Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Chemical 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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

In-situ thermodynamics measurements at metal oxides-solution interfaces using Flow Adsorption Microcalorimetry.

Mineral-fluid interfaces are the principal sites of geochemical processes near Earth’s surface, hosting chemical reactions that play a fundamental role in (bio)geochemical cycles and in the fate and transport of anthropogenic contaminants, and that effectively control the compositions of soil and water environments. These complex interfaces are critical for our energy and environmental future. The mineral-fluid interface has been studied in an unprecedented level of detail with both experimental and computational approaches, separately and in combination. However, conspicuously missing from studies of the mineral-fluid interface are direct measurements of the energies of ion sorption and exchange. The literature on energetics and enthalpies of exchange, adsorption, dissolution, precipitation, and surface protonation reactions, especially those directly supported by experimental data, remains scarce despite their fundamental nature. The overarching goal of this project is to complete a systematic study of the thermodynamics properties of interfacial reactions at four MO surfaces (Rutile (α-TiO2), Quartz (SiO2), boehmite (γ-AlOOH) and goethite (α-FeOOH)) through the application and construction of novel flow adsorption microcalorimetry techniques and instrumentations. These unique and specialized microcalorimeters will operate at various temperatures and solution chemical compositions allowing for in-situ measurements across metal oxides and ligands of various characteristics. The overall research goal will be accomplished by completing the following three specific objectives (O): O1) Determine the energetics of surface protonation and deprotonation, ion exchange and ligand sorption reactions; O2) Investigate the surface charge thermodynamic properties under a range of temperature and solution chemical compositions; and O3) Develop predictive trends of the interplay between MO structure, surface coverage and surface reactivity. In addition to key thermodynamics parameters, calorimetric measurements provide a wealth of mechanistic information about reactions energetics and kinetics, surface charge characteristics, and structure-reactivity or selectivity relationships, all obtained in-situ and in real-time. This report includes science highlights from various projects completed over the performance period of the project. Also listed are dissemination opportunities, people supported on the grant and the impact on available physical resources and the discipline as a whole.

58 GEOSCIENCES↗
DOE OSTI2022

Effect of atomic size mismatch and chemical complexity on the local lattice distortion of BCC solid solution alloys

Here, the effects of atomic size mismatch and chemical complexity on the local lattice distortion of solid-solution alloys VNbTa, TiVNbMo, TiVNbMoTa and TiVNbMoTaWRe with body-centered cubic (BCC) structure are quantitatively studied with time-of-flight neutron total scattering, extended X-ray absorption fine structure (EXAFS) measurements and first principles calculations. Neutron atomic pair distribution function (PDF) measurements found that the local lattice distortion in the ternary solid-solution alloy VNbTa is 1.1 %, obviously larger than that of the most complicated solid-solution alloy (0.27% for TiVNbMoTaWRe). Our results suggested that atomic size mismatch in high entropy alloys is more critical to the local lattice distortion than chemical complexity. Both EXAFS analysis and theoretical calculations indicate that there is a maximum of ~4 % difference between the bonding length of different atomic pairs in VNbTa.

36 MATERIALS SCIENCE↗
NASA NTRS1996

Recycle of Inorganic Nutrients for Hydroponic Crop Production Following Incineration of Inedible Biomass

