the later stages of the evolution of the system, when the dynamics are beyond the linear regime. Implications of these results for the natural systems are discussed, particularly in the context of karst formation in terra rossa-covered carbonate bedrock.

58 GEOSCIENCES↗
DOE OSTI2018

Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers

In this paper, the preparation and characterization of modified LiMn 2 O 4 (LMO) cathodes utilizing chemisorbed alkylphosphonic acids to chemically modify their surfaces are reported. Electrochemical methods to study ionic and molecular mobility through the alkylphosphonate self-assembled monolayers (SAMs) for different alkyl chain compositions, in order to better understand their impact on the lithium-ion electrochemistry, are utilized. Electrochemical trends for different chains correlate to trends observed in contact angle measurements and solvation energies obtained from computational methods, indicating that attributes of the microscopic wettability of these interfaces with the battery electrolyte have an important impact on ionic mobility. The effects of surface modification on Mn dissolution are also reported. The alkylphosphonate layer provides an important mode of chemical stabilization to the LMO, suppressing Mn dissolution by 90% during extended immersion in electrolytes. A more modest reduction in dissolution is found upon galvanostatic cycling, in comparison to pristine LMO cathodes. Finally, taken together, the data suggest that alkylphosphonates provide a versatile means for the surface modification of lithium-ion battery cathode materials allowing the design of specific interfaces through modification of organic chain functionalities.

25 ENERGY STORAGE↗
DOE OSTI2018

The Relationship between the Relative Solvating Power of Electrolytes and Shuttling Effect of Lithium Polysulfides in Lithium–Sulfur Batteries

Abstract Relative solvating power, that is, the ratio of the coordination ratios between a solvent and the reference solvent, was used to probe the quantitative structure–activity relationship of electrolyte solvents and the lithium polysulfide (LiPS) dissolution in lithium–sulfur batteries. Internally referenced diffusion‐ordered nuclear magnetic resonance spectroscopy (IR‐DOSY) was used to determine the diffusion coefficient and coordination ratio, from which the relative solvating power can be easily measured. The higher the relative solvating power of an ethereal solvent, the more severe will be the LiPS dissolution and the lower the coulombic efficiency of the lithium–sulfur battery. A linear relationship was established between the logarithm of relative solvating power of a solvent and the degree of LiPS dissolution, rendering relative solvating power an important parameter in choosing the electrolyte solvent for lithium–sulfur batteries.

Su, Chi‐Cheung↗
DOE OSTI2022

On the Role of Interfacial Water Dynamics for Electrochemical Stability of RuO 2 and IrO 2

Abstract Based on the coincident onsets of oxygen evolution reaction (OER) and metal dissolution for many metal‐oxide catalysts it was suggested that OER triggers dissolution. It is believed that both processes share common intermediates, yet exact mechanistic details remain largely unknown. For example, there is still no clear understanding as to why rutile IrO 2 exhibits such an exquisite stability among water‐splitting electrocatalysts. Here, we employ density functional theory calculations to analyze interactions between water and the (110) surface of rutile RuO 2 and IrO 2 as a response to oxygen evolution involving lattice oxygen species. We observe that these oxides display qualitatively different interfacial behavior that should have important implications for their electrochemical stability. Specifically, it is found that IrO 2 (110) becomes further stabilized under OER conditions due to the tendency to form highly stable low oxidation state Ir(III) species. In contrast, Ru species at RuO 2 (110) are prone to facile reoxidation by solution water. This should facilitate the formation of high Ru oxidation state intermediates (>IV) accelerating surface restructuring and metal dissolution.

Evazzade, Iman↗
DOE OSTI2015

Reactive fluid flow in CO 2 storage reservoirs: A 2‐D pore network model study

Abstract Water acidifies in the presence of CO 2 and prompts mineral dissolution. A 2‐D pore network model scheme is developed to investigate reactive fluid flow in CO 2 storage reservoirs during injection when advective transport prevails. Mineral dissolution satisfies kinetic rate laws and continues until thermodynamic equilibrium is reached. In advection‐dominant regimes, network simulation results show that species concentration, tube enlargement and flow rate can be summarized in terms of the dimensionless Damköhler number Da which is the ratio between advection time along a pore and the reaction time. Reservoirs will tend to experience localized enlargement near injection wells (before water drying) and compact dissolution in the far‐field. The Damköhler number couples with initial pore‐size variability to distort the relationship between mean tube diameter and either local or network‐average flow rates. Both the Damköhler number and pore‐size variability should be considered in field‐scale numerical simulators.

