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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Diol-enhanced natural deep eutectic solvents for efficient poplar pretreatment

Natural deep eutectic solvents (NDESs) are promising biomass pretreatment media, but their industrial application is often hindered by high viscosity. To address this limitation, diol-enhanced ternary DESs (TDESs) were prepared by incorporating 1,4-butanediol (1,4-BDO) or ethylene glycol (EG) into a choline chloride (ChCl) and 3,4-dihydroxybenzoic acid (DHBA) system. The applied TDESs maintained a liquid state at room temperature and had significantly reduced viscosity compared to the binary DES (BDES). In addition, the applied diols increased lignin solubility and suppressed lignin condensation by intercepting reactive carbocation intermediates. As a result, the recovered lignins from diol-induced TDES pretreatments showed better preservation of β-O-4 linkages and reduced condensation, improving their potential for downstream valorization. The diol-assisted DES systems showed a synergistic effect from the reduced viscosity, enhanced lignin solubility, and suppression of unwanted condensation, resulting in more effective biomass pretreatment performance, including the enhanced delignification and higher enzymatic digestibility compared to BDES. The 1,4-BDO-enhanced DES was also successfully applied to DHBA-enriched transgenic poplar, highlighting its potential for the processing of engineered biomass feedstocks.

3,4-dihydroxybenzoic acid↗
DOE OSTI2023

Determination and Comparison of Parameters from Cyclic Voltammetry of LaCl 3 in Eutectic LiCl-KCl

Electrochemical measurements of LaCl 3 were obtained in eutectic LiCl-KCl at 773 K. Cyclic voltammetry data were acquired using a tungsten electrode LaCl 3 amounts in the molten salt in the range of 0.5 to 3.0 wt%. Both cyclic voltammetry and Tafel analyses of the data resulted in calculation of values for the charge transfer coefficient (0.262), diffusion coefficient (1.67 × 10 -5 cm 2 s -1 ), exchange current density (0.0148 to 0.0473 A cm -2 ), and charge transfer resistance (0.404 to 1.99 Ω) related to lanthanum ions in the molten salt. Calculated values were compared to those available in the literature. The values of parameters found in literature varied significantly in comparison to those in the present study due to dissimilar experimental conditions, e.g., electrode material, temperature, and LaCl 3 concentration.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Electrochemical Study of BaCl{sub 2} and CsCl on a Liquid Bismuth Cathode in LiCl-KCl Eutectic Salt

Pyro-processing has been proposed and studied for recycling nuclear fuel. In pyro-processing, uranium and other actinides are recovered by electrolytic reduction in molten LiCl-KCl salts within the electro-refiner. However, over time the molten salts experience a buildup of other fission products, mostly alkali/alkaline-earths and rare earths. These products accumulate and degrade the efficiency of the electro-refiner, therefore capture and removal of these products is attractive. However, before a removal system can be designed and studied, fundamental physiochemical and electrochemical knowledge of the behavior of the fission products in the molten salts must be acquired. This project has studied the mass transport and electrochemical properties of BaCl{sub 2} and CsCl within LiCl- KCl eutectic salt on a liquid bismuth electrode. The diffusion coefficient and apparent standard potential of BaCl{sub 2} on the bismuth electrode has been determined from cyclic voltammetry. Charge transfer resistance and exchange current density values have also been obtained from electrochemical impedance spectroscopy (EIS) experiments.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2017

First-Principles-Based Computational Study on Nucleation and Growth Mechanisms of U on Mo(110) Surface Solvated in an Eutectic LiCl-KCl Molten Salt

