Search NASA⌕ Search

SEARCH · Search NASA

Results for “water structure and dynamics”

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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Molecular dynamics simulation studies of 1,3-dimethyl imidazolium nitrate ionic liquid with water

The fundamental understanding of intermolecular interactions of ionic liquids (ILs) with water is essential in predicting IL–water thermodynamic properties. In this study, intermolecular or noncovalent interactions were studied for 1,3-dimethyl imidazolium [DMIM]+ cation and nitrate [NO 3 ] – anion with water, employing quantum mechanics and molecular dynamics simulations. Molecular dynamics simulations were performed using a revised multipolar polarizable force field. The effect of water on ionic liquids was evaluated in terms of thermodynamic and dynamic properties. Thermodynamic properties included liquid densities ρ, excess molar volumes ΔV E , and liquid structures g(r)⁠. Dynamic properties included self-diffusion coefficients D of mixture constituents as a function of water concentration. The density of ionic liquid–water mixtures monotonically decrease with increasing concentration of water. A negative excess volume was obtained for low and high water concentrations, demonstrating strong intermolecular interactions of water with ionic liquid components. Liquid structures of ionic liquid–water mixtures revealed a tendency for anions to interact with cations at shorter intermolecular distances when the water concentration is increased. Diffusion rates were found to increase for all mixture components with increase in the fraction of water. A significant change in the diffusion rate was found at ~0.3 weight fraction of water. However, the water self-diffusion coefficient was dominant at all concentrations. Furthermore, the ratio of water/anion and anion/cation self-diffusion coefficients was found to decrease linearly with increasing concentration of water molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Oxide– and Silicate–Water Interfaces and Their Roles in Technology and the Environment

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by “anomalies” or “non-idealities” such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide– and silicate–water interfaces. This critical review discusses how science progresses from understanding ideal solid–water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. Further, we anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

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

Revealing the Dynamics and Roles of Iron Incorporation in Nickel Hydroxide Water Oxidation Catalysts

We report the surface of an electrocatalyst undergoes dynamic chemical and structural transformations under electro-chemical operating conditions. There is a dynamic exchange of metal cations between the electrocatalyst and electrolyte. Understanding how iron in the electrolyte gets incorporated in the nickel hydroxide electrocatalyst is critical for pinpointing the roles of Fe during water oxidation. Here, we report that iron incorporation and oxygen evolution reaction (OER) are highly coupled, especially at high working potentials. The iron incorporation rate is much higher at OER potentials than that at the OER dormant state (low potentials). At OER potentials, iron incorporation favors electrochemically more reactive edge sites, as visualized by synchrotron X-ray fluorescence microscopy. Using X-ray absorption spectroscopy and density functional theory calculations, we show that Fe incorporation can suppress the oxidation of Ni and enhance the Ni reducibility, leading to improved OER catalytic activity. Our findings provide a holistic approach to understanding and tailoring Fe incorporation dynamics across the electrocatalyst-electrolyte interface, thus controlling catalytic processes.

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

Lattice-scale variations in viscosity are correlated with solution structure at mineral-water interfaces

At solid-liquid interfaces, the viscosity increases markedly from the bulk due to the collective interactions of ions and water molecules, influencing phenomena relevant to nanofluidics, colloidal dynamics, and electrochemistry. Here, in this study, we investigated dissipative forces at the boehmite-water interface using 3D atomic force microscopy. We observed an increase in interfacial solution viscosity, η, by 10-100-fold as the nanoprobe approached the surface in normal direction, with up to four oscillatory features showing average peaks of η/η bulk = 44-71. Moreover, the viscosity showed sub-nanometer variations within 0.5 nm from the interface, templated by the underlying crystal lattice and correlated with the interfacial solution structure. Beyond a near-wall region of approximately 1.2 nm, the dissipative response was comparable to that in bulk solution. Molecular dynamics simulations, along with statistical mechanical analyses, provided details on hydrodynamic structures near the interface. Specifically, the lattice-dependent dissipative responses are correlated with extensive hydrogen bonding by interfacial water molecules, which increased friction, particularly along the [001] direction. These results demonstrate how solution viscosity at mineral-water interfaces is anisotropic and correlated with the local solution structure, providing insights into the dynamics of nanocrystal attachment.

