Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Aqueous solution”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,387 records · Page 77
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Phase diagrams and microstructures of aqueous short alkyl chain polyethylene glycol ether carboxylate and carboxylic acid triblock surfactant solutions

The surfactant C 8 Eo 8 CH 2 COOH (Akypo LF2) and its salts have a small hydrophobic and a significantly longer hydrophilic part. As a consequence, there must be a significant steric constraint, once these surfactant molecules form micelles. In addition, the partially charged headgroups should bring some additional fine-tuning via electrostatic interactions to this "essentially non-ionic" surfactant. Experiments: Phase diagrams of binary mixtures of water and C 8 Eo 8 CH 2 COOH are established over large concentration and temperature ranges, also at different pHs and in the presence of sodium and calcium ions. Surface tensions and osmotic pressures are measured to understand the systems. To evaluate the microstructures, also Dynamic Light Scattering and Small-Angle X-ray Scattering are performed.

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

Water Defect Stabilizes the Bi 3+ Lone-Pair Electronic State Leading to an Unusual Aqueous Hydration Structure

In this work, the aqueous hydration structure of Bi 3+ is probed using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) simulations of ion-water clusters and of condensed-phase solutions. Anomalous features in the EXAFS spectra are found to be associated with a highly asymmetric first-solvent water shell. The aqueous chemistry and structure of the Bi 3+ ion is dramatically controlled by the water stabilization of a lone-pair electronic state involving the mixed 6s and 6p orbitals. This leads to a distinct multi-modal distribution of waters in the first shell that are separated by about 0.2Å. The lone-pair structure is stabilized by a collective response of multiple waters that are localized near the lone-pair anti-bonding site. The findings indicate that the lone-pair stereochemistry of aqueous Bi 3+ plays a major role in the binding of water and ligands in aqueous solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

The Stability of Nd Hydroxyl Complexes at Near Neutral to Alkaline pH from 25 to 75 °C: Implications for Monazite Solubility in Hydrothermal Aqueous Fluids

Speciation of rare earth elements (REE) in aqueous fluids controls their mobilization during fluid-rock interaction. Thermodynamic modeling provides important insights into the factors controlling REE mobility and fractionation in aqueous fluids, in which aqueous REE hydroxyl complexes are particularly important across a broad pH range. However, the stability of these REE hydroxyl complexes remains poorly determined due to limited experimental data above ambient temperature. In this work, UV–vis spectrophotometry experiments were conducted to determine the cumulative hydrolysis constants for neodymium (Nd) from 25 to 75 °C in near-neutral to alkaline solutions. The color indicator m -cresol purple was used to determine in situ pH. Alkaline NaOH-bearing aqueous solutions were doped with varying initial Nd concentrations (0 to ∼0.155 mmol/kg), which resulted in the release of protons (H + ) and pH decrease during hydrolysis of Nd 3+ according to Nd 3+ + n H 2 O = Nd(OH) n 3– n + H + . The average OH – ligand number coordinated to Nd 3+ was found to increase from 1.0 to 1.6 at 25 °C and from 1.2 to 2.8 at 75 °C over a pH range from 6.3 to 9.0. The measured speciation shows an increased predominance of Nd(OH) 3 0 over the Nd(OH) 2 + and Nd(OH) 2+ species with increased temperature and pH. The increasing cumulative formation constants (log*β° n , n = 1 to 3) retrieved from 25 to 75 °C differ by 0.1 to 1.9 logarithmic units in comparison to existing thermodynamic databases. These updated thermodynamic data have important implications for geochemical modeling of the speciation of Nd hydroxyl complexes and the solubility of monazite as a function of pH.

58 GEOSCIENCES↗
NASA NTRS1986

A new technique for collection, concentration and determination of gaseous tropospheric formaldehyde

This article describes an improved technique for making in situ measurements of gaseous tropospheric formaldehyde (CH2O). The new technique is based on nebulization/reflux principles that have proved very effective in quantitatively scrubbing water soluble trace gases (e.g., CH2O) into aqueous mediums, which are subsequently analyzed. Atmospheric formaldehyde extractions and analyses have been performed with the nebulization/reflux concentrator using an acidified dinitrophenylhydrazine solution that indicate that quantitative analysis of CH2O at global background levels (about 0.1 ppbv) is feasible with 20-min extractions. Analysis of CH2O, once concentrated, is accomplished using high performance liquid chromatography with ultraviolet photometric detection. The CH2O-hydrazone derivative, produced by the reaction of 2,4-dinitrophenylhydrazine in H2SO4 acidified aqueous solution, is detected as CH2O.