Kim, Seunghee↗
DOE OSTI2015

On the mobilization of metals by CO 2 leakage into shallow aquifers: exploring release mechanisms by modeling field and laboratory experiments

The dissolution of CO 2 in water leads to a pH decrease and a carbonate content increase in affected groundwater, which in turn can drive the mobilization of metals from sediments. The mechanisms of metal release postulated in various field and laboratory studies often differ. Drawing primarily on previously published results, we examine contrasting metal mobilization behaviors at two field tests and in one laboratory study, to investigate whether the same mechanisms could explain metal releases in these different experiments. Numerical modeling of the two field tests reveals that fast Ca-driven cation exchange (from calcite dissolution) can explain the release of most major and trace metal cations at both sites, and their parallel concentration trends. The dissolution of other minerals reacting more slowly (superimposed on cation exchange) also contributes to metal release over longer time frames, but can be masked by fast ambient groundwater velocities. Therefore, the magnitude and extent of mobilization depends not only on metal-mineral associations and sediment pH buffering characteristics, but also on groundwater flow rates, thus on the residence time of CO 2 -impacted groundwater relative to the rates of metal-release reactions. Sequential leaching laboratory tests modeled using the same metal-release concept as postulated from field experiments show that both field and laboratory data can be explained by the same processes. Finally, the reversibility of metal release upon CO 2 degassing by de-pressurization is also explored using simple geochemical models, and shows that the sequestration of metals by resorption and re-precipitation upon CO 2 exsolution is quite plausible and may warrant further attention.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Numerical investigation of Lower Tuscaloosa Sandstone and Selma Chalk caprock under geological CO 2 sequestration conditions: mineral precipitation and permeability evolution

Abstract A numerical model was developed using CrunchFlow to simulate reactive transport and porosity and permeability changes of sandstone and carbonate rock samples taken from the Lower Tuscaloosa Formation and the Selma Chalk Formation, Jackson County, MS, USA. The model predicted a permeability decrease from 2190 mD to 2038 mD for the Lower Tuscaloosa Sandstone sample in a static batch reactor after 180 days of exposure to CO 2 ‐saturated brine, which is consistent with measured permeability results. The model predicted a negligible permeability change from 2.00 mD to 2.08 mD for the Selma Chalk carbonate sample after 180 days of exposure to CO 2 ‐saturated brine. Based on model prediction, key mineral dissolution and precipitation reactions in the Lower Tuscaloosa Sandstone sample include dissolution of quartz, chlorite, and feldspar, as well as precipitation of amorphous silica and kaolinite. For the Selma Chalk carbonate sample, key predicted reactions include dissolution of calcite, quartz and chlorite, and precipitation of kaolinite and amorphous silica. Initial porosity, initial feldspar content and the exponent n value (related to pore structure and tortuosity) used in permeability calculations were three important factors affecting permeability evolution of sandstone samples under CO 2 sequestration conditions. The small permeability change predicted for both the Lower Tuscaloosa Sandstone and the Selma Chalk caprock after exposure to CO 2 ‐saturated brine suggests that poro‐permeability changes during CO 2 injection into the Lower Tuscaloosa Formation are not likely to significantly affect reservoir and seal quality. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd.

Zhang, Liwei↗
DOE OSTI2023

Improvements in iridium target chemistry

Abstract We developed and optimized the dissolution and separation chemistry of iridium (Ir) from irradiated Ir pellets and prepared Ir counting samples for analysis by a silicon drift detector. Previous Ir chemistry techniques used on the irradiated Ir pellets are tedious, lengthy, and require extra safety precautions and planning due to the use of perchloric acid in the dissolution step. The dissolution and separations method described in this paper are safer, eliminating the use of perchloric acid, more efficient, and can successfully replace the previous procedure.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Quantification of uranium metal and total uranium in U-UO 2 mixtures using H 3 PO 4 -HCl

