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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.

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At least 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Electrochemical characterization of the plasma-water interface

Nonthermal atmospheric pressure plasmas generated using noble gases act as gaseous electrodes capable of promoting electrochemical reactions when in contact with aqueous media. Despite overwhelming evidence in favor of the interfacial region between the plasma and solution being a reducing environment, the plasma-liquid interface has not been evaluated from an electrochemical perspective. Herein, we present an electrochemical method to measure the overpotential at the plasma-liquid interface of solutions containing organic redox couples. Negative overpotentials indicate that the interfacial region is a reducing environment, which is consistent with the results of colorimetric assays using redox indicators. The reaction rates are related to the magnitude of the overpotential, as expected from electrochemical kinetic models. The ability to characterize the overpotential of plasma-liquid interfaces adds to the plasma electrochemistry toolkit and contributes to efforts being made to tune gaseous electrodes for the rational control of redox reactions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

The scaling of kinetic and transport behaviors in the solution-phase chemistry of a plasma–liquid interface

The reactions at a plasma–liquid interface often involve species such as the solvated electron or the hydroxyl radical, which initiate the reduction or oxidation of solution-phase reactants (so-called scavengers) or are consumed by their own second-order recombination. Here, the mathematical scaling of the reaction–diffusion equations at the interface is used to obtain a characteristic time that can be used to determine the transition from highly efficient scavenger reduction or oxidation to lower efficiencies due to transport limitations. The characteristic time (tc) is validated using numerical solutions of the reaction–diffusion equations. When the scavenger kinetics are faster than second-order recombination, this characteristic transition time scales proportionally with the scavenger diffusivity (Ds) and the square of the scavenger bulk concentration (SB) and inversely proportional to the electron flux (J) squared; that is, t c = D s S B 2 F 2 /J 2 , where F is Faraday’s constant. However, when the scavenger kinetics are comparable or slower than second-order recombination, this scaling does not hold. Extending this analysis to three-dimensional systems shows that the profile of the electron flux on the surface affects the spatial location where reactions are most effective. Finally, the assessment of the implications of these behaviors for the reactor design highlights how effectively controlling the electron flux and solution transport may be necessary to improve the efficiency of scavenger reactions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Direct Determination of Absolute Absorption Cross Sections at the L-Edge of Dilute Mn Complexes in Solution Using a Transmission Flatjet

The 3d transition metals play a pivotal role in many charge transfer processes in catalysis and biology. X-ray absorption spectroscopy at the L-edge of metal sites probes metal 2p–3d excitations, providing key access to their valence electronic structure, which is crucial for understanding these processes. In this paper, we report L-edge absorption spectra of Mn II (acac) 2 and Mn III (acac) 3 complexes in solution, utilizing a liquid flatjet for X-ray absorption spectroscopy in transmission mode. With this, we derive absolute absorption cross-sections for the L-edge transitions with peak magnitudes as large as 12 and 9 Mb for Mn II (acac) 2 and Mn III (acac) 3 , respectively. We provide insight into the electronic structure with ab initio restricted active space calculations of these L-edge transitions, reproducing the experimental spectra with excellent agreement in terms of shapes, relative energies, and relative intensities for the two complexes. Crystal field multiplet theory is used to assign spectral features in terms of the electronic structure. Comparison to charge transfer multiplet calculations reveals the importance of charge transfer in the core-excited final states. Finally, on the basis of our experimental observations, we extrapolate the feasibility of 3d transition metal L-edge absorption spectroscopy using the liquid flatjet approach in probing highly dilute biological solution samples and possible extensions to table-top soft X-ray sources.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Ionic-Liquid-Assisted Microwave Synthesis of Solid Solutions of Sr 1– x Ba x SnO 3 Perovskite for Photocatalytic Applications

Nanocrystalline Sr 1–x Ba x SnO 3 (x = 0, 0.2, 0.4, 0.8, 1) perovskite photocatalysts were prepared by microwave synthesis in an ionic liquid (IL) and subsequent heat-treatment. The influence of the Sr/Ba substitution on the structure, crystallization, morphology, and photocatalytic efficiency was investigated and the samples were fully characterized. On the basis of X-ray diffraction results, as the Ba content in the SrSnO 3 lattice increases, a symmetry increase was observed from the orthorhombic perovskite structure for SrSnO 3 to the cubic BaSnO 3 structure. The analysis of the sample morphology by SEM reveals that the Sr 1–x Ba x SnO 3 samples favor the formation of nanorods (500 nm–5 μm in diameter and several micrometers long). The photophysical properties were examined by UV/Vis diffuse reflectance spectroscopy. The band gap decreases from 3.85 to 3.19 eV with increasing Ba 2+ content. Furthermore, the photocatalytic properties were evaluated for the hydroxylation of terephthalic acid (TA). The order of the activities for TA hydroxylation was Sr 0.8 Ba 0.2 SnO 3 > SrSnO 3 > BaSnO 3 > Sr 0.6 Ba 0.4 SnO 3 > Sr 0.2 Ba 0.8 SnO 3 . Here, the highest photocatalytic activity was observed for Sr 0.8 Ba 0.2 SnO 3 , and this can be attributed to the synergistic impacts of the modification of the crystal structure and morphology, the relatively large surface area associated with the small crystallite size, and the suitable band gap and band-edge position.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Effects of Si solute on the glass formation and atomic structure of Pd liquid