Viscosity↗
DOE OSTI2023

Molecular Dynamics Simulations of Calcite Fracture in Water

Calcite (CaCO 3 ) is one of the most common minerals in geologic and engineered systems. It is often in contact with aqueous solutions, causing chemically assisted fracture that is critical to understanding the stability of subsurface systems and manmade structures. Calcite fracture was evaluated with reactive molecular dynamics simulations, including the impacts of crack tip geometry (notch), the presence of water, and surface hydroxyl groups. Chemo-mechanical weakening was assessed by comparing the loads where fracture began to propagate. Our analyses show that in the presence of a notch, the load at which crack growth begins is lower, compared to the effect of water or surface hydroxyls. Additionally, the breaking of two adjacent Ca–O bonds is the kinetic limitation for crack initiation, since transiently broken bonds can reform, not resulting in crack growth. In aqueous environments, fresh (not hydroxylated) calcite surfaces exhibited water strengthening. Manual addition of H + and/or OH – species on the (104) calcite surface resulted in chemo-mechanical weakening of calcite by 9%. Achieving full hydroxylation of the calcite surface was thermodynamically and kinetically limited, with only 0.17–0.01 OH/nm 2 surface hydroxylation observed on the (104) surface at the end of the simulations. In conclusion, the limited reactivity of pure water with the calcite surface restricts the chemo-mechanical effects and suggests that reactions between physiosorbed water and localized structural defects may be dominating the chemo-mechanical process in the studies where water weakening has been reported.

Calcite↗
DOE OSTI2023

NMR relaxometry characterization of water adsorption in corn stover anatomical fractions

Nuclear magnetic resonance (NMR) relaxometry is applied to provide direct measurement of water adsorption in anatomical fractions of corn stover. NMR transverse T 2 relaxation time distribution measurements indicate multiple water populations, which vary with anatomical fraction and water adsorption. Measured T 2 data are used to calculate thermodynamic properties of Brunauer-Emmet-Teller adsorption theory using a model to estimate mono and bilayer relaxation. T 2 data are used directly to determine rotational diffusion correlation times indicating adsorption interaction strength. T 1 -T 2 longitudinal-transverse relaxation time correlation measurements quantify differences in the molecular level structural order of the adsorbate surface water as a function of water activity, i.e. relative humidity or water vapor partial pressure. The T 1 /T 2 ratio provides a measure of the surface energy related to the adsorption strength and surface diffusive mobility of the water adsorbate and differentiates the anatomical fractions. Furthermore, the results indicate that direct measurement of NMR relaxation times can be used to characterize corn stover biomass water adsorption, data relevant to processing and handling considerations.

09 BIOMASS FUELS↗
DOE OSTI2021

Behavior of Water Near Multimodal Chromatography Ligands and Its Consequences for Modulating Protein–Ligand Interactions

Multimodal chromatography is a powerful approach for purifying proteins that uses ligands containing multiple modes of interaction. Recent studies have shown that selectivity in multimodal chromatographic separations is a function of the ligand structure and geometry. Here, we performed molecular dynamics simulations to explore how the ligand structure and geometry affect ligand–water interactions and how these differences in solution affect the nature of protein–ligand interactions. Our investigation focused on three chromatography ligands: Capto MMC, Nuvia cPrime, and Prototype 4, a structural variant of Nuvia cPrime. First, the solvation characteristics of each ligand were quantified via three metrics: average water density, fluctuations, and residence time. We then explored how solvation was perturbed when the ligand was bound to the protein surface and found that the probability of the phenyl ring dewetting followed the order: Capto MMC > Prototype 4 > Nuvia cPrime. To explore how these differences in dewetting affect protein–ligand interactions, we calculated the probability of each ligand binding to different types of residues on the protein surface and found that the probability of binding to a hydrophobic residue followed the same order as the dewetting behavior. This study illustrates the role that wetting and dewetting play in modulating protein–ligand interactions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Extracted Water Induces Concentration Fluctuations in Model Ternary Liquid–Liquid Extraction System