Here, the selective dissolution of uranium metal from its mixtures with UO 2 was studied to establish a simple and rapid quantitative method. Uranium metal was found to selectively dissolve as U(IV) into a solution of phosphoric and hydrochloric acids, with quantitative dissolution occurring within 1 h. Total dissolution of uranium as U(VI) could then be obtained by nitric acid addition and heating for 0.5–1 h. Analysis of the resulting U(IV) and U(VI) solutions by ICP-OES or UV–Vis spectroscopy yielded uranium metal-to-UO 2 ratios with an accuracy of ± 10% or better. Accuracy of the ICP-OES method was slightly better than UV–Vis, but the simplicity of the latter makes it an attractive option for some applications.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Ultrasound-Assisted Leaching and Kinetic Study of Blended Copper Slag

This article deals with the dissolution of blended copper slag (flash and converter furnace) in hydrogen peroxide and acetic acid in the presence of ultrasound. The parameters that are effective on leaching efficiency, such as leaching temperature, leaching time, ultrasound power, acetic acid concentration, and hydrogen peroxide concentration, were investigated. The optimum leaching conditions for maximum copper dissolution (93 pct) and minimum iron dissolution (3 pct) were determined as follows: 2 M H{sub 2}O{sub 2}, 4 M CH{sub 3}COOH, 10 pct of ultrasound power, 65 °C of leaching temperature, 60 minutes of leaching time, and 1:25 of solid–liquid ratio. According to the Brunauer–Emmett–Teller (BET) analysis results on the original sample and leaching residue, the ultrasound caused formation of microcracks on the particle surface; however, the BET surface area increased and the mean adsorption pore width decreased. The apparent activation energy was found to be 55.35 kJ/mol, and the kinetics equations of the processes were established.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Antifouling Properties and Release of Dissolved Copper of Cold Spray Cu/Cu{sub 2}O Coatings for Ships and Steel Structures in Marine Environment

At the submarine screen doors of ships, the flow of water was fast and organic coatings were easy to peel off. To solve the problems of biofouling, the Cu/Cu{sub 2}O coatings were prepared by cold spray technology. In this paper, the release mechanism of effective antifouling components of the coatings was studied by micro-domain electrochemical potential scanning technique. Cuprous oxide in the coatings and the surrounding copper constituted micro-cells which accelerated the local electrochemical dissolution of copper. Cuprous oxide acted as the cathode, and the surrounding copper acted as the anode. Meanwhile, under the action of current, chloride ions were transferred from cathode to the anode and promoted local electrochemical dissolution of copper. Experiments show that the higher the Cu{sub 2}O content in the coatings, the greater the release rate of dissolved copper and inhibitory effect on diatoms. In the environments varied in dissolved oxygen, salinity, temperature and flow rate, the coatings maintained sufficient release rate of dissolved copper, unless the salinity was very low. Most of the dissolved copper was provided by the electrochemical dissolution process of copper. Whether in the indoor test or marine environment experiments, 30% Cu{sub 2}O coatings show the best performance. After insulating layer was sprayed, the effect of antifouling was improved evidently and the coatings were applied to the submarine screen doors of ships.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Gas sorption and non-Darcy flow in shale reservoirs

Gas sorption and non-Darcy flow are two important issues for shale gas reservoirs. The sorption consists of dissolution and adsorption. Dissolved gas and adsorbed gas are different. The former is dissolved in the shale matrix, while the latter is concentrated near the solid walls of pores. In this paper, the Langmuir equation is used to describe adsorption and Henry’s law is used to describe dissolution. The K coefficient in Henry’s law of 0.052 mmol/(MPa g TOC) is obtained by matching experimental data. The amount of dissolved gas increases linearly when pressure increases. Using only the Langmuir equation without considering dissolution can lead to a significant underestimation of the amount of sorbed gas in shales. For non-Darcy gas flow, the apparent permeability model for free gas is established by combining slip flow and Knudsen flow. For adsorbed gas, the surface diffusion effect is also considered in this model. Here, the surface diffusion coefficient is suggested to be of the same scale as the gas self-diffusion coefficient, and the corresponding effective permeability is derived. When

02 PETROLEUM↗
DOE OSTI2024

Melting and solidification dynamics during laser melting of reaction-based metal matrix composites uncovered by in-situ synchrotron X-ray diffraction