Molecular dynamics simulations were performed to study the effects of Si solute on the glass formation and crystallization of Pd liquid. Pure Pd sample prepared by quenching process with cooling rate of 10 13 K/s can be in an amorphous state but the structural analysis indicates there is nearly no glass-forming motif in the sample. However, doping a small amount Si (Si concentration ~ 4%) the sample can be vitrified at a cooling rate of 10 12 K/s. The glass-forming motifs such as Pd-centered Z13, Si-centered Z9-like and Mixed-ICO-Cube clusters with 5-fold local symmetry are found to be the dominant short-range orders in the glassy samples. With the increasing of the Si-doping concentration, these glass-forming motifs tend to aggregate and connect with each other forming a network structure. Our calculated results revealed that Si solutes in liquid Pd can significantly enhance the glass-forming ability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Numerical Modeling of Fiber-Reinforced Metal Matrix Composite Processing by the Liquid Route: Literature Contribution

One of the technologies used to produce metal matrix composites (MMCs) is liquid route processing. One solution is to inject a liquid metal under pressure or at constant rate through a fibrous preform. This foundry technique overcomes the problem of the wettability of ceramic fibers by liquid metal. The liquid route can also be used to produce semiproducts by coating a filament with a molten metal. These processes involve physical phenomena combined with mass and heat transfer and phase change. The phase change phenomena related to solidification and also to the melting of the metal during the process notably result in modifications to the permeability of porous media, in gaps in impregnation, in the appearance of defects (porosities), and in segregation in the final product. In this article, we provide a state-of-the-art review of numerical models and simulation developed to study these physical phenomena involved in MMC processing by the liquid route.

36 MATERIALS SCIENCE↗
DOE OSTI2012

First-Principles Calculation of Thermodynamic Stability of Acids and Bases under pH Environment: A Microscopic pH Theory

Despite being one of the most important thermodynamic variables, pH has yet to be incorporated into first-principles thermodynamics to calculate stability of acidic and basic solutes in aqueous solutions. By treating the solutes as defects in homogeneous liquids, we formulate a first-principles approach to calculate their formation energies under proton chemical potential, or pH, based on explicit molecular dynamics. The method draws analogy to first-principle calculations of defect formation energies under electron chemical potential, or Fermi energy, in semiconductors. From this, we propose a simple pictorial representation of the general theory of acid-base chemistry. By performing first-principles molecular dynamics of liquid water models with solutes, we apply the formulation to calculate formation energies of various neutral and charged solutes such as H{sup +}, OH{sup -}, NH{sub 3}, NH{sub 4}{sup +}, HCOOH, and HCOO{sup -} in water. The deduced auto-dissociation constant of water and the difference in the pKa values of NH{sub 3} and HCOOH show good agreement with known experimental values. Our first-principles approach can be further extended and applied to other bio- and electro-chemical molecules such as amino acids and redox reaction couples that could exist in aqueous environments to understand their thermodynamic stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

High-Performance First-Principles Molecular Dynamics for Predictive Theory and Modeling

This project focused on developing high-performance software tools for First-Principles Molecular Dynamics (FPMD) simulations, and applying them in investigations of materials relevant to energy conversion processes. FPMD is an atomistic simulation method that combines a quantum-mechanical description of electronic structure with the statistical description provided by molecular dynamics (MD) simulations. This reliance on fundamental principles allows FPMD simulations to provide a consistent description of structural, dynamical and electronic properties of a material. This is particularly useful in systems for which reliable empirical models are lacking. FPMD simulations are increasingly used as a predictive tool for applications such as batteries, solar energy conversion, light-emitting devices, electro-chemical energy conversion devices and other materials. During the course of the project, several new features were developed and added to the open-source Qbox FPMD code. The code was further optimized for scalable operation of large-scale, Leadership-Class DOE computers. When combined with Many-Body Perturbation Theory (MBPT) calculations, this infrastructure was used to investigate structural and electronic properties of liquid water, ice, aqueous solutions, nanoparticles and solid-liquid interfaces. Computing both ionic trajectories and electronic structure in a consistent manner enabled the simulation of several spectroscopic properties, such as Raman spectra, infrared spectra, and sum-frequency generation spectra. The accuracy of the approximations used allowed for direct comparisons of results with experimental data such as optical spectra, X-ray and neutron diffraction spectra. The software infrastructure developed in this project, as applied to various investigations of solids, liquids and interfaces, demonstrates that FPMD simulations can provide a detailed, atomic-scale picture of structural, vibrational and electronic properties of complex systems relevant to energy conversion devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