Organic phase aggregation and phase splitting are two important (and connected) phenomena in liquid–liquid extraction of metal ions. Previously, we demonstrated how structure in binary mixtures of extractant and diluent originates from concentration fluctuations associated with the so-called “third-phase formation” liquid–liquid phase instability. For more complex systems, we sought to understand how extracted aqueous components affect these concentration fluctuations. Here, in this study, we use small-angle X-ray scattering and molecular dynamics simulations to investigate organic phase structural changes upon contact with water in a model ternary system of water/alkane/extractant. Critical exponents were determined from scattering with temperature variation and were consistent with mean field values. Then, by controlling the water content in the organic phase through direct dissolution of fixed quantities at constant temperature, we relate the observed increase in the fluctuation length scale to changes to the spinodal temperature of the third-phase formation phase boundary. We find a roughly linear relationship between water concentration and the spinodal temperature and a similar slope in that relationship for different linear alkane diluents. This suggests that the mechanism by which water extraction impacts the organic phase structure is to enhance concentration fluctuations through the introduction of additional polar extractant-water complexes, which increases the spinodal temperature and thereby decreases the reduced temperature, i.e., the distance to the instability. This explanation for how solutes induce aggregation in liquid–liquid extraction organic phases may extend to more complex systems, explaining the large increases in correlation lengths reported under high acid and metal loading.

Bonnett, Brittany L. [Argonne National Laboratory ↗
DOE OSTI2020

Kilometer-Scale Hydrologic Exchange Flows in a Gravel Bed River Corridor and Their Implications to Solute Migration

In this work, a well-characterized field site along a major river corridor was used to investigate the dynamic pathways and impacts of subsurface hydrogeologic structures on kilometer-scale hydrologic exchange flows between river water and groundwater. A aqueous uranium (U aq ) plume exists at the site that discharges to the Columbia River. We performed temporally intensive monitoring of specific conductance (SpC) and U aq concentrations within the plume at increasing distances from the river shoreline and at locations both within and outside a presumed subsurface pathway of lateral hydrologic exchange. Specific conductance and U aq were utilized as in-situ tracers of hydrologic exchange and associated groundwater-surface water mixing. Monitoring data was collected for an approximate two year period during which seasonal river elevations varied by more than 2 m causing distinct events of river water intrusion and retreat from the near-shore aquifer, and large temporal variations in well-water analyte concentrations. Statistical clustering analysis was applied to identify well groupings exhibiting common time series behaviors. PFLOTRAN was implemented within a modeling domain of 3.3 x 1.9 km with dynamic flow boundary conditions and accurate subsurface topography for the basal aquitard underlying the aquifer. In-silico calculations of river water tracer behavior were performed to assess predominant flow directions and velocities influenced by river stage variations and variable aquitard topography, and their collective influences on SpC and U aq concentrations. We demonstrate complicated multidirectional flow behaviors at the kilometer scale resulting from hydrologic exchange and subsurface structure that influence plume dynamics and determine the overall system behavior.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Potential environmental effects of deepwater floating offshore wind energy facilities

Over the last few decades, the offshore wind energy industry has expanded its scope from turbines mounted on fixed platforms driven into the seafloor and standing in less than 50 meters of water, to floating turbines moored in 120 meters of water, to prospecting the development of floating turbines moored in ~1000 meters of water. Since there are few prototype turbines and mooring systems of these deepwater, floating offshore wind energy facilities (OWFs) currently deployed, their effects on the marine environment are largely unknown. Using the available scientific literature concerning appropriate analogs, this study provides the first synthesis of the potential environmental effects of deepwater, floating OWFs during operation, as well as potential mitigation measures to some of the risks. Potential effects we identify and evaluate include changes to atmospheric and oceanic dynamics, electromagnetic fields, habitat alterations, noise, structural impediments, and changes to water quality that could affect a variety of marine species across trophic levels. Our synthesis suggests that many of these potential effects could be mitigated to pose a low risk to the marine environment if developers adopt appropriate mitigation strategies and best-practice protocols. This review takes the necessary first steps in summarizing the available information on the potential environmental effects of deepwater, floating OWFs and can serve as a valuable reference document for marine scientists and engineers, the energy industry, permitting agencies and regulators of the energy industry, project developers, and concerned stakeholders such as coastal residents, conservationists, and fisheries.

