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At least 1,495 records · Page 83
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

The origin of passivity in aluminum-manganese solid solutions

In this work, the effects of manganese on the aqueous corrosion of aluminum-manganese alloys were investigated by experiments and atomistic simulations. Electrochemical measurements, x-ray photoelectron spectroscopy, and atom probe tomography analysis indicate that manganese addition enhanced the corrosion resistance of aluminum without participating in the surface oxidation. Furthermore, the selective dissolution of manganese was believed to increase the free volume at the metal/oxide interface to facilitate the formation of a denser, thinner oxide layer with closer to stoichiometry composition. Atomistic simulations showed that the oxide layer compactness increased, and defect density decreased with increasing free volume content in Al, resulting in enhanced barrier characteristics.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Dimensionality effects on multicomponent ionic transport and surface complexation in porous media

Coulombic interactions between charged species in pore water and at surface/solution interfaces are of pivotal importance for multicomponent reactive transport in porous media. In this study, we investigate the impact of domain dimensionality on electrostatically coupled dispersion and surface-solution reactions during transport of acidic plumes and major ions in porous media. Column and quasi two-dimensional flow-through experiments were performed, with identical silica porous media and under the same advection-dominated conditions. Equal mass fluxes of different electrolyte solutions (i.e., HCl - pH ~ 2.8, NaBr - 100 mM, HCl - pH ~ 2.8 plus NaBr - 100 mM) were continuously injected in the 1-D and 2-D experiments and breakthrough curves of pH and major ions were measured at the outlet of the domains. The presence of pronounced ionic strength gradients in the transverse direction in the 2-D setup caused distinct retardation and transport behaviors of protons and major ions which were not observed in the one-dimensional column experiments. Furthermore, in the cases of salt electrolytes injection, considerably enhanced release of H + (>61%) from the quartz surface was observed in the multidimensional system compared to the one-dimensional setup. Reactive transport modeling was performed to reproduce the experimental outcomes and to analyse the coupling between transport processes, based on the Nernst-Planck formulation of diffusive/dispersive fluxes and on surface complexation reactions at the solid-solution interface. Electrostatic interactions between Na + , B – , and H + , and deprotonation of the quartz surface upon the formation of sodium outer-sphere complexes, are the primary controllers of the spatial and temporal features displayed by the pH and major ions measurements. The reactive transport simulations allowed us to interpret the experimental observations, to visualize the distribution and spatio-temporal evolution of dissolved and solid species, to identify a spatially heterogeneous zonation of Coulombic interactions with distinct behavior at the fringe and core of the injected plumes in the multidimensional setup, and to quantify the different components of the Nerst-Planck fluxes of the charged solutes. This study demonstrates that the domain dimensionality directly affects electrostatic interactions between charged aqueous species in the pore water and surface complexation reactions at the solid-solution interface. The non-trivial effects of dimensionality on multicomponent ionic transport result in a significantly different behavior in 1-D and 2-D systems.

58 GEOSCIENCES↗
DOE OSTI2024

Oxidized Sulfur Species in Slab Fluids as a Source of Enriched Sulfur Isotope Signatures in Arcs

Recycling of oxidized sulfur from subducting slabs to the mantle wedge provides simultaneous explanations for the elevated oxygen fugacity (fO 2 ) in subduction zones, their high hydrothermal and magmatic sulfur outputs, and the enriched sulfur isotopic signatures (i.e., δ 34 S > 0‰) of these outputs. However, a quantitative understanding of the abundance and speciation of sulfur in slab fluids consistent with high pressure experiments is lacking. Here we analyze published experimental data for anhydrite solubility in H 2 O-NaCl solutions to calibrate a high-pressure aqueous speciation model of sulfur within the framework of the deep earth water model. We characterize aqueous complexes, required to account for the high experimental anhydrite solubilities. We then use this framework to predict the speciation and solubility of sulfur in chemically complex fluids in equilibrium with model subducting mafic and ultramafic lithologies, from 2 to 3 GPa and 400 to 800°C at log fO 2 from FMQ-2 to FMQ+4. We show that sulfate complexes of calcium and sodium markedly enhance the stability of sulfate in moderately oxidized fluids in equilibrium with pyrite at fO 2 conditions of FMQ+1 to +2, causing large sulfur isotope fractionations up to 10‰ in the fluid relative to the slab. Such fluids could impart oxidized, sulfur-rich and high δ 34 S signatures to the mantle wedge that are ultimately transferred to arc magmas, without the need to invoke 34 S-rich subducted lithologies.

