Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “complex aqueous solutions”

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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Topological controls on aluminosilicate glass dissolution: Complexities induced in hyperalkaline aqueous environments

Abstract Fly ash, an aluminosilicate composite consisting of disordered (major) and crystalline (minor) compounds, is a low‐carbon alternative that can partially replace ordinary portland cement (OPC) in the binder fraction of concrete. Therefore, understanding the reactivity of fly ash in the hyperalkaline conditions prevalent in concrete is critical to predicting concrete's performance; including setting and strength gain. Herein, temporal measurements of the solution composition (using inductively coupled plasma‐optical emission spectrometry: ICP‐OES) are used to assess the aqueous dissolution rate of monophasic synthetic aluminosilicate glasses analogous to those present in technical fly ashes, under hyperalkaline conditions (10 ≤ pH ≤ 13) across a range of temperatures (25°C ≤ T≤45°C). The dissolution rate is shown to depend on the average number of topological constraints per atom within the glass network (n c , unitless), but this dependence weakens with increasing pH (>10). This is postulated to be on account of: (a) time‐dependent changes in the glass’ surface structure, that is, the number of topological constraints; and/or (b) a change in the dissolution mechanism (eg from network hydrolysis to transport control). The results indicate that the topological description of glass dissolution is most rigorously valid only at very short reaction times (ie at high undersaturations), especially under conditions of hyperalkalinity. These findings provide an improved basis to understand the underlying factors that affect the initial and ongoing reactivity of aluminosilicate glasses such as fly ash in changing chemical environments, for example, when such materials are utilized in cementitious composites.

Oey, Tandré↗
DOE OSTI2020

Effect of Bicarbonate, Calcium, and pH on the Reactivity of As(V) and U(VI) Mixtures

Natural or anthropogenic processes can increase the concentration of uranium (U) and arsenic (As) above the maximum contaminant levels in water sources. Bicarbonate and calcium (Ca) can have major impacts on U speciation and can affect the reactivity between U and As. We therefore investigated the reactivity of aqueous U and As mixtures with bicarbonate and Ca for acidic and neutral pH conditions. In experiments performed with 1 mM U and As mixtures, 10 mM Ca, and without added bicarbonate (pCO 2 = 3.5), aqueous U decreased to <0.25 mM at pH 3 and 7. Aqueous As decreased the most at pH 3 (~0.125 mM). Experiments initiated with 0.005 mM As and U showed similar trends. X-ray spectroscopy (i.e., XAS and EDX) and diffraction indicated that U-As-Ca- and U-Ca-bearing solids resemble uranospinite [Ca(UO 2 ) 2 (AsO 4 ) 2 ·10H 2 O] and becquerelite [Ca(UO 2 ) 6 O 4 (OH) 6 ·8(H 2 O)]. These findings suggest that U-As-Ca-bearing solids formed in mixed solutions are stable at pH 3. However, the dissolution of U-As-Ca and U-Ca-bearing solids at pH 7 was observed in reactors containing 10 mM bicarbonate and Ca, suggesting a kinetic reaction of aqueous uranyl-calcium-carbonate complexation. Our study provides new insights regarding U and As mobilization for risk assessment and remediation strategies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Capturing Carbonation: Understanding Kinetic Complexities through a New Era of Electron Microscopy