In nuclear engineering and industry electrochemical methods have been intensively employed in pyro-processing technology to recycle used nuclear fuels for substantial alleviation of the concern with the safe treatment of high-level radioactive nuclear wastes. Pyro-processing is based on sequential electrochemical reactions at high temperature (typically above 700 K at ambient pressure) to enhance the efficiency for decoupling nuclear fuels from unfavorable fission fragments. Using a molten salt in electrorefining process, at which actinides can be selectively deposited in solid cathode from ionic states, gives several advantages over an aqueous solution: higher thermal conductivity (it is liquid phase at high temperature, molten salt plays a role as medium at high temperature over 773 K in electrochemical reaction, lower kinetic barrier in ionic diffusion mobility and better stability against undesired side reactions with radioactive materials. Therefore, the volume of high-level nuclear wastes to be, otherwise, disposed into secured sites is dramatically reduced. Most of all it conforms to nuclear non-proliferation treaty. Electrochemical reactions in a molten salt medium are, however, much more complicated than in aqueous solution rendering the accurate understanding of thermodynamic and kinetic properties formidably challenging. It is represented by extensive researches in experiments and computations to identify underlying mechanisms on how U and other fission fragments behave in the electrorefining system. Regardless of the researches there is a general agreement that the initial stage of the nucleation and growth process of the U deposit is critical for determining the properties of final product and the electrorefining efficiency. In spite of the focused studies it still remains unclear. Theoretical and computational researches have been often carried out with various empirical parameter for interatomic potential energy, which are unknown variables until numerical fits to experimental measurements or just assumption is made. Thus, empirical simulations sometimes predicted outcomes are inconsistent depending on materials of interest with experimental measurements. This may be largely because the accuracy of an empirical interatomic potential energy models critically depends on the input parameters and thus, can be limited in transferability of the results. Furthermore, it may be devoid of fundamental physics or chemistry. This situation requires special caution when an electrorefining system is studied to recycle spent nuclear fuels because of the extreme difficulty in reliable acquisition of thermodynamic and kinetic data from direct experimental measurements. In this presentation, we extensively utilized first principles density functional theory (DFT) calculations and ab-initio molecular dynamic (AIMD) simulations to figure out underlying mechanisms of the initial stage of nucleation and growth behaviors of U on Mo(110) surface in a eutectic LiCl-KCl molten salt at T = 773 K. To rigorously investigate the effect of the molten salt electrolyte we compared the results with those calculated under vacuum condition.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

SPC-70734 Rev 1 MARVEL Primary Coolant System (PCS) Fill and Eutectic NaK Procurement

This specification contains the requirements for the filling the Microreactor Applications Research Validation and Evaluation (MARVEL) reactor Primary Coolant System (PCS) with eutectic sodium-potassium (NaK). The subcontractor will design and fabricate a NaK filling system (referred to herein as the PCS Fill System), the requisite volume of high purity NaK, and perform filling operations in conjunction with the Contractor Operations. The MARVEL reactor system will be operated by the Contractor, and the PCS fill system will be operated by Subcontractor personnel.

21 - SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLAN↗
DOE OSTI2026

Phase Transitions of Eutectic High Entropy Alloy AlCoCrFeNi 2.1 Under Shock Compression

High entropy alloys (HEAs) are a new class of metals that exhibit unique mechanical performance. Among HEAs, additively manufactured eutectic high entropy alloys (AM EHEAs) have recently emerged as candidate materials for use in extreme conditions due to their simultaneous high strength and ductility. However, the deformation and structural evolution of AM EHEAs under conditions of high pressure have not been well characterized, limiting their use in extreme applications. Dynamic compression experiments and molecular dynamics simulations are presented to study the structural evolution of AM EHEA AlCoCrFeNi 2.1 when compressed to pressures up to 400 GPa. In situ X-ray diffraction measurements capture the appearance of face-centered cubic and body-centered cubic phases at different pressure conditions, with pure- and mixed-phase regions. Furthermore, understanding the phase stability and structural evolution of the AM EHEA offers new insights to guide the development of high-performance complex materials for extreme conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Thermodynamic Framework for Water in Deep Eutectic Solvents and Ionic Liquids