3D-printed sheet jet for stable megahertz liquid sample delivery at X-ray free-electron lasers

X-ray free-electron lasers (XFELs) can probe chemical and biological reactions as they unfold with unprecedented spatial and temporal resolution. A principal challenge in this pursuit involves the delivery of samples to the X-ray interaction point in such a way that produces data of the highest possible quality and with maximal efficiency. This is hampered by intrinsic constraints posed by the light source and operation within a beamline environment. For liquid samples, the solution typically involves some form of high-speed liquid jet, capable of keeping up with the rate of X-ray pulses. However, conventional jets are not ideal because of radiation-induced explosions of the jet, as well as their cylindrical geometry combined with the X-ray pointing instability of many beamlines which causes the interaction volume to differ for every pulse. This complicates data analysis and contributes to measurement errors. An alternative geometry is a liquid sheet jet which, with its constant thickness over large areas, eliminates the problems related to X-ray pointing. Since liquid sheets can be made very thin, the radiation-induced explosion is reduced, boosting their stability. These are especially attractive for experiments which benefit from small interaction volumes such as fluctuation X-ray scattering and several types of spectroscopy. Although their use has increased for soft X-ray applications in recent years, there has not yet been wide-scale adoption at XFELs. Here, gas-accelerated liquid sheet jet sample injection is demonstrated at the European XFEL SPB/SFX nano focus beamline. Its performance relative to a conventional liquid jet is evaluated and superior performance across several key factors has been found. This includes a thickness profile ranging from hundreds of nanometres to 60 nm, a fourfold increase in background stability and favorable radiation-induced explosion dynamics at high repetition rates up to 1.13 MHz. Its minute thickness also suggests that ultrafast single-particle solution scattering is a possibility.

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

Methods and systems for treating an aqueous solution

A method of treating an aqueous solution comprises forming a treatment stream comprising a condensable material. The treatment stream is introduced to an aqueous solution comprising water and a solute to fractionally precipitate the solute out of the aqueous solution and form a solids stream comprising the solute and an aqueous liquid stream comprising at least one solute-depleted solution of the water and the condensable material. The condensable material of at least a portion of the aqueous liquid stream is separated from the water of the at least a portion of the aqueous liquid stream to at least partially reform the treatment stream and form an aqueous liquid product stream depleted in the solute. Aqueous solution treatment systems and additional methods of treating an aqueous solution are also described.

Wilson, Aaron D.↗
DOE OSTI2022

Thermodynamic modeling of aqueous lithium salt solutions with association electrolyte nonrandom two-liquid activity coefficient model

The high charge density of lithium ion and the resulting strong association phenomena make thermodynamic modeling of aqueous lithium electrolyte solutions extremely challenging. In this study, the association electrolyte nonrandom two-liquid activity coefficient model of Lin et al. (AIChE J. 2022, 68(2), e17422) is utilized to correlate and predict thermodynamic properties and solubility behavior of aqueous single electrolyte solutions of LiCl, LiBr, LiI, and LiNO 3 , and their mixed electrolyte solutions. Capturing self-association of water, cross-association of ion and water for hydration, and cross-association of cation and anion for ion-pairing, the association model accurately represents the literature experimental data up to saturation concentrations and at the temperature ranging from 263 K to 523 K. Here, this study further investigated the effect of anions of the lithium salts, and re-confirmed that the order of solution non-ideality as LiI > LiBr > LiCl > LiNO 3 because the anions with stronger association strengths are more likely to form ion pairs and thus lower the mean ionic activity coefficients.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Atmospheric-pressure ionization and fragmentation of peptides by solution-cathode glow discharge