58 GEOSCIENCES↗
DOE OSTI2026

Power conversion in SnS photocathodes made by electrochemical growth is limited by recombination at (002) buried facets

Herzenbergite α-SnS is a promising p-type semiconductor for photovoltaic and solar fuel applications, but current devices are plagued by substantial photovoltage losses. Here we use vibrating Kelvin probe surface photovoltage for the first time to study the recombination losses in microcrystalline SnS photoelectrodes. α-SnS films of varied crystal orientation, size, and shape are obtained by electrochemical growth from aqueous tin( II ) chloride and sodium thiosulfate solutions near room temperature. After application of a CdS passivation layer, the films function as photocathodes for the methylviologen reduction reaction. Photoelectrochemical and surface photovoltage measurements reveal that the performance of these devices is sensitively controlled by mainly the SnS crystal orientation and to a lesser extent by the grain size. For example, the highest charge recombination rates of 8.97 × 10 14 s −1 cm −2 and lowest photocurrent (0.73 mA cm −2 ) and lowest photovoltage (0.12 V) occur for SnS films containing 500 nm crystals with irregular shapes and SnS lattices tilted away from the (001) orientation. On the other hand, the best performance (1.62 mA cm −2 , 0.16 V, 3.32 × 10 12 s −1 cm −2 ) is seen for 1100 nm fully (001) oriented SnS nanoplates. Furthermore, these findings agree with improved charge carrier mobility in the 001 direction and they also show that charge recombination in SnS films occurs mainly at dangling Sn–S bonds at buried (002) facets. Such buried interfaces need to be suppressed for optimized solar energy conversion with SnS.

Najaf, Zainab [University of California, Davis, CA↗
NASA NTRS1983

An electrochemical rebalance cell for Redox systems

An electrochemical rebalance cell for maintaining electrochemical balance, at the system level, of the acidified aqueous iron chloride and chromium chloride reactant solutions in the redox energy storage system was constructed and evaluated. The electrochemical reaction for the cathode is Fe(+3) + e(-) yields Fe(+2), and that for the anode is 1/2H2 yields H(+) + e(-). The iron (carbon felt) electrode and the hydrogen (platinized carbon) electrode are separated by an anion exchange membrane. The performance of the rebalance cell is discussed as well as the assembly of a single rebalance cell and multicell stacks. Various cell configurations were tested and the results are presented and discussed. The rebalance cell was also used to demonstrate its ability, as a preparative tool, for making high purity solutions of soluble reduced metal ionic species. Preparations of titanium, copper, vanadium and chromium ions in acidified solutions were evaluated.

Acevedo, J. C.↗
NASA NTRS1984

Electrokinetic potential and stability of SiC suspensions in electrolyte solutions

The dependence of zeta potential on pH of an aqueous Si carbide suspension was studied by an electroosmosis method. The effect of pH on the Si carbide electrical double layer is attributed to the participation of H and OH ions in the surface dissociation reactions of weak acid OH groups on an oxidized carbide surface. Maximum stability of the suspensions was observed at maximum negative zeta potentials.

Eremenko, B. V.↗
DOE OSTI2020

Ion-Exchange Modeling of Crystalline Silicotitanate for Cesium Removal - 20283

The Tank Closure Cesium Removal (TCCR) system is a Savannah River Site (SRS) demonstration 'at-tank' process designed to remove {sup 137}Cs from the high-level aqueous tank waste so that the decontaminated solution can be disposed as low-level waste. Cesium is removed by ion exchange (IX) columns using engineered IONSIV{sup TM} R9120-B form of the Crystalline Silicotitanate (CST) media. The TCCR system is deployed at Tanks 10 and Tank 11 in the SRS H Tank Farm. Water is added to the salt-cake in Tank 10 H to dissolve it. The dissolved salt solution waste is pumped out of Tank 10H (feed tank), through filters and IX columns. The decontaminated salt solution is transferred to Tank 11 (receipt tank), and on to Tank 50H for final disposal in the Saltstone Production Facility. The current TCCR can accommodate lead-lag (two-column) or lead-lag-guard (three-column) configurations to optimize media utilization and achieve the target decontamination. To assist the TCCR operations, a parametric study was conducted to evaluate the impact of different parameters (e.g., column configurations (single column, two columns or three columns in series), waste characteristics, operating temperature, process flow rate, CST average particle size) on the IX column performance including CST bed utilization. The initial results indicate that the IX column performance is improved at slower process flow rate, at lower operating temperature, and with smaller CST average particle size. Multi-column configurations are recommended, because the single-column configuration does not utilize CST bed effectively. This paper demonstrates the versatility of the ion exchange modeling to evaluate the effects of CST characteristics and operational parameters on IX column performances. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Soft x-ray spectroscopy of ammonium sulfate aerosols at varied pH conditions