Recovery of resources from waste streams is essential for future implementation and reliance on a regenerative life support system. The major waste streams of concern are from human activities and plant wastes. Carbon, water and inorganics are the primary desired raw materials of interest. The goal of resource recovery is maintenance of product quality to insure support of reliable and predictable levels of life support function performance by the crop plant component. Further, these systems must be maintained over extended periods of time, requiring maintenance of nutrient solutions to avoid toxicity and deficiencies. Today, reagent grade nutrients are used to make nutrient solutions for hydroponic culture and these solutions are frequently changed during the life cycle or sometimes managed for only one crop life cycle. The focus of this study was to determine the suitability of the ash product following incineration of inedible biomass as a source of inorganic nutrients for hydroponic crop production. Inedible wheat biomass was incinerated and ash quality characterized. The incinerator ash was dissolved in adequate nitric acid to establish a consistent nitrogen concentration in all nutrient solution treatments. Four experimental nutrient treatments were included: control, ash only, ash supplemented to match control, and ash only quality formulated with reagent grade chemicals. When nutrient solutions are formulated using only ash following-incineration of inedible biomass, a balance in solution is established representing elemental retention following incineration and nutrient proportions present in the original biomass. The resulting solution is not identical to the control. This imbalance resulted in suppression of crop growth. When the ash is supplemented with nutrients to establish the same balance as in the control, growth is identical to the control. The ash appears to carry no phytotoxic materials. Growth in solution formulated with reagent grade chemicals but matching the quality of the ash only treatment resulted in growth similar to that of the ash only treatment. The ash product resulting from incineration of inedible biomass appears to be a suitable form for recycle of inorganic nutrients to crop production.

Bubenheim, David L.↗
NASA NTRS1981

The chemical behavior of acidified chromium (3) solutions

A unique energy-storage system has been developed at NASA's Lewis Research Center called REDOX. This NASA-REDOX system is an electrochemical storage device that utilized the oxidation and reduction of two fully soluble redox couples for charging and discharging. The redox couples now being investigated are acidified chloride solutions of chromium (Cr(+2)/Cr(+3)) and iron (Fe(+2)/Fe(+3)).

Terman, D. K.↗
DOE OSTI2026

Dynamics of iodine geminate recombination in supercritical xenon solvent: Caging effect

Understanding the dynamics of chemical reactions in solutions is vital, as their rates and kinetics are significantly affected by the solvent environment. Supercritical solvents offer extensive applications in chemical reactions by enabling the manipulation of the solution environment. Here, in this study, we investigate the geminate recombination of iodine in a supercritical xenon solvent by using ReaxFF-based molecular dynamics simulations. Our findings reveal that the highest iodine recombination rate occurs near supercritical conditions, while lower-pressure conditions lead to reduced collision rates and unstable recombination, and higher-pressure conditions hinder iodine diffusion, resulting in a lower recombination rate. Our analysis shows that the xenon local density at the time of recombination is at least 2.5 times higher than the global density, confirming the presence of xenon clusters surrounding the Iodine atoms. This observation is further supported by coordination number analysis, which confirms an elevated xenon local density during recombination. In addition, the correlation between the total energy of xenon atoms within a cluster and recombined iodine atoms underscores the kinetic energy transfer process, validating the occurrence of geminate recombination. The excess kinetic energy from the recombining iodine atoms is transferred to the surrounding xenon atoms. Our examination of geminate recombination demonstrates that iodine atoms confined within xenon clusters—whether through manual insertion of atoms or the fast dissociation of an iodine molecule within xenon clusters—are more likely to recombine as primary geminate recombination. However, extending the iodine molecule dissociation time allows iodine atoms to diffuse out of the cluster, and the recombination to shift toward secondary geminate recombination.

Cage effect↗
DOE OSTI2024

Toward a quantitative description of solvation structure: a framework for differential solution scattering measurements

Appreciating that the role of the solute–solvent and other outer-sphere interactions is essential for understanding chemistry and chemical dynamics in solution, experimental approaches are needed to address the structural consequences of these interactions, complementing condensed-matter simulations and coarse-grained theories. High-energy X-ray scattering (HEXS) combined with pair distribution function analysis presents the opportunity to probe these structures directly and to develop quantitative, atomistic models of molecular systems in situ in the solution phase. However, at concentrations relevant to solution-phase chemistry, the total scattering signal is dominated by the bulk solvent, prompting researchers to adopt a differential approach to eliminate this unwanted background. Though similar approaches are well established in quantitative structural studies of macromolecules in solution by small- and wide-angle X-ray scattering (SAXS/WAXS), analogous studies in the HEXS regime—where sub-ångström spatial resolution is achieved—remain underdeveloped, in part due to the lack of a rigorous theoretical description of the experiment. To address this, herein we develop a framework for differential solution scattering experiments conducted at high energies, which includes concepts of the solvent-excluded volume introduced to describe SAXS/WAXS data, as well as concepts from the time-resolved X-ray scattering community. Our theory is supported by numerical simulations and experiment and paves the way for establishing quantitative methods to determine the atomic structures of small molecules in solution with resolution approaching that of crystallography.