Cofer, W. R., III↗
DOE OSTI2021

Enhanced electro-osmosis in propylene carbonate salt solutions

Properties of solid–liquid interfaces and surface charge characteristics mediate ionic and molecular transport through porous systems, affecting many processes such as separations. Herein, we report experiments designed to probe the electrochemical properties of solid–liquid interfaces using a model system of a single polyethylene terephthalate (PET) pore in contact with aqueous and propylene carbonate solutions of LiClO 4 . First, the existence and polarity of surface charges were inferred from current–voltage curves recorded when a pore was placed in contact with a LiClO4 concentration gradient. Second, the electro-osmotic transport of uncharged polystyrene particles through the PET pore provided information on the polarity and the magnitude of the pore walls’ zeta potential. Our experiments show that the PET pores become effectively positively charged when in contact with LiClO 4 solutions in propylene carbonate, even though in aqueous LiClO 4 , the same pores are negatively charged. Additionally, the electro-osmotic velocity of the particles revealed a significantly higher magnitude of the positive zeta potential of the pores in propylene carbonate compared to the magnitude of the negative zeta potential in water. The presented methods of probing the properties of solid–liquid interfaces are expected to be applicable to a wide variety of solid and liquid systems.

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

Zinc-iodine secondary energy storage methods, devices, and electrolytes

Disclosed are cathodes having electron-conductive high-surface-area materials, aqueous non-halide-containing electrolytes, secondary zinc-iodine energy storage devices using the same, and methods for assembling the same. The disclosed high-surface-area materials and the aqueous non-halide-containing electrolyte solutions can contribute together to the confinement of the active iodine species in the cathode and to the minimization of shuttle effects and self-discharging. The non-halide-containing electrolyte salts can facilitate preferential adsorption of the iodine species to the cathode material rather than dissolution in the aqueous electrolyte solution, thereby contributing to the confinement of the active iodine species.

25 ENERGY STORAGE↗
DOE OSTI2020

Recovery of High Purity Rare Earth Elements (REE) from Coal Ash via a Novel Electrowinning Process (Final Report)

The goal of this project was to produce a high purity, separated (>90%) rare earth oxide (REO) product from coal-based sources. This product was achieved using the following three steps: 1. Battelle’s ADP: The ADP process involves pretreatment of ash (milling and caustic leaching), leaching of pretreated ash with nitric acid, roasting of loaded acid solution containing REE, and water leaching of residual from roasting step, resulting in a REE pregnant solution. 2. Solvent Extraction (SX) Upgrading: The SX involves the extraction of REE from a pregnant REE solution using an organic extractant (note after extraction, the aqueous phase was a residual solution and the organic phase contained REE), and stripping of REE from the organic phase product obtained from the extraction using an acid solution (the stripped solution was the final purified product containing REE, organic traces, and traces of other metals for further separation in the electrowinning process). 3. Rare Earth Salts’ (RES) Electrochemical Separation and Purification Process: The staged electrochemical process was separated REO products from the mixed REE solution. Testing by RES was also included in the investigation of options to minimize the solvent extraction steps. This report covers laboratory testing, production of a high purity coal-based REO, process design of the overall REE recovery and purification process, technoeconomic assessment (TEA), and a commercialization plan discussing the overall REE recovery and purification process.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Structural Evidence of Interanionic Hydrogen Bonding in Phosphoric Acid Solutions