Farr, Hayley K.↗
DOE OSTI2024

Additive Molar Volumes in Amorphous Ca/Sr Carbonate Solid Solutions

The development of predictive models of minor element incorporation in crystalline carbonate end products requires an understanding of the fundamental controls on metastable intermediate phase composition. In this study, we used small-angle X-ray scattering (SAXS), X-ray pair distribution function (PDF), thermogravimetric analysis (TGA), inductively coupled plasma mass spectrometry (ICP-MS), and transmission electron microscopy (TEM) to determine the composition-dependent density of an amorphous calcium–strontium carbonate (ACSC) solid solution. The amorphous calcium carbonate (ACC) and strontium carbonate (ASC) measured densities were ρ ACC = 2.19 ± 0.04 g/cm 3 and ρ ASC = 2.97 ± 0.05 g/cm 3 . Throughout our work, the experiments showed a dependence of the water content of the amorphous solid solution on the Sr mole fraction. An equation that relates the molar volume to the average cation radius, the carbonate ion radius, and the water volume was parameterized for hydrated crystalline carbonates and predicted well the molar volume of the ACSC solid solution. This finding indicates that, as for hydrated crystalline carbonates, the molar volumes of amorphous carbonates are additive and that water is a structural component of ACSC. Ab initio molecular dynamics (AIMD) simulations of the ACSC solid solutions showed strong linear correlations between calculated molar volumes and Sr and H 2 O contents, thus supporting the experimental results. In conclusion, our findings highlight the need to consider the full CaCO 3 –MeCO 3 –H 2 O ternary when quantifying metal cation incorporation in ACC.

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

Shear-induced polydomain structures of nematic lyotropic chromonic liquid crystal disodium cromoglycate

Lyotropic chromonic liquid crystals (LCLCs) represent aqueous dispersions of organic disk-like molecules that form cylindrical aggregates. Despite the growing interest in these materials, their flow behavior is poorly understood. Here, we explore the effect of shear on dynamic structures of the nematic LCLC, formed by 14 wt% water dispersion of disodium cromoglycate (DSCG). We employ in situ polarizing optical microscopy (POM) and small-angle and wide-angle X-ray scattering (SAXS/WAXS) to obtain independent and complementary information on the director structures over a wide range of shear rates. The DSCG nematic shows a shear-thinning behavior with two shear-thinning regions (Region I at $\dot{\gamma}$ < 1 s -1 and Region III at $\dot{\gamma}$ > 10 s -1 ) separated by a pseudo-Newtonian Region II (1 s-1 < $\dot{\gamma}$ < 10 s -1 ). The material is of a tumbling type. In Region I, $\dot{\gamma}$ < 1 s -1 , the director realigns along the vorticity axis. An increase of [small gamma, Greek, dot above] above 1 s -1 triggers nucleation of disclination loops. The disclinations introduce patches of the director that deviates from the vorticity direction and form a polydomain texture. Extension of the domains along the flow and along the vorticity direction decreases with the increase of the shear rate to 10 s -1 . Above 10 s -1 , the domains begin to elongate along the flow. At $\dot{\gamma}$ > 100 s -1 , the texture evolves into periodic stripes in which the director is predominantly along the flow with left and right tilts. The period of stripes decreases with an increase of $\dot{\gamma}$. The shear-induced transformations are explained by the balance of the elastic and viscous energies. In particular, nucleation of disclinations is associated with an increase of the elastic energy at the walls separating nonsingular domains with different director tilts. The uncovered shear-induced structural effects would be of importance in the further development of LCLC applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The “good,” the “bad,” and the “hidden” in neutron scattering and molecular dynamics of ionic aqueous solutions

We characterize a concentrated 7.3 m CaCl 2 solution, combining neutron diffraction with chloride isotopic substitution (Cl-NDIS) in null water and molecular dynamics (MD) simulations. We elucidate the solution structure, thermodynamic properties, and extent of ion pairing previously suggested as concentration-dependent and often not observed at lower concentrations. Our Cl-NDIS measurements designate the solvent-shared ion pairing as dominant and the contact ion pairing (CIP) as insignificant even under conditions close to the solubility limit. The MD models parameterized against neutron diffraction with calcium isotopic substitution (Ca-NDIS) overestimate CIP despite successfully reproducing most of the Cl-NDIS signal. This drawback originates from the fact that Ca 2+ –Cl - interactions were primarily “hidden” in the Ca-NDIS signal due to overlapping with Ca 2+ –O w and Ca 2+ –H w contributions to the total scattering. Contrary, MD models with moderate CIP and possessing generally good performance at high concentrations fail to reproduce the NDIS measurements accurately. Therefore, the electronic polarization, introduced in most of the recent MD models via scaling ionic charges, resolves some but not all parameterization drawbacks. We conclude that despite improving the quality of MD models “on average,” the question “which model is the best” has not been answered but replaced by the question “which model is better for a given research.” An overall “good” model can still be inappropriate or, in some instances, “bad” and, unfortunately, produce erroneous results. Additionally, the accurate interpretation of several NDIS datasets, complemented by MD simulations, can prevent such mistakes and help identify the strengths, weaknesses, and convenient applications for corresponding computational models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Water Impact Test and Simulation of a Composite Energy Absorbing Fuselage Section