Water is widely recognized as critical to the tunability and electrochemical stability of nonaqueous solvents such as deep eutectic solvents (DESs) and ionic liquids (ILs). Traditionally, the water content of these solvents has been controlled by either drying or adding small amounts of water to control their bulk properties to meet specific application requirements. The total water content by itself, does not provide sufficient information about the chemical reactivity and molecular interactions within DES– and IL–water mixtures. In this concept article, water activity is highlighted as a thermodynamically more rigorous descriptor to quantify the influence of the co‐solvent water on DES– and IL–water mixtures. Water activity relates measurable physical properties, such as vapor pressure, density, viscosity, electrochemical stability, and conductivity of DESs and ILs to the underlying molecular interactions between their components. Furthermore, water activity of DESs and ILs correlates with changes in local solvent structures and thermodynamic excess properties, including excess molar volume, enthalpy, and Gibbs energy.

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

Engineered Sorghum Bagasse Enables a Sustainable Biorefinery with p-Hydroxybenzoic Acid-Based Deep Eutectic Solvent

Integrating multidisciplinary research in plant genetic engineering and renewable deep eutectic solvents (DESs) can facilitate a sustainable and economic biorefinery. In this work, we leveraged a plant genetic engineering approach to specifically incorporate C6C1 monomers into the lignin structure. By expressing the bacterial ubiC gene in sorghum, p-hydroxybenzoic acid (PB)-rich lignin was incorporated into the plant cell wall while this monomer was completely absent in the lignin of the wild-type (WT) biomass. A DES was synthesized with choline chloride (ChCl) and PB and applied to the pretreatment of the PB-rich mutant biomass for a sustainable biorefinery. The release of fermentable sugars was significantly enhanced (~190 % increase) compared to untreated biomass by the DES pretreatment. In particular, the glucose released from the pretreated mutant biomass was up to 12 % higher than that from the pretreated WT biomass. Lignin was effectively removed from the biomass with the preservation of more than half of the β-Ο-4 linkages without condensed aromatic structures. Hydrogenolysis of the fractionated lignin was conducted to demonstrate the potential of phenolic compound production. In addition, a simple hydrothermal treatment could selectively extract PB from the same engineered lignin, showing a possible circular biorefinery. These results suggest that the combination of PB-based DES and engineered PB-rich biomass is a promising strategy to achieve a sustainable closed-loop biorefinery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Efficient Fast Fractionation of Biomass Using a Diol-Based Deep Eutectic Solvent for Facilitating Enzymatic Hydrolysis and Obtaining High-Quality Lignin

Current DES pretreatment is often performed under relatively severe conditions with high temperature, long time, and high DES usage. This work studied a short-time diol DES (deep eutectic solvent) pretreatment under mild conditions to fractionate the bamboo, facilitate enzymatic hydrolysis, and obtain high-quality lignin. At an optimized condition of 130 °C for only 10 min, lignin and xylan removal reached 61.34% and 84.15 %, with residual glucan showing a ~90% enzymatic hydrolysis yield. Equally important, the dissolved lignin could be readily recovered with 97.51% yield, exhibiting 96.65 % β-O-4 preservation. The fractionation and lignin protection mechanisms were unveiled by XRD, FTIR, cellulose-DP, 2D HSQC NMR, 31 P NMR and GPC analysis. Finally, this study highlighted that short-time fractionation of bamboo can be achieved by a diol-based DES which is an ideal strategy to upgrade the lignocellulose biomass for high enzymatic hydrolysis yields and high-quality lignin stream.