Cryogenic plasma focused ion beam (PFIB) electron microscopy analysis is applied to visualizing ex situ (surface industrial) and in situ (subsurface geologic) carbonation products, to advance understanding of carbonation kinetics. Ex situ carbonation is investigated using NIST fly ash standard #2689 exposed to aqueous sodium bicarbonate solutions for brief periods of time. In situ carbonation pathways are investigated using volcanic flood basalt samples from Schaef et al. (2010) exposed to aqueous CO 2 solutions by them. The fly ash reaction products at room temperature show small amounts of incipient carbonation, with calcite apparently forming via surface nucleation. Reaction products at 75° C show beginning stages of an iron carbonate phase, e.g., siderite or ankerite, common phases in subsurface carbon sequestration environments. This may suggest an alternative to calcite in carbonation low calcium-bearing fly ashes. Flood basalt carbonation reactions show distinct zonation with high calcium and calcium-magnesium bearing zones alternating with high iron-bearing zones. The calcium-magnesium zones are notable with occurrence of localized pore space. Oscillatory zoning in carbonate minerals is distinctly associated with far-from-equilibrium conditions where local chemical environments fluctuate via a coupling of reaction with transport. The high porosity zones may reflect a precursor phase (e.g., aragonite) with higher molar volume that then “ripens” to the high-Mg calcite phase-plus-porosity. These observations reveal that carbonation can proceed with evolving local chemical environments, formation and disappearance of metastable phases, and evolving reactive surface areas. Together this work shows that future application of cryo-PFIB in carbonation studies would provide advanced understanding of kinetic mechanisms for optimizing industrial-scale and commercial-scale applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

A Highly Soluble Iron–Based Posolyte Species with High Redox Potential for Aqueous Redox Flow Batteries

A novel iron-based posolyte redox species are presented for an aqueous redox flow battery, (Tetrakis(2-pyridylmethyl)ethylenediamine)iron(II) dichloride, which is obtained by a simple synthetic route, shows a high redox potential of 0.788 V versus SHE, and exhibits exceptional aqueous solubility of 1.46 M. Paired with bis(3-trimethylammonio)propyl viologen tetrachloride at neutral pH, the battery demonstrates an open-circuit voltage of 1.19 V and delivers good cycling performance, with a capacity fade rate of 0.28% per day and coulombic efficiency of 99.3%. Postmortem chemical and electrochemical analyses of the posolyte species suggest future routes for stabilization of the complex. Among all the iron complexes with a redox potential above 0.4 V versus SHE, this compound exhibits the highest solubility. Furthermore, these results offer valuable insights that can be applied to the development of future posolyte species for sustainable energy storage solutions.

25 ENERGY STORAGE↗
DOE OSTI2024

Ion pair extractant selective for LiCl and LiBr

Improved methods for achieving the selective extraction of lithium salts from lithium sources, including rocky ores, salt-lake brines, and end-of-life lithium-ion batteries, could help address projected increases in the demand for lithium. Here, we report an ion pair receptor (2) capable of extracting LiCl and LiBr into an organic receiving phase both from the solid state and from aqueous solutions. Ion pair receptor 2 consists of a calix[4]pyrrole framework, which acts as an anion binding site, linked to a phenanthroline cation binding motif via ether linkages. Receptor 2 binds MgBr 2 and CaCl 2 with high selectivity over the corresponding lithium salts in a nonpolar aprotic solvent. The preference for Mg 2+ and Ca 2+ salts is reversed in polar protic media, allowing receptor 2 to complex LiCl and LiBr with high selectivity and affinity in organic media containing methanol or water. The effectiveness of receptor 2 as an extractant for LiCl and LiBr under liquid–liquid extraction (LLE) conditions was found to be enhanced by the presence of other potentially competitive salts in the aqueous source phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1973

Aqueous chloride stress corrosion cracking of titanium: A comparison with environmental hydrogen embrittlement

The physical characteristics of stress corrosion cracking of titanium in an aqueous chloride environment are compared with those of embrittlement of titanium by a gaseous hydrogen environment in an effort to help contribute to the understanding of the possible role of hydrogen in the complex stress corrosion cracking process. Based on previous studies, the two forms of embrittlement are shown to be similar at low hydrogen pressures (100 N/sqm) but dissimilar at higher hydrogen pressures. In an effort to quantify this comparison, tests were conducted in an aqueous chloride solution using the same material and test techniques as had previously been employed in a gaseous hydrogen environment. The results of these tests strongly support models based on hydrogen as the embrittling species in an aqueous chloride environment. Further, it is shown that if hydrogen is the causal species, the effective hydrogen fugacity at the surface of titanium exposed to an aqueous chloride environment is equivalent to a molecular hydrogen pressure of approximately 10 N/sqm.