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

Modeling Equilibrium Solid–Liquid Interfaces under Effective Constant Chemical Potential Using Machine Learning Interatomic Potentials

The chemical potential (μ) of species in solution is essential for understanding various chemical processes at interfaces. Molecular dynamics (MD) simulations, constrained by fixed compositions, cannot maintain constant chemical potential with reference to a targeted concentration or chemical potential under nonequilibrium or dynamic conditions, as solute species can migrate to the interface and deplete (or enrich) the bulk due to solute-interface interactions. In this study, we introduce a simple and computationally efficient approach named iterative quasi-constant chemical potential molecular dynamics (iqCμMD) simulation, which helps simulate targeted molar concentrations of species in solution. iqCμMD overcomes the limitations of conventional MD by adjusting the number of species in the solution to reach a target bulk concentration (chemical potential), which allows simulation of the interface under the bulk conditions comparable to experiment. We demonstrate our approach using machine learning interatomic potential (MLIP)-based MD simulations of the Na 2 SO 4,aq –graphene interface, and to show the transferability of our approach, we also perform classical force field-based MD simulations of NaCl aq –air and NaCl aq –graphite interfaces, which produce comparable results to previous CμMD simulations. Our results also show that the iqCμMD approach efficiently achieves the desired bulk ion concentration within two iterations, and by utilizing MLIPs, we can achieve converged results using relatively small-scale simulations compared to previous CμMD simulations. By combining iqCμMD with MLIP-driven simulations, solid–liquid interfaces can be modeled under an effective constant chemical potential with DFT-level accuracy. Here, we show that iqCμMD offers a robust and simple computational framework for constant chemical potential simulations, as its only requirement is to be able to converge interfacial simulations with a measurable bulk region.

Chemical structure↗
DOE OSTI2023

Minimum Free-Energy Shapes of Ag Nanocrystals: Vacuum vs Solution

Here, we use two variants of replica-exchange molecular dynamics (MD) simulations, parallel tempering MD and partial replica exchange MD, to probe the minimum free-energy shapes of Ag nanocrystals containing 100–200 atoms in a vacuum, ethylene glycol (EG) solvent, and EG solvent with a PVP polymer containing 100 repeat units. Our simulations reveal a shape intermediate between a Dh and an Ih, a Dh-Ih, that has distinct structural signatures and magic sizes. We find several prominent features associated with entropy: pure FCC nanocrystals are less common than FCC crystals containing stacking faults, and crystals with the minimum potential energy are not always preferred over the range of relevant temperatures. The shapes of the nanocrystals in solution are influenced by the chemical identities of the solution-phase molecules. Comparing Ag nanocrystal shapes in EG to those in an EG+PVP solution, we find more icosahedra in EG and more decahedra in EG+PVP across all of the nanocrystal sizes probed in this study. At certain critical sizes, nanocrystal shapes can change dramatically with the addition and removal of a single atom or with a change in temperature at a fixed size. The information in our study could be useful in efforts to devise processing routes to achieve selective nanocrystal shapes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

R-Value Measurements Performed on Actinide Targets Irradiated using the GODIVA IV Critical Assembly in FY22