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

Tuning the Properties of Lignin‐Derived Deep Eutectic Solvents for Biomass Processing

Lignin-derived deep eutectic solvents (DESs) have been investigated as sustainable green media for biomass processing. However, the properties and processability of DESs have not been fully understood with the chemical structures of their constituents for biomass fractionation. Here, in this article, the properties of the phenolic DESs are discussed with different numbers of functional groups, such as –OCH 3 and –CHO in their hydrogen bond donor (HBD) structures. The formation of DES is significantly related to the hydrogen bond between its constituents, identified by nuclear magnetic resonance (NMR) analysis and density functional theory calculation (DFT). Lower viscosity and net basicity of DES are achieved with fewer –OCH 3 on HBD structures, resulting in enhanced processability and fractionation efficiency. The thermal stability of the DES is also influenced by the –OCH 3 and –CHO of HBD, as indicated by its onset temperature. The recyclability of the phenolic DES is confirmed by the fractionation performance of the recycled DES. Understanding the structural impacts of DES constituents on the properties and performance is crucial for designing solvents in biorefinery applications.

Ryu, Jiae [State University of New York (SUNY), Sy↗
DOE OSTI2020

Thermal Stability of a Eutectic Mixture of Bis(2,2-dinitropropyl) Acetal and Formal: Part C. Kinetic Compensation Effect

Here, the aging behavior of a eutectic mixture of bis(2,2-dinitropropyl) acetal and formal [called NP here] has been studied in various atmospheres [dry (air or nitrogen) versus wet] at temperatures 70 °C and below. The properties of aged samples were analyzed using Fourier transform infrared (FTIR) spectroscopy, Karl Fischer (KF) titration, liquid chromatography/mass spectrometry (LC/MS), and thermogravimetric analysis (TGA) over a period of three years. The results indicate that at aging temperatures up to 55 °C, the initial rates of water production from nitrous acid (HONO) formation and decomposition into the water, NO, and NO 2 follows a 1st order rate law and the rate constants follow an Arrhenius law as a function of temperature. The activation energies and pre-factors for water and volatiles production yield a single linear kinetic compensation plot, suggesting a common degradation pathway between NP and the various combinations of its constituents. Within a narrow temperature range, around 55 °C, a trace amount of water in NP stabilizes its properties by preventing HONO elimination. When the aging temperature is substantially higher than 55 °C, the nature of the degradation mechanism changes. It is suspected that the degradation products of NO x , water, and HNO 3 serve as catalysts to auto-catalyze (kinetics beyond the 1st order) and further degrade NP. The effect of headspace volume on this auto-catalytic process will be discussed.

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

Liquid Chromatography Mass Spectrometry study of eutectic bis(2,2-dinitropropyl) acetal/formal

This study is the first attempt to document methodology development undergone using liquid chromatography tandem quadrupole time of flight mass spectrometry (LC-QTOF) to investigate degradation products of eutectic bis(2,2-dinitropropyl) acetal/formal nitroplasticizer (called NP here). Method properties investigated are: desolvation temperature (°C) and spray voltage (V) of the electrospray ionization source, and the development of an acetone system rinse to prevent any residual contamination between sample injections. Details are given on why it is essential to investigate method optimization with changes shown in MS/MS analysis in addition to MS results. Trends in MS/MS analytic results reveal important relationships between baseline and aged materials. In addition to verification of previously proposed fragments, insights offered by this newly developed methodology will also identify new degradation products and shed light on the complexity of NP degradation chemistry.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Identification of 2,2-dinitropropanol, a Hydrolyzed Product of Aged Eutectic Bis(2,2-dinitropropyl) Acetal – Bis(2,2-dinitropropyl) Formal Mixture