Nelson, H. G.↗
NASA NTRS1974

Aqueous chloride stress corrosion cracking of titanium - A comparison with environmental hydrogen embrittlement

The physical characteristics of stress corrosion cracking of titanium in an aqueous chloride environment are compared with those of embrittlement of titanium by a gaseous hydrogen environment in an effort to help contribute to the understanding of the possible role of hydrogen in the complex stress corrosion cracking process. Based on previous studies, the two forms of embrittlement are shown to be similar at low hydrogen pressures (100 N/sq m) but dissimilar at higher hydrogen pressures. In an effort to quantify this comparison, tests were conducted in an aqueous chloride solution using the same material and test techniques as had previously been employed in a gaseous hydrogen environment. The results of these tests strongly support models based on hydrogen as the embrittling species in an aqueous chloride environment.

Nelson, H. G.↗
DOE OSTI2023

Binding of uranyl cations to a Zr-based metal-organic framework by density functional theory

Zr-based metal–organic frameworks (Zr-MOFs) have been widely used as ion adsorbents for the removal or extraction of toxic and/or radionuclide species from aqueous solutions. However, the mechanisms by which uranyl cations (UO 2 2+ ) interact with Zr-MOFs have not been established. In this work, the nature of the bonding of uranyl cations with a Zr-MOF was determined using density functional theory for nineteen structurally distinct candidate complexes. Further, the results showed that in all cases the binding energy was of the order of 1.5 eV, but depended on the specific bonding site. The most stable structure involved coordination of the uranyl cation and two structurally distinct oxygens in the Zr-MOF metal node. It was also found that higher degree of deprotonation in Zr-MOF correlated with higher binding energy between the Zr-MOF and uranyl cations. These insights can aid in the design of Zr-MOFs with optimized features for efficient capture of uranyl cations.

36 MATERIALS SCIENCE↗
DOE OSTI2026

CMPO-Functionalized Silica Sorbents for pH-Tunable Separation and Enrichment of Rare-Earth Elements from Environmental Matrices

Rare-earth elements (REEs) are crucial in many applications, yet mutual separation is challenging due to their similar chemical behavior. Octylphenyl- N,N-diisobutyl carbamoyl methyl phosphine oxide (CMPO) is an organophosphorus ligand originally developed for extracting actinides and lanthanides from spent nuclear fuel. Here, we report a pH-tunable CMPOfunctionalized silica sorbent for selective REE separation from complex aqueous matrices. A CMPO-associated silica gel sorbent was synthesized and characterized by Brunauer−Emmett−Teller (BET) surface area, scanning electron microscopy, and X-ray photoelectron spectroscopy to confirm the surface functionalization and binding behavior. Sorbent performance was evaluated by using a synthetic 46- element solution and a real phosphate rock fertilizer leachate. Notably, REEs were successfully eluted with ultrapure water, demonstrating reversible desorption controlled by pH adjustment. Packed-bed column studies increased the REE mass fraction from 3.6% to 64% (20-fold enrichment), with up to 30-fold enrichment of neodymium. The adsorption process follows the Langmuir isotherm behavior and follows pseudo-second-order kinetics. The uptake capacity of 1 μmol of REEs per 4.2 μmol of CMPO supports the formation of a predominantly 4:1 ligand:rare earth element(III) pseudocomplex. These results demonstrate CMPO-functionalized silica as a selective, water-elutable, and low-chemical-input platform for sustainable REE recovery from environmental and industrial sources.

chelating ligands↗
DOE OSTI2021

The pervasive impact of critical fluctuations in liquid–liquid extraction organic phases