In March 2002, a 25-ft/s vertical drop test of a composite fuselage section was conducted onto water. The purpose of the test was to obtain experimental data characterizing the structural response of the fuselage section during water impact for comparison with two previous drop tests that were performed onto a rigid surface and soft soil. For the drop test, the fuselage section was configured with ten 100-lb. lead masses, five per side, that were attached to seat rails mounted to the floor. The fuselage section was raised to a height of 10-ft. and dropped vertically into a 15-ft. diameter pool filled to a depth of 3.5-ft. with water. Approximately 70 channels of data were collected during the drop test at a 10-kHz sampling rate. The test data were used to validate crash simulations of the water impact that were developed using the nonlinear, explicit transient dynamic codes, MSC.Dytran and LS-DYNA. The fuselage structure was modeled using shell and solid elements with a Lagrangian mesh, and the water was modeled with both Eulerian and Lagrangian techniques. The fluid-structure interactions were executed using the fast general coupling in MSC.Dytran and the Arbitrary Lagrange-Euler (ALE) coupling in LS-DYNA. Additionally, the smooth particle hydrodynamics (SPH) meshless Lagrangian technique was used in LS-DYNA to represent the fluid. The simulation results were correlated with the test data to validate the modeling approach. Additional simulation studies were performed to determine how changes in mesh density, mesh uniformity, fluid viscosity, and failure strain influence the test-analysis correlation.

Fasanella, Edwin L.↗
DOE OSTI2024

Attosecond-pump attosecond-probe x-ray spectroscopy of liquid water

Attosecond-pump/attosecond-probe experiments have long been sought as the most straightforward method for observing electron dynamics in real time. Although there has been much success with overlapped near-infrared femtosecond and extreme ultraviolet attosecond pulses combined with theory, true attosecond-pump/attosecond-probe experiments have been limited. Here we used a synchronized attosecond x-ray pulse pair from an x-ray free-electron laser to study the electronic response to valence ionization in liquid water through all x-ray attosecond transient absorption spectroscopy (AX-ATAS). Our analysis showed that the AX-ATAS response is confined to the subfemtosecond timescale, eliminating any hydrogen atom motion and demonstrating experimentally that the 1b 1 splitting in the x-ray emission spectrum is related to dynamics and is not evidence of two structural motifs in ambient liquid water.

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

Molecular insights into the structure-property relationships of 3D printed polyamide reverse-osmosis membrane for desalination

3D-printing is an emerging method for manufacturing polyamide (PA) reserve osmosis (RO) membranes for water treatment and desalination, which can precisely control membrane structural properties, such as thickness, roughness, and resolution. However, the synthesis-structure (i.e., degree of cross-linking (DC), m-phenylenediamine/trimesoyl chloride (MPD/TMC) ratio, and membrane thickness) to property (permeability and water-salt selectivity) relationships for these membranes has not been well understood. At the same time, a microscopic understanding of the physical mechanism of water and salt transport is needed to guide the design of high-performance 3D-printed membranes and improve the printing efficiency. Furthermore, the atomic-scale transport features and energetics of water and salt ions are studied at high pressure for the 3D-printed PA RO membranes with the different DCs and MPD/TMC ratios through non-equilibrium molecular dynamics (NEMD) simulations. Factoring in membrane structure properties, rejection ratio of salt ions and pressure-dependent water flux, 3D-printed PA membranes having an MPD/TMC ratio of 3.0:2.0 and a DC between 80%~90% attains ideal performance: high water flux, high rejection of salt ions, and excellent structural integrity. Mechanistically, water permeability for highly cross-linked PA RO membranes depends on the temporary on-and-off channels that allow water molecules to jump from one cavity to another at high pressure. In addition, higher pressures cause rapid compaction of PA membranes’ free volume and membrane thickness. Membrane failure at high pressure is determined by the DC and MPD/TMC ratios-dependent compressive yield strength. In short, these findings provide physical insights for optimizing existing PA membranes and designing next-generation desalination membranes at the molecular level.

3D-printed PA RO membrane↗