Interanionic hydrogen bonding (IAHB) is a noncovalent interaction between like-charged ions that challenges conventional electrostatic understanding. This study provides direct structural evidence of IAHB in concentrated aqueous phosphoric acid (PA) solutions, which exhibit >60% dissociation under these conditions. Oxygen K-edge X-ray absorption fine structure spectroscopy, combined with electron affinity time-dependent density functional theory calculations, reveals the formation of stable, cyclic phosphate-phosphate IAHB dimers at PA concentrations ≥7 M. Extended X-ray absorption fine structure data show distinct long-range ordering consistent with these dimers, and near-edge X-ray absorption fine structure spectra confirm a concentration-dependent transition from monomeric to dimeric species. Energy decomposition analysis through density functional theory shows that the formation of solution-phase IAHB is energetically favored and is attributed to polarization of and the charge transfer between the two fragments driven by the surrounding solvent molecules, in addition to the permanent electrostatics. These findings offers crucial structural insights into the H-bonded networks in concentrated PA, highlighting the critical role of solvent in facilitating anion–anion association.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

Isomolybdate conversion coatings

A conversion coating solution and process forms a stable and corrosion-resistant layer on metal substrates or layers or, more preferably, on a boehmite layer or other base conversion coating. The conversion coating process involves contacting the substrate, layer or coating with an aqueous alkali metal isomolybdate solution in order to convert the surface of the substrate, layer or coating to a stable conversion coating. The aqueous alkali metal molybdates are selected from sodium molybdate (Na.sub.2 MoO.sub.4), lithium molybdate (Li.sub.2 MoO.sub.4), potassium molybdate (K.sub.2 MoO.sub.4), or combinations thereof, with the most preferred alkali metal molybdate being sodium molybdate. The concentration of alkali metal molybdates in the solution is preferably less than 5% by weight. In addition to the alkali metal molybdates, the conversion coating solution may include alkaline metal passivators selected from lithium nitrate (LiNO.sub.3), sodium nitrate (NaNO.sub.3), ammonia nitrate (NH.sub.4 NO.sub.3), and combinations thereof; lithium chloride, potassium hexafluorozirconate (K.sub.2 ZrF.sub.6) or potassium hexafluorotitanate (K.sub.2 TiF.sub.6).

Minevski, Zoran↗
NASA NTRS1995

Hydrophobic, Porous Battery Boxes

Boxes made of porous, hydrophobic polymers developed to contain aqueous potassium hydroxide electrolyte solutions of zinc/air batteries while allowing air to diffuse in as needed for operation. Used on other types of batteries for in-cabin use in which electrolytes aqueous and from which gases generated during operation must be vented without allowing electrolytes to leak out.

Bragg, Bobby J.↗
DOE OSTI2024

Preparation of acid-deficient uranyl nitrate solutions

A solution of acid deficient uranyl nitrate has a formula of UO2(OH)y(NO3)2-y, where y ranges from 0.1 to 0.5. The solution is prepared by placing UxOz in aqueous nitric acid to produce a uranium solution, wherein x is 1 to 3 and z is 2 to 8; placing the uranium solution under a pressure greater than atmospheric pressure in a sealed reaction chamber; and heating the uranium solution to a desired temperature of between 150° C. and 250° C. by applying microwave energy to the uranium solution. The uranium solution is maintained at the desired temperature under a pressure of from 5 atmospheres to 40 atmospheres for a hold time of 15 minutes to 6 hours to produce the desired acid deficient uranyl nitrate.

Brown, Daniel↗
DOE OSTI2020

High Pressure Infiltration/Expulsion of Aqueous NaCl in Planar Hydrophobic Nanopores

Pressure-driven permeation of water in a poorly wettable material results in a conversion of mechanical work into surface free energy representing a new form of energy storage, or absorption. When water is replaced by a concentrated electrolyte solution, the storage capacity of a nanoporous medium becomes comparable to high-end supercapacitors. The addition of salt can also reduce the hysteresis of the infiltration/expulsion cycle. Our molecular simulations provide a theoretical perspective into the mechanisms involved in the process, and underlying structures and interactions in compressed nanoconfined solutions. Specifically, we consider aqueous NaCl in planar confinements of widths of 1.0 nm and 1.64 nm and pressures of up to 3 kbar. Open ensemble Monte Carlo simulations utilizing fractional exchanges of molecules for efficient additions/removal of ions have been utilized in conjunction with pressure-dependent chemical potentials to model bulk phases under pressure. Confinements open to these pressurized bulk, aqueous electrolyte phases show reversibility at narrow pore sizes and irreversibility in wider ones, consistent with experiment, as well as strong hysteresis at both pore size. The addition of salt results in significant increases in the solid/liquid interfacial tension in narrower pores and associated infiltration and expulsion pressures. Furthermore, these changes are consistent with strong desalination effects at the lower pore size observed irrespective of external pressure and initial concentration.