Liquid-liquid extraction is an essential chemical separation technique where polar solutes are extracted from an aqueous phase into a nonpolar organic solvent by amphiphilic extractant molecules. A fundamental limitation to the efficiency of this important technology is third phase formation, wherein the organic phase splits upon sufficient loading of polar solutes. The nanoscale drivers of phase splitting are challenging to understand in the complex hierarchically structured organic phases. In this study, we demonstrate that the organic phase structure and phase behavior are fundamentally connected in a way than can be understood with critical phenomena theory. For a series of binary mixtures of trialkyl phosphate extractants with linear alkane diluents, we combine small angle x-ray scattering and molecular dynamics simulations to demonstrate how the organic phase mesostructure over a wide range of compositions is dominated by critical concentration fluctuations associated with the critical point of the third phase formation phase transition. These findings reconcile many longstanding inconsistencies in the literature where small angle scattering features, also consistent with such critical fluctuations, were interpreted as reverse micellar-like particles. Altogether, this study shows how the organic phase mesostructure and phase behavior are intrinsically linked, deepening our understanding of both and providing a new framework for using molecular structure and thermodynamic variables to control mesostructure and phase behavior in liquid-liquid extraction.

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

Hydrothermal solubility of Dy hydroxide as a function of pH and stability of Dy hydroxyl aqueous complexes from 25 to 250 °C

The rare earth elements (REE) have important applications in green energy technologies. The formation of mineral deposits in geologic systems commonly involves hydrothermal fluids which can mobilize the REE. However, the REE speciation is not well known as a function of pH. The thermodynamic properties of REE hydroxyl complexes used in geochemical models are based on the Helgeson-Kirkham-Flowers (HKF) equation of state parameters which were derived by extrapolation of low temperature experimental and estimated data. In this study, Dy hydroxide solubility experiments are combined with available literature data to improve these models from 25 to 250 °C and optimize the thermodynamic properties of Dy 3+ and Dy hydroxyl complexes using GEMSFITS. Batch-type solubility experiments were conducted from 150 to 250 °C and at saturated water vapor pressure in perchloric acid solutions with initial pH values of 2 to 5 in 0.5 pH unit increments. The measured solubility of Dy hydroxide is retrograde with temperature and decreases with pH. The logarithm of total dissolved Dy molality ranges from –2.3 to –5.3 at 150 °C (pH 4.7–5.5), from –2.4 to –5.6 at 200 °C (pH 3.9–5.1), and from –3.7 to –6.9 at 250 °C (pH of 3.4 and 5.0). The optimized standard partial molal Gibbs energies of formation (Δ f G° T ) derived for Dy 3+ and DyOH 2+ display a close to linear relationship with temperature, fitting with previous optimizations based on DyPO 4 solubility data in the literature. A comparison of the optimized ΔfG°T values for aqueous Dy species with predictions from available HKF parameters indicates significant differences ranging from +11 to –26 kJ/mol between 25 and 250 °C. The experimental fits are used to derive the Dy hydroxide solubility products (K s0 ) and formation constants for the hydrolysis of Dy (β n with n = 1 to 3; Dy 3+ + nOH – = DyOH n 3-n ) as a function of temperature. The optimization method presented yields accurate thermodynamic properties for the Dy 3+ aqua ions and the DyOH 2+ species at the acidic to mildly acidic pH studied whereas more experimental work is needed at near-neutral and alkaline conditions to better constrain the other hydroxyl complexes. Furthermore, the optimized thermodynamic data have a significant impact on geochemical modeling of the mobility and solubility of REE minerals in acidic hydrothermal fluids.

58 GEOSCIENCES↗
DOE OSTI2021

Expanding manganese(iv) aqueous chemistry: unusually stable water-soluble hexahydrazide clathrochelate complexes

Mn cage complexes are rare, and the ones successfully isolated in the solid state are not stable in water and organic solvents. In this work, we present the first report of mononuclear Mn clathrochelates, in which the encapsulated metal exists in the oxidation state +4. The complexes are extremely stable in the crystalline state and in solutions and show rich redox chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1980

Silicon oxidation in fluoride solutions

Silicon is produced in a NaF, Na2SiF6, and Na matrix when SiF4 is reduced by metallic sodium. Hydrogen is evolved during acid leaching to separate the silicon from the accompanying reaction products, NaF and Na2SiF6. The hydrogen evolution reaction was studied under conditions simulating leaching conditions by making suspensions of the dry silicon powder in aqueous fluoride solutions. The mechanism for the hydrogen evolution is discussed in terms of spontaneous oxidation of silicon resulting from the cooperative effects of (1) elemental sodium in the silicon that reacts with water to remove a protective silica layer, leaving clean reactive silicon, and (2) fluoride in solution that complexes with the oxidized silicon in solution and retards formation of a protective hydrous oxide gel.