Modern “-omics” (e.g., proteomics, glycomics, metabolomics, etc.) analyses rely heavily on electrospray ionization and tandem mass spectrometry to determine the structural identity of target species. Unfortunately, these methods are limited to specialized mass spectrometry instrumentation. Here in this paper, a novel approach is described that enables ionization and controlled, tunable fragmentation of peptides at atmospheric pressure. In the new source, a direct-current plasma is sustained between a tapered metal rod and a flowing sample-containing solution. As the liquid stream contacts the electrical discharge, peptides from the solution are volatilized, ionized, and fragmented. At high discharge currents (e.g., 70 mA), electrospray-like spectra are observed, dominated by singly and doubly protonated molecular ions. At lower currents (35 mA), many peptides exhibit extensive fragmentation, with a-, b-, c-, x-, and y-type ion series present as well as complex fragments, such as d-type ions, not previously observed with atmospheric-pressure dissociation. Though the mechanism of fragmentation is currently unclear, observations indicate it could result from the interaction of peptides with gas-phase radicals or ultraviolet radiation generated within the plasma.

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

Scalable Enrichment of 48 Ca at the Solid/liquid Interface by Chemical and Electrochemical Methods

This award targets to develop methods to enrich 48 Ca, which is a critical isotope for synthesizing superheavy elements and testing the standard model through neutrinoless double beta decay. The team first tested chemical exchange-based separation between solids and liquids, which is based on the free energy change due to the different vibrational frequencies caused by Ca isotopes in a material. However, the separation factor (alpha), which is defined as the ratio of 40 Ca/ 48 Ca ratios in the two phases, only reach ~1.01. The team then developed liquid centrifugation-based isotope separation, where a Ca salt aqueous solution is centrifuged at a speed of ~60 kRPM, and 48 Ca is enriched at the bottom of a centrifuge tube due to its larger mass. A high α of ~1.2-1.4 is achieved for 40 Ca/ 48 Ca at 40 °C. This method is further approved to be generic for any isotope that can be dissolved in a liquid solution or form liquid chemicals near room temperature. The experimental results also align well with modeling prediction. The team further develop a model to evaluate isotope separation in countercurrent liquid centrifugation. The team found that the countercurrent configuration can also enhance isotope separation in liquids, similar with gas centrifugation, which boost separation for isotopes which are difficult to be gasified near room temperature.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2019

A fundamental understanding of whole biomass dissolution in ionic liquid for regeneration of fiber by solution-spinning

Materials made from renewable resources are interesting and attractive substitutes for petroleum-based materials. Recently, regeneration of cellulose fibers using ionic liquids (ILs) as green solvents has been a topic of interest to both industrial and academic sectors. However, extraction of cellulose from lignocellulosic biomass requires numerous energy intensive processing steps. Additionally, the deconstruction and removal of lignin and hemicellulose components from lignocellulosic biomass usually involve corrosive pretreatment and the solvation of specific biomass components. Instead, utilization of the whole biomass—particularly woody residues—to manufacture high-performance materials offers an attractive value-proposition. In this study, we demonstrated fiber regeneration of whole hybrid poplar (HP) biomass by a sustainable method. We developed an environmentally friendly approach by partially auto-hydrolyzing the biomass with water before its dissolution in 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) ionic liquid, for large-scale, roll-to-roll production of fibers by solution spinning. We discuss, for the first time, a fundamental understanding of the inter- and intramolecular interactions in HP biomass–IL solutions, as well as their corresponding spinnability, structural reformation, and mechanical performance of the regenerated fibers. Particularly, the molecular alignment, recrystallization, and crystallinity of the spun fibers were correlated to the chain entanglement, molecular relaxation, and rheological properties of the HP biomass–IL solutions. A window of entangled concentration (4–6.5 wt%) of biomass in the IL was determined to be favorable for fiber spinning.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

The Development and Prevention of Channel Segregation During Alloy Solidification

During alloy solidification, interdendritic microsegregation causes density differences between entrapped liquid and bulk liquid which provides a driving force for convection. One of the consequences of this effect is the formation of long, nearly vertical liquid channels, rich in solute, flowing through the solid-liquid mushy zone somewhat as a river and tributary system. In ingot castings where the heat flow is vertically downwards and the solute less dense than the solute the convective flow is antiparallel with the flow caused by contraction on freezing. Identification of the mechanisms involved in these two problems is discussed. It is known that certain types of bulk liquid movements can inhibit channel development and the mechanism by which they do so are examined.

Hellawell, A.↗
NASA NTRS1986

An exact solution for the solidification of a liquid slab of binary mixture

The time dependent temperature and concentration profiles of a one dimensional finite slab of a binary liquid alloy is investigated during solidification. The governing equations are reduced to a set of coupled, nonlinear initial value problems using the method outlined by Meyer. Two methods will be used to solve these equations. The first method uses a Runge-Kutta-Fehlberg integrator to solve the equations numerically. The second method comprises of finding closed form solutions of the equations.

Antar, B. N.↗