The separation and characterization of two irradiated uranium targets, a depleted uranium (DU) and a highly enriched uranium (HEU) target as well as a plutonium (Pu) target, was conducted in April of 2022. The three targets were assembled at Los Alamos National Laboratory (LANL) and irradiated using the GODIVA critical assembly at the National Criticality Experiments Research Center (NCERC). Splits of the dissolved targets were received by Pacific Northwest National Laboratory (PNNL) after which the PNNL and LANL teams chemically separated the solutions using independent separation schemes and analyzed the separated fractions for short lived actinides and fission products. Chemical separations were traced with stable or radioactive tracers to allow for the determination of chemical yields, analyzing using either inductively coupled plasma optical emission spectroscopy (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS) or gamma emission analysis (GEA) depending on the nature of the tracer. The Pu target solution was traced with stable elements at LANL to follow elemental fractionation during a Pu removal step. Many analytical techniques were used by PNNL including kinetic phosphorescence analysis (KPA), ICP-OES, ICP-MS, GEA, and thermal ionization mass spectrometry (TIMS) depending on the analyte’s need.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Dislocation loop evolution and radiation hardening in nickel-based concentrated solid solution alloys

Effects of chemical composition, ion irradiation dose and temperature on unfaulting of irradiation induced Frank dislocation loops to perfect loops in two nickel based single-phase solid solution alloys, Ni–20Fe and NiFe–20Cr, have been studied. The fraction of Frank loops decreases with irradiation dose from 7.2 to 38.4 dpa at 500°C, but with more Frank loops remaining in the ternary alloy. However, perfect loops and dislocation networks become the dominant features of defects at 580°C in both alloys. The results indicate a thermally assisted loop unfaulting process that may be hindered by more sluggish defect motion in the alloy with more chemical components. Nano-indentation with both continuous stiffness method and single indentation method are used to measure radiation hardening. Loop unfaulting in both alloys irradiated at 580°C reduced radiation hardening while significant hardening is observed after irradiation at 500°C. The quasi-static single indentation method exhibits lower hardness results compared to continuous stiffness method, because dislocations induced from the cyclic loading in the latter method get relaxed and stabilized, resulting in higher resistance to the indenter.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The role of excess vacancies in stabilizing solute clusters in low-alloy steels

The formation of solute clusters in irradiated low-alloy steels, such as reactor pressure vessel steels, is a critical cause of radiation hardening and embrittlement. However, the chemical interactions among solute elements and excess vacancies remain to be fully understood. This study employs density functional theory, cluster expansion, and lattice-based Monte Carlo simulations to examine the stability and morphology of nano-size coherent solute clusters with excess vacancies. The findings reveal that excess vacancies are crucial in stabilizing and promoting the growth of Mn-Ni-Si-vacancy clusters. A minimum of seven vacancies is required for stable nucleation and growth of these clusters. These Mn-Ni-Si clusters act as defect sinks, effectively trapping and absorbing mobile vacancies generated under irradiation. Furthermore, phosphorus (P) preferentially dissolves in Mn-Ni-Si clusters due to chemical coupling with vacancies. In conclusion, this study offers new insights into solute-vacancy interactions, enhancing our understanding of solute-defect cluster formation and embrittlement in low-alloy steels.

36 - MATERIALS SCIENCE↗
DOE OSTI2023

Triboelectric nanogenerator for harvesting energy from water

An apparatus including a first member including a first electrode, a second member coupled to the first member about an axis, including a second electrode, and a surface layer between the first electrode and the second electrode, the second member is rotatable with respect to the axis by an energy flow to change triboelectric charges on the electrodes, and to affect a flow of electrons between the electrodes. A self-powered sensor for detecting a chemical including a generator having an electrode, and a superhydrophobic surface layer for receiving an energy flow carrying triboelectric charges, the surface layer includes a TiO 2 layer with nanostructures, and a power indicator indicative of whether the chemical is present based on power output of the triboelectric generator, the energy flow is a solution flow, the solution comprising the chemical and water, and the chemical removes at least one triboelectric charge from the water.