Sancier, K. M.↗
DOE OSTI2025

pH-SWITCHABLE DYNAMIC BINARY COMPLEXES AS VISCOSITY MODIFYING AGENTS

The study of supramolecular structures has been gaining a lot of momentum in recent years due to their potential application in several interesting areas such as medicine, catalysis, energy, oil and gas, etc. Hydraulic fracturing is one area where the ongoing demand for novel viscosity modifiers has prompted researchers to explore various facets of chemistry. In this study, a dynamic binary complex (DBC) solution is presented, with the potential to be useful in the hydraulic fracturing domain. It has a supramolecular structure that is formed by the self-assembly of oleic acid and diethylenetriamine into an elongated network under alkaline conditions. With less than 2 wt% of constituents in aqueous solution, a viscous gel that exhibits high viscosities even under shear was formed. It was sensitive to pH and salinity, and its zero-shear viscosity could be tuned by a factor of ~280 by changing the pH. Furthermore, its viscous properties were pronounced in the presence of salt. Sand settling tests revealed its potential to hold up sand particles for extended periods of time, longer than 24 hours. In conclusion, this DBC solution system has potential to be utilized as a smart pH-switchable hydraulic fracturing fluid that can be prepared using seawater.

02 PETROLEUM↗
DOE OSTI2021

Supramolecular dynamic binary complexes with pH and salt-responsive properties for use in unconventional reservoirs

Hydraulic fracturing of unconventional reservoirs has seen a boom in the last century, as a means to fulfill the growing energy demand in the world. The fracturing fluid used in the process plays a substantial role in determining the results. Hence, several research and development efforts have been geared towards developing more sustainable, efficient, and improved fracturing fluids. Herein, we present a dynamic binary complex (DBC) solution, with potential to be useful in the hydraulic fracturing domain. It has a supramolecular structure formed by the self-assembly of low molecular weight viscosifiers (LMWVs) oleic acid and diethylenetriamine into an elongated entangled network under alkaline conditions. With less than 2 wt% constituents dispersed in aqueous solution, a viscous gel that exhibits high viscosities even under shear was formed. Key features include responsiveness to pH and salinity, and a zero-shear viscosity that could be tuned by a factor of ~280 by changing the pH. Furthermore, its viscous properties were more pronounced in the presence of salt. Sand settling tests revealed its potential to hold up sand particles for extended periods of time. In conclusion, this DBC solution system has potential to be utilized as a smart salt-responsive, pH-switchable hydraulic fracturing fluid.

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

Unraveling pH-Dependent Changes in Adsorption Structure of Uranyl on Alumina (012)

Mitigating uranium transport in groundwater is imperative for ensuring access to clean water across the globe. Here, in situ resonant anomalous X-ray reflectivity is used to investigate the adsorption of uranyl on alumina (012) in acidic aqueous solutions, representing typical U VI concentrations of contaminated water near mining sites. The analyses reveal that U VI adsorbs at two distinct heights of 2.4-3.2 and 5-5.3 angstrom from the surface terminal oxygens. The former is interpreted as the mixture of inner-sphere and outer-sphere complexes that adsorb closest to the surface. The latter is interpreted as an outer-sphere complex that shares one equatorial H 2 O with the terminal surface oxygen. With increasing pH, we observe an increasing prevalence of these outer-sphere complexes, indicating the enhanced role of the hydrogen bond that stabilizes adsorbed uranyl species. Finally, the presented work provides a molecular-scale understanding of sorption of uranyl on Al-based-oxide surfaces that has implications for environmental chemistry and materials science.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