Laser additive manufacturing (AM) of reaction-based metal matrix composites (MMCs) involves highly complex and non-equilibrium material transformation behavior, including melting, dissolution, precipitation, and solidification. Yet, the dynamics and interplay of these phase transformation processes remain poorly understood, posing substantial challenges in identifying the microstructure formation mechanism, and predicting and controlling the microstructure in the printed parts. Here, in this study, we performed the in-situ X-ray diffraction experiment to characterize the phase evolution dynamics of the 316L + 10 vol.%TiC system during laser melting, which provides direct and quantitative insights of the complex phase reaction and evolution dynamics under rapid heating and cooling conditions relevant to additive manufacturing of reaction-based MMCs. Further in-depth thermodynamic and kinetic calculations revealed that most of the phase evolution behavior observed in the in-situ X-ray diffraction experiment cannot be solely explained by widely used equilibrium thermodynamic models, and diffusion-controlled nonequilibrium dissolution and precipitation kinetics must be considered to elucidate the complex phase evolution behavior, including incomplete TiC dissolution, and three-step TiC precipitation. The three distinct types of precipitates generate unique hierarchical TiC micro- and nanostructures, which enhances the yield strength from 513 MPa to 877 MPa by 71 %, tensile strength from 628 MPa to 1054 MPa by 68 %, and Young's modulus from 193 GPa to 221 GPa by 14 %. The findings of our research provide the knowledge foundation for the design of unique microstructures and advanced MMC materials through laser AM.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Effect of oxygen co-injected with carbon dioxide on Gothic shale caprock–CO 2 –brine interaction during geologic carbon sequestration

Co-injection of oxygen, a significant component in CO 2 streams produced by the oxyfuel combustion process, can cause a significant alteration of the redox state in deep geologic formations during geologic carbon sequestration. The potential impact of co-injected oxygen on the interaction between synthetic CO 2 –brine (0.1 M NaCl) and shale caprock (Gothic shale from the Aneth Unit in Utah) and mobilization of trace metals was investigated at ~ 10 MPa and ~ 75 °C. A range of relative volume percentages of O 2 to CO 2 (0, 1, 4 and 8%) were used in these experiments to address the effect of oxygen on shale–CO 2 –brine interaction under various conditions. Major mineral phases in Gothic shale are quartz, calcite, dolomite, montmorillonite, and pyrite. During Gothic shale–CO 2 –brine interaction in the presence of oxygen, pyrite oxidation occurred extensively and caused enhanced dissolution of calcite and dolomite. Pyrite oxidation and calcite dissolution subsequently resulted in the precipitation of Fe(III) oxides and gypsum (CaSO 4 ·2H 2 O). In the presence of oxygen, dissolved Mn and Ni were elevated because of oxidative dissolution of pyrite. The mobility of dissolved Ba was controlled by barite (BaSO 4 ) precipitation in the presence of oxygen. Dissolved U in the experimental brines increased to ~ 8–14 μg/L, with concentrations being slightly higher in the absence of oxygen than in the presence of oxygen. Experimental and modeling results indicate the interaction between shale caprock and oxygen co-injected with CO 2 during geologic carbon sequestration can exert significant impacts on brine pH, solubility of carbonate minerals, stability of sulfide minerals, and mobility of trace metals. The major impact of oxygen is most likely to occur in the zone near CO 2 injection wells where impurity gases can accumulate. Finally, oxygen in CO 2 –brine migrating away from the injection well will be continually consumed through the reactions with sulfide minerals in deep geologic formations.

Carbon sequestration↗
DOE OSTI2016

Impacts of elevated dissolved CO 2 on a shallow groundwater system: Reactive transport modeling of a controlled-release field test

We report one of the risks that CO 2 geological sequestration imposes on the environment is the impact of potential CO 2 /brine leakage on shallow groundwater. The reliability of reactive transport models predicting the response of groundwater to CO 2 leakage depends on a thorough understanding of the relevant chemical processes and key parameters affecting dissolved CO 2 transport and reaction. Such understanding can be provided by targeted field tests integrated with reactive transport modeling. A controlled-release field experiment was conducted in Mississippi to study the CO 2 -induced geochemical changes in a shallow sandy aquifer at about 50 m depth. The field test involved a dipole system in which the groundwater was pumped from one well, saturated with CO 2 at the pressure corresponding to the hydraulic pressure of the aquifer, and then re-injected into the same aquifer using a second well. Groundwater samples were collected for chemical analyses from four monitoring wells before, during and after the dissolved CO 2 was injected. In this paper, we present reactive transport models used to interpret the observed changes in metal concentrations in these groundwater samples. A reasonable agreement between simulated and measured concentrations indicates that the chemical response in the aquifer can be interpreted using a conceptual model that encompasses two main features: (a) a fast-reacting but limited pool of reactive minerals that responds quickly to changes in pH and causes a pulse-like concentration change, and (b) a slow-reacting but essentially unlimited mineral pool that yields rising metal concentrations upon decreased groundwater velocities after pumping and injection stopped. During the injection, calcite dissolution and Ca-driven cation exchange reactions contribute to a sharp pulse in concentrations of Ca, Ba, Mg, Mn, K, Li, Na and Sr, whereas desorption reactions control a similar increase in Fe concentrations. Finally, after the injection and pumping stops and the groundwater flow rate decreases, the dissolution of relatively slow reacting minerals such as plagioclase drives the rising concentrations of alkali and alkaline earth metals observed at later stages of the test, whereas the dissolution of amorphous iron sulfide causes slowly increasing Fe concentrations.