Wang, Zhong Lin↗
NASA NTRS1994

LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 1: Theory and numerical solution procedures

LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 1 of a series of three reference publications that describe LENS, provide a detailed guide to its usage, and present many example problems. Part 1 derives the governing equations and describes the numerical solution procedures for the types of problems that can be solved. The accuracy and efficiency of LSENS are examined by means of various test problems, and comparisons with other methods and codes are presented. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

Radhakrishnan, Krishnan↗
DOE OSTI2026

Pulse radiolysis and transient absorption spectra of aqueous solutions of sodium sulfamate

Chemical kinetics for the reactions of sulfamate ions (NH 2 SO 3 − ) with the primary products of water and nitric acid radiolysis were measured in aqueous solutions at ambient temperature. Using time-resolved electron pulse radiolysis techniques with a custom multichannel detection system, we examined the reactivity of NH 2 SO 3 − with the hydroxyl radical ( • OH), hydrogen atom (H • ), and nitrate radical (NO 3 • ). The sulfamate ion was found to react with • OH and H • with second-order rate coefficients of k • OH = (5.60 ± 0.04) × 10 6 M −1 s −1 and k H • = (7.96 ± 0.10) × 10 6 M −1 s −1 , respectively, and with NO 3 • with a rate coefficient of k NO 3 • = (1.67 ± 0.06) × 10 7 M −1 s −1 . The reactions of NH 2 SO 3 − with • OH and H • resulted in the formation of two transient radical species, one with maximum absorbance at 300 nm and a second with maxima at both 300 nm and 600 nm. These spectra are tentatively assigned to • NH 2 SO 3 and • NHSO 3 − , respectively. By measuring the absorbance of these radicals as a function of pH, the radical pK a was determined to be 9.5 ± 0.1. Overall, this work has implications for the longevity and performance of ferrous sulfamate, Fe(NH 2 SO 3 ) 2 , as a plutonium reductant in the reprocessing of used nuclear fuel.

Conrad, Jacy K. [Idaho National Laboratory (INL), ↗
NASA NTRS1977

Rapid kinetics

Hybrid program for chemical kinetics provides rapid solution to problems involving flowing or static, chemically reacting, gas mixtures.

Mclain, A. G.↗
DOE OSTI2022

R-Value Measurements Performed on Uranium Targets Irradiated with Fission Spectrum Neutrons FY 2021 for F2019 Project

The separation and characterization of two irradiated uranium targets, a depleted uranium (DU) and a highly enriched uranium (HEU) target, was conducted in April of 2021. The two targets were assembled at Los Alamos National Laboratory (LANL) and irradiated using the critical assembly at the National Criticality Experiments Research Center (NCERC). Splits of the dissolved targets were received by Pacific Northwest National Laboratory (PNNL) after which the PNNL and LANL teams chemically separated the solutions using independent separation schemes and analyzed the separated fractions for short lived actinides and fission products. Chemical separations at PNNL were traced with stable or radioactive tracers to allow for the determination of chemical yields, analyzing using either inductively coupled plasma optical emission spectroscopy (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS) or gamma emission analysis (GEA) depending on the nature of the tracer. Several other analytical techniques were used by PNNL including kinetic phosphorescence analysis (KPA) and thermal ionization mass spectrometry (TIMS) depending on the analyte’s need. Comparisons were made between current and historical PNNL and LANL, as well as literature values. Overall, there was agreement between the two laboratories for the bulk of analytes, with some notable exceptions such as 111 Ag, and 141,143,144 Ce. Included in these comparisons were the short-lived actinides 237 U, 239 Np, the fission products 89 Sr, 91 Y, 95/97 Zr, 99 Mo, 111 Ag, 115/115 mCd, 136/137 Cs, 140 Ba, 141/143/144 Ce, 147 Nd, 153 Sm, 156 Eu, and 161 Tb, providing both total atoms as well as the R-values. The data presented in this report represents the sixth NCERC irradiation of HEU and DU (FY13, FY14, FY15, FY17, FY18, FY21), and their subsequent separation and analysis.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