Aqueous aerosols are useful model systems for understanding the physical chemistry that takes place in the Earth’s atmosphere, as well as the chemistry of other solar system objects. Ammonium sulfate aerosols are impacted by anthropogenic sources such as farming and shipping and are understood to be important seeds of cloud nucleation in the atmosphere, affecting climate. X-ray photoelectron spectroscopy and near edge x-ray absorption fine structure spectroscopy were used in tandem to probe the surface and bulk properties of aqueous (NH 4 ) 2 SO 4 , respectively. Aerosolized solutions of (NH 4 ) 2 SO 4 , some altered with NaOH to modify pH, were introduced via an aerodynamic lens to a velocity map imaging instrument for detection. The results show that as pH and sodium cation concentration increase, sulfate anion and ammonia become more prevalent at the surface, and the aerosol surface appears to become drier. However, most of the aerosol remains aqueous, with ion concentrations insensitive to the addition of NaOH. Density functional theory calculations were also performed to probe the coordination environment at the aerosol surfaces to understand the underlying phenomena. Finally, the changes seen on the surface of the aerosol underscore the importance of pH in regulating the structure and chemical properties of atmospherically relevant aerosols.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Corrosion Prevention of Additively Manufactured Aluminum Packing Devices Developed for Process Intensification of CO 2 Capture by Aqueous Amines

Corrosion of additively manufactured (i.e., 3D printed) aluminum packing devices, developed to enhance heat and mass transfer in CO 2 absorption columns using amine-CO 2 scrubbing solutions, is investigated in this paper. The aluminum structures printed by selective laser melting with Al-10Si-0.3Mg feed powder are susceptible to corrosion in aqueous monoethanolamine, both fresh and used CO 2 -saturated solutions. The efficacy of corrosion-protective surface layers of aqueous polyether–ketone–ketone (PEKK) dip coating to provide amine corrosion resistance to the 3D printed aluminum structure is also evaluated. PEKK nanothick layers were coated on the corrugated surface of a 3D printed structure, identical to that of the intensified device, yielding 27 times higher corrosion resistance than the uncoated Al alloy surface. Finally, a systematic long-term electrochemical corrosion analysis revealed that a multilayer PEKK dip coating protocol enables protection of the 3D printed Al alloy surface in various CO 2 –monoethanolamine solutions.

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

Thermodynamic modeling of MDEA(aq)-NH 3 (aq)-K 2 CO 3 (aq)-CO 2 (aq) using the Extended UNIQUAC model

Here, the development of advanced processes for carbon dioxide capture requires reliable thermodynamic models to ensure accurate process design. This work presents an optimized parameter set of the Extended UNIQUAC model for advanced mixed solvent solutions containing CO 2 -MDEA-NH 3 -K 2 CO 3 in water. The model was parameterized using vapor–liquid equilibrium, pure component saturation pressure, excess enthalpy, heat of absorption, molar heat capacity, apparent molar heat capacity, and solid–liquid equilibrium. These thermal and equilibrium properties cover temperatures between 253.6 K to 600 K and pressures up to 75.6 bar. The current model represents an extension of previous versions that were suitable for modeling aqueous NH 3 and K 2 CO 3 solutions. This parametrization accounts for molecular interactions between MDEA and these two components, which allows for the design of advanced capture processes. This paper demonstrates that the new model parameters are valid within the range of operational conditions typically found in CO 2 capture processes.

42 ENGINEERING↗
DOE OSTI2020

Phyllosilicate mineral dissolution upon alkaline treatment under aerobic and anaerobic conditions