58 GEOSCIENCES↗
DOE OSTI2018

Mass balance implies Holocene development of a low-relief karst patterned landscape

We constructed mass balances of both calcium and phosphorus for two watersheds in Big Cypress National Preserve in southwest Florida (USA) to evaluate the time scales over which its striking landscape pattern developed. This low-relief carbonate landscape is dotted with evenly spaced, evenly sized, shallow surface depressions that annually fill with surface water and thus support wetland ecosystems (e.g. cypress domes) embedded in a pine-dominated upland matrix with exposed bedrock. Local and landscape scale feedbacks between hydrology, ecological dynamics and limestone dissolution are hypothesized to explain this karst dissolution patterning. This hypothesis requires the region to be wet enough to initiate surface water storage, which constrains landscape formation to interglacial periods. The time scale therefore would be relatively recent if creation of the observed pattern occurred in the current interglacial period (i.e. Holocene), and older time scales could reflect inherited patterns from previous inter-glacial periods, or from other processes of abiotic karstification. We then determined phosphorus stocks across four landscape compartments and estimated the limestone void space (i.e., wetland depression volume) across the landscape to represent cumulative calcium export. We calculated fluxes in (e.g., atmospheric deposition) and out (i.e., solute export) of the landscape to determine landscape denudation rates through mass balance. Comparing stocks and annual fluxes yielded independent estimates of landscape age from the calcium and phosphorus budgets. Our mass balance results indicate that the landscape began to develop in the early-mid Holocene (12,000–5000 ybp). Radiocarbon dating estimates implied similar rates of dissolution (~1 m per 3000–3500 years), and were in agreement with Holocene origin. This supports the hypothesis that ecohydrologic feedbacks between hydrology and vegetation occurring during the present interglacial period are sufficient to shape this landscape into the patterns we see today, and more broadly suggests the potential importance of biota in the development of macro-scale karst features.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Optimizing a chemical cleaning protocol to determine the nickel isotopic composition of ancient seawater from carbonates

Reconstructing the ancient marine cycle of Ni, a trace metal in the oceans essential to enzymes regulating the C, N, and O cycles, would inform how Ni bioavailability shaped early life. The Ni isotopic composition of seawater (δ 60 Ni SW ) through time could provide insight, but this approach requires sedimentary archives that faithfully record δ 60 Ni SW . Carbonates are an often-used record of seawater chemistry, but contaminants could bias the measured δ 60 Ni of bulk sediment. To isolate the true carbonate-bound δ 60 Ni signal, we optimized a chemical cleaning protocol designed to minimize non‑carbonate Ni contributions and maximize carbonate recovery. We analyzed ODP Site 1007 sediments and evaluated oxidative and reductive pre-cleaning steps and carbonate dissolution protocols. Our results show that only reductive cleaning significantly altered the subsequent carbonate leachate composition, lowering Ni/Ca ratios by up to 60% and δ 60 Ni values by as much as 0.4 ‰. In contrast, δ 60 Ni values were largely insensitive to premature carbonate dissolution during pre-cleaning or to partial leaching of silicates during carbonate dissolution, even at higher acid molarities or longer reaction times. We recommend an evidence-based protocol that removes hydro-soluble salts and clays, applies reductive cleaning and oxidative cleaning for certain sample compositions, and dissolves carbonate using 0.5 M acetic acid, adjusted to pH 5. Using these results, we infer a ∼ 0.9 ‰ Ni isotopic fractionation between chemically cleaned deep-water carbonates (+0.4 ± 0.1 ‰) and deep seawater. This method development is a key step toward accurately reconstructing ancient marine Ni cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