25 ENERGY STORAGE↗
DOE OSTI2025

Uranyl fluorescence in acidic solution: quenching effects by tetramethylammonium (TMA + )

The quenching of uranyl luminescence by various cation species was studied in aqueous media at low pH. Solutions with different nitrate salts, held at constant uranyl nitrate, nitric acid, and ion concentration, were tested to examine the quenching effects of the cations from the nitrate salts. Alkali metal (Li + , Na + , Rb + ) and quaternary ammonium cations (NH 4 + ), (CH 3 ) 4 N + (TMA + ), (C 2 H 5 ) 4 N + (TEA + ) were investigated. Solutions containing TMA + reduced the lifetime of uranyl fluorescence significantly more than the other cations. Uranyl emission spectra also showed that TMA + increased the complex formation between uranyl and nitrate ions. Fluorescence decay lifetime measurements for most solutions yielded values between 1.4–1.9 μs at 20 °C, while 1.8 M TMA + reduced the lifetime of uranyl fluorescence to 0.6 μs. Decay rate versus concentration data (Stern–Volmer plots) indicated a dynamic quenching process with increasing fluorescence decay rates at higher cation concentrations for Li + , TMA + , and TEA + . The temperature dependencies of the decay rates and the kinetics in D 2 O were also examined.

Persinger, Thomas D. [Argonne National Laboratory ↗
NASA NTRS1999

Wash Solution Bath Life Extension for the Space Shuttle Rocket Motor Aqueous Cleaning System

A spray-in-air aqueous cleaning system, which replaced 1,1,1 trichloroethane (TCA) vapor degreasing, is used for critical cleaning of Space Shuttle Redesigned Solid Rocket Motor (RSRM) metal parts. Small-scale testing demonstrated that the alkaline-based wash solution possesses adequate soil loading and cleaning properties. However, full-scale testing exhibited unexpected depletion of some primary components of the wash solution. Specifically, there was a significant decrease in the concentration of sodium metasilicate which forced change-out of the wash solution after eight days. Extension of wash solution bath life was necessary to ease the burden of frequent change-out on manufacturing. A laboratory study supports a depletion mechanism that is initiated by the hydrolysis of sodium tripolyphosphate (STPP) lowering the pH of the solution. The decrease in pH causes polymerization and subsequent precipitation of sodium metasilicate (SM). Further investigation showed that maintaining the pH was the key to preventing the precipitation of the sodium metasilicate. Implementation to the full scale operation demonstrated that periodic additions of potassium hydroxide (KOH) extended the useful bath life to more than four months.

Saunders, Chad↗
DOE OSTI2022

Specific Ion Effects in Lanthanide–Amphiphile Structures at the Air–Water Interface and Their Implications for Selective Separation

The use of surfactants to attract dissolved ions to water surfaces and interfaces is an essential step in both solvent-based and solvent-free separation processes. Here, we have studied the interactions of lanthanide ions in the aqueous subphase with monolayers of dihexadecyl phosphate at air–water interfaces. With heavier lanthanides (atomic number Z ≥ 65) in the subphase, the floating layer can be compressed to an area/molecule of about half the molecular cross section, indicating bilayer formation. X-ray fluorescence and reflectivity data support this conclusion. In the presence of lighter lanthanides (Z < 65), only monolayers are observed. Subphase-concentration-dependent studies using Er 3+ (heavier) and Nd 3+ (lighter) lanthanides show a stepwise progression, with ions attaching to the monolayer only when the solution concentration is >3 × 10 –7 M. Above ~10 –5 M, bilayers form but only in the presence of the heavier lanthanide. Grazing incidence X-ray diffraction shows evidence of lateral ion–ion correlations in the bilayer structure but not in monolayers. Explicit solvent all-atom molecular dynamics simulations confirm the elevated ion–ion correlation in the bilayer system. This bilayer structure isolates heavier lanthanides but not lighter lanthanides from an aqueous solution and is therefore a potential mechanism for the selective separation of heavier lanthanides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Resolving the Solvation Structure and Transport Properties of Aqueous Zinc Electrolytes from Salt-in-Water to Water-in-Salt Using Neural Network Potential