The dissolution of phyllosilicate minerals exposed to high-pH environments has been studied to determine the influence of alkaline treatments and variable redox conditions on clay dissolution and the potential formation of new phases via incongruent dissolution phenomena. The present study focused on the dissolution of phyllosilicate minerals (illite, muscovite, and montmorillonite) under anaerobic and aerobic conditions using comparative solutions (sodium hydroxide and ammonium hydroxide) at similar ionic strength in the presence and absence of oxygen. Our batch data show that there is a rapid decrease in aluminum dissolution (< 240 hrs) and slow increase in silica over time (up to 1440 hrs). This trend was particularly evident for montmorillonite which shows the greatest dissolution for ammonium hydroxide, likely due to intercalation of the polyatomic cation ammonium into the mineral’s expandable layers. When comparing alkaline treatments, the strong base, sodium hydroxide, dissolved more of the mica minerals, illite and muscovite, likely due to ion-pairing between the silicate tetrahedra [SiO4]n- and Na+ cations in solution. In addition, redox conditions affect the systems similarly with treatment, although the sodium hydroxide treatment results in greater variability in solution redox conditions. For all investigated phyllosilicates, the calculated aqueous aluminum and silicon ratios over time are significantly different from the minerals’ stoichiometric ratios. As a result, we conclude that incongruent dissolution occurred and suggest formation of secondary precipitates. Understanding the potential for clay mineral alterations from interaction with alkaline solutions has implications for in situ remediation, mining operations, and waste interactions with the subsurface. This research shows that incongruent dissolution is likely and will lead to secondary precipitation which may have long term physical and chemical impacts in the subsurface.

mineral dissolution, phyllosilicate, alkaline, amm↗
DOE OSTI2023

Methods of recovering an elemental rare earth metal, and methods of forming a rare earth metal

A method of recovering an elemental rare earth metal comprises placing a rare earth-containing material comprising a rare earth metal in a reaction solution comprising a reducing agent and a non-aqueous solvent comprising an ionic liquid or a eutectic mixture, reducing the rare earth metal with the reducing agent to form a metallic rare earth metal and cations of the reducing agent, transferring the cations of the reducing agent from the reaction solution to an electrochemical cell through an ion exchange membrane, and reducing the cations of the reducing agent in the electrochemical cell. Related methods of forming an elemental rare earth metal, and related systems are disclosed.

Case, Mary E.↗
NASA NTRS1992

Soil mineralogy and chemistry on Mars - Possible clues from salts and clays in SNC meteorites

If the shergottite, nakhlite, and chassignite (SNC) meteorites' parent planet is Mars, then the aqueous precipitates found in them imply that oxidizing, water-based solutions may have been chemically active on that planet over the past 200-1300 million yrs. It is suggested that the mixture of aqueous precipitates found in the SNCs furnish a self-consistent model for the bulk elemental composition of surface sediments at the Viking Lander sites. Further mineralogical and stable-isotope studies of the secondary minerals may establish the limits for biological activity over the last 1300 million years of Mars' water-based chemistry.

Gooding, James L.↗
DOE OSTI2023

Diffusion of Hydrophilic to Hydrophobic Forms of Nile Red in Aqueous C 12 EO 10 Gels by Variable Area Fluorescence Correlation Spectroscopy

In this work, solute diffusion within lyotropic liquid crystal gels prepared from a series of water and decaethylene glycol monododecyl ether (C 12 EO 10 ) mixtures was explored by variable area fluorescence correlation spectroscopy. Aqueous C 12 EO 10 gels were prepared in concentrations ranging from 55:45 to 70:30 wt% of surfactant and water. Small angle X-ray scattering revealed that these gels comprise hexagonal mesophases of cylindrical micelles. Micelle spacing was found to decrease with increasing C 12 EO 10 concentration. Three different Nile red (NR) dyes were employed as model solutes and were separately doped into the gels at nanomolar levels. These include a hydrophilic form of NR incorporating an anionic sulfonate group (NRSO 3 - ), a hydrophobic form incorporating a fourteen-carbon alkane tail (NRC 14 ), and commercial NR as an intermediate case. FCS data acquired from the gels revealed that NRSO 3 - diffused primarily in 3D. Its diffusion coefficient exhibited a monotonic decrease with increasing gel concentration and micelle packing density, consistent with confinement of its motions as a result of its exclusion from the micelle cores. NRC 14 exhibited the smallest diffusion coefficient, most likely due to its larger size and enhanced interactions with the micelle cores. NR yielded an intermediate diffusion coefficient and the most anomalous behavior of the three dyes, attributable to its facile partitioning between core and corona regions, and greater participation by 1D diffusion. The results of these studies afford an improved understanding of molecular mass transport through soft-matter nanomaterials like those being developed for use in drug delivery and membrane based chemical separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Viscous flow properties and hydrodynamic diameter of phenothiazine-based redox-active molecules in different supporting salt environments

We report viscous flow properties of a redox-active organic molecule, N-(2-(2-methoxyethoxy)ethyl)phenothiazine (MEEPT), a candidate for non-aqueous redox flow batteries, and two of its radical cation salts. A microfluidic viscometer enabled the use of small sample volumes in determining viscosity as a function of shear rate and concentration in the non-aqueous solvent, acetonitrile, both with and without supporting salts. All solutions tested show Newtonian behavior over shear rates of up to 30 000 s−1, which was rationalized by scaling arguments for the diffusion-based relaxation time of a single MEEPT molecule without aggregation. Neat MEEPT is flowable but with a large viscosity (412 mPa⋅s at room temperature), which is ∼1000 times larger than that of acetonitrile. MEEPT solutions in acetonitrile have low viscosities; at concentrations up to 0.5 M, the viscosity increases by less than a factor of two. From concentration-dependent viscosity measurements, molecular information was inferred from intrinsic viscosity (hydrodynamic diameter) and the Huggins coefficient (interactions). Model fit credibility was assessed using the Bayesian Information Criterion. It is found that the MEEPT and its charged cations are “flowable” and do not flocculate at concentrations up to 0.5 M. MEEPT has a hydrodynamic diameter of around 8.5 Å, which is almost insensitive to supporting salt and state of charge. This size is comparable to molecular dimensions of single molecules obtained from optimized structures using density functional theory calculations. The results suggest that MEEPT is a promising candidate for redox flow batteries in terms of its viscous flow properties.

Wang, Yilin (ORCID:0000000316102995)↗
DOE OSTI2023

Solid–Adsorbed Polymer–Electrolyte Interphases for Stabilizing Metal Anodes in Aqueous Zn and Non–Aqueous Li Batteries

Polymers are known to adsorb spontaneously from liquid solutions in contact with high-energy substrates to form configurationally complex, but robust phases that often exhibit higher durability than might be expected from the individual physical bonds formed with the substrate. Rational control of the physical, chemical, and transport properties of such interphases has emerged as a fundamental opportunity for scientific and technological advances in energy storage technology but requires in-depth understanding of the conformation states and electrochemical effect of the adsorbed polymers. Here, we analyze the interfacial adsorption of oligomeric polyethylene glycol (PEG) chains of moderate sizes dissolved in protic and aprotic liquid electrolytes and find that there is an optimum polymer molecular weight of approximately 400 Da at which the highest columbic efficiency is achieved for both Zn and Li deposition. Furthermore, these findings point to a simple, versatile approach for extending the lifetime of batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1987

Atmospheric H2O2 measurement: comparison of cold trap method with impinger bubbling method

Collection of atmospheric H2O2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5 l min-1 for approximately 2 h. Collection efficiency was > 99% and negligible interferences by O3, SO2 or organic matter with the collected H2O2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir. Sci. Technol. 12, 1072-1080). The measured total peroxide (H2O2 + organic peroxide) values in a series of aim samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H2O2 and organic peroxide in the impinger solution by a reaction of atmospheric O3 with olefinic and aromatic compounds. If these O3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H2O2 in clouds and rainwater.

NASA Discipline Exobiology↗
DOE OSTI2024

3D Printing of Functional Hydrogel Devices for Screenings of Membrane Permeability and Selectivity

Developing a fundamental understanding of the effects of varying ligand chemistries on mass transport rates is key to designing membranes with solute-specific selectivity. While permeation cells offer a robust method to characterize membrane performance, they are limited to assessing a single membrane chemistry or salt solution per test. As a result, investigating the effects of varying ligand chemistries on membrane performance can be a tedious process, involving both the preparation of multiple samples and numerous, time-consuming permeation tests. This study uses digital light processing (DLP) 3D printing to fabricate a millifluidic flow-based permeation device made from a hydrogel active ester network that can be easily functionalized with ion-selective ligands. Without the need for bonding or assembly steps, ligands can be introduced and tested in the permeation device by simply injecting a small volume of a ligand solution. Various salt concentrations and molecular species can be cycled through a single device by switching the solution feeding into the salt reservoir, thereby reducing the number of samples needed for permeability and selectivity screenings. This research sets the groundwork for formulation development and postprocessing methods to 3D-print functional millifluidic devices capable of assessing solute selectivity in membranes and polymer adsorbents for aqueous separations. In this work, comparable salt permeability trends were observed with both 3D-printed devices and traditional assays. Devices were functionalized with an imidazole ligand to investigate salt permeability and selectivity of monovalent and divalent salts. Measurements showed increasing permeability for monovalent salts (NaCl) relative to divalent salts (MgCl 2 , CuCl 2 ) in functionalized membranes, with higher monovalent/divalent selectivity at increasing imidazole grafting densities. Here, the methods and findings described here represent a step toward developing higher-throughput methods with 3D-printed devices for screening the effects of ligand chemistry on mass transport rates in membrane materials.

36 MATERIALS SCIENCE↗