Zn Cl 2 solutions are promising electrolytes for aqueous zinc-ion batteries. Here, we report a joint computational and experimental study of the structural and dynamic properties of aqueous Zn Cl 2 electrolytes with concentrations ranging from salt-in-water to water-in-salt (WIS). By developing a neural network potential (NNP) model, we perform molecular dynamics (MD) simulations with accuracy but at much larger lengths and longer timescales. The NNP predicted structures are validated by the structure factors measured by X-ray total scattering experiments. The MD trajectories provide a comprehensive and quantitative picture of the Zn 2 + solvation shell structures. Additionally, we find that the O − H covalent bonds in water are strengthened with increasing salt concentration, thus expanding the electrochemical stability window of aqueous electrolytes. In terms of dynamic properties, the calculated and experimentally measured conductivities are in good agreement. Through the analysis of the calculated cation transference number, we propose a three-stage charge carrier transport mechanism with increasing concentration: independent ion transport, strongly correlated ion transport, and small positive charge carrier diffusion through negatively charged polymeric clusters. Our study provides fundamental atomic scale insights into the structure and transport properties of the Zn Cl 2 electrolyte that can aid the optimization and development of WIS electrolytes. Published by the American Physical Society 2025

25 ENERGY STORAGE↗
NASA NTRS2021

Dissolution Rates of Allophane with Variable Fe Contents: Implications for Aqueous Alteration and the Preservation of X-ray Amorphous Materials on Mars

Recent measurements from Mars document X-ray amorphous/nano-crystalline materials in multiple locations across the planet. However, despite their prevalence, little is known about these materials or what their presence implies for the history of Mars. The X-ray amorphous component of the martian soil in Gale crater has an X-ray diffraction pattern that can be partially fit with allophane (approximately Al2O3•(SiO2)1.3-2•(H2O)2.5-3), and the low-temperature water release data are consistent with allophane. The chemical data from Gale crater suggest that other silicate materials similar to allophane, such as Fe-substituted allophane (approximately (Fe2O3)0.01-0.5(Al2O3)0.5-0.99•(SiO2)2•3H2O), may also be present. In order to investigate the properties of these potential poorly crystalline components of the martian soil, Fe-free allophane (Fe:Al = 0), Fe-poor allophane (Fe:Al = 1:99), and Fe-rich allophane (Fe:Al = 1:1) were synthesized and then characterized using electron microscopy and Mars-relevant techniques, including infrared spectroscopy, X-ray diffraction, and evolved gas analysis. Dissolution experiments were performed at acidic (initial pH values pH0 = 3.01, pH0 = 5.04), near-neutral (pH0 = 6.99), and alkaline (pH0 = 10.4) conditions in order to determine dissolution kinetics and alteration phases for these poorly crystalline materials. Dissolution rates (rdiss), based on the rate of Si release into solution, show that these poorly crystalline materials dissolve approximately an order of magnitude faster than crystalline phases with similar compositions at all pH conditions. For Fe-free allophane, logrdiss = -10.65 – 0.15 × pH; for Fe-poor allophane, logrdiss = -10.35 – 0.22 × pH; and for Fe-rich allophane, logrdiss = -11.46 – 0.042 × pH at 25°C, where rdiss has the units of mol m-2 s-1. The formation of incipient phyllosilicate-like phases was detected in Fe-free and Fe-rich allophane reacted in aqueous solutions with pH0 = 10.4 (steady-state pH ≈ 8). Mars-analog instrument analyses demonstrate that Fe-free allophane, Fe-poor allophane, and Fe-rich allophane are appropriate analogs for silicate phases in the martian amorphous soil component. Therefore, similar materials on Mars must have had limited interaction with liquid water since their formation. Combined with chemical changes expected from weathering, such as phyllosilicate formation, the rapid alteration of these poorly crystalline materials may be a useful tool for evaluating the extent of aqueous alteration in returned samples of martian soils.

S J Ralston↗