Eutectic bis(2,2-dinitropropyl) acetal - bis(2,2-dinitropropyl) formal mixture, nitroplasticizer (herein called NP) has historically been produced by either the ter Meer or oxidative nitration synthesis process, wherein 2,2-dinitropropanol (DNPOH) is produced as an intermediate step in both processes. Therefore that DNPOH, could be present in NP either as a production or hydrolysis degradation product is worth investigation. Here, we synthesized DNPOH, validated the synthesis using NMR, and identified DNPOH in aged NP using liquid chromatography tandem time of flight – quadrupole mass spectrometry (LC-QTOF). Using these results, for the first time we positively identify that DNPOH is absent from NP after its production, but is present as a degradation product through hydrolysis from a thermo-chemical aging profile of NP. To hydrolyze NP, prerequisite is the presence of both water and acid. Despite the presence of water in NP, DNPOH is only generated in the late stage of the aging process, when acid concentration is sufficiently high. It has been previously shown both theoretically and experimentally that a primary step of NP degradation is HONO elimination followed by decomposition, wherein nitric acid, nitrous acid, and water are produced (NP→NP’+2HONO and 2HONO→NO+NO 2 +H 2 O). It is shown from this reaction series that water slows HONO decomposition and therefore in small quantities, 100 s of ppm, water actually stabilizes NP against hydrolysis by equilibrium and reducing acidity.

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

Anodization Compatibility of Eutectic Aluminum–Cerium Alloys

Anodizing is the most common method for producing corrosion resistant layer coatings for aluminum alloys. It is possible to use anodizing with most commercial aluminum alloys to increase material corrosion resistance, but often the brittle, passive oxide layer formed during anodization does not adhere well to the material, reducing effectiveness, and overall compatibility. Therefore, it is important for the compatibility and effect of anodization to be studied for any newly developed alloys. Recently developed eutectic Al–Ce alloys offer advantages like high castability, limited or no heat treatment requirements, and high-temperature strength retention. In this work, Al–Ce alloys are shown to have good compatibility with current processes and may exhibit improved adhesion of passivated layer because intermetallic phases anchor the anodized product to unconverted bulk. The source of these phenomena and their effect on material corrosion and layer adhesion properties of Al–Ce alloys will be discussed and compared with results from common commercial aluminum alloys.

Sims, Zachary↗
DOE OSTI2019

La2USe3S2: A Serendipitously Grown Lanthanide/Actinide Chalcogenide from a Eutectic Halide Flux

La 2 USe 3 S 2 , exact composition La 2 USe 2.96 S 2.04 , crystallized from a reaction between USe2 and La 2 S 3 in a molten CsCl/KCl eutectic flux and was characterized by single crystal X-ray diffraction. La 2 USe 3 S 2 crystallizes in the orthorhombic space group Pnma in the U 3 S 5 structure type with lattice parameters a = 12.3284(3) Å, b = 8.4028(2) Å, and c = 7.3452(2) Å. In La 2 USe 3 S 2 all the anion sites have mixed S and Se occupancy and, henceforth, will be simply referred to as Q sites. The compound exhibits sigmoidal sheets built from LaQ 8 (Q= S, Se) bicapped trigonal prisms that edge-share down the a-axis forming rectangular-shaped channels or tunnels. Lastly, these tunnels are occupied by UQ 6 (Q = S, Se) octahedra that edge-share to form infinite, one-dimensional chains running down the b-axis.

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

A study of deformation and strain induced in bulk by the oxide layers formation on a Fe-Cr-Al alloy in high-temperature liquid Pb-Bi eutectic

At elevated temperatures, heavy liquid metals and their alloys are known to create a highly corrosive environment that causes irreversible degradation of most iron-based materials. In this paper, it has been found that an appropriate concentration of oxygen in the liquid alloy can significantly reduce this issue by creating a passivating oxide scale that controls diffusion, especially if Al is present in Fe-based materials (by Al-oxide formation). However, the increase of the temperature and of oxygen content in liquid phase leads to the increase of oxygen diffusion into bulk, and to promotion of the internal Al oxidation. This can cause a strain in bulk near the oxide layer, due either to mismatch between the thermal expansion coefficients of the oxides and bulk material, or to misfit of the crystal lattices (bulk vs. oxides). This work investigates the strain induced into proximal bulk of a Fe-Cr-Al alloy by oxide layers formation in liquid lead-bismuth eutectic utilizing synchrotron X-ray Laue microdiffraction. Finally, it is found that internal oxidation is the most likely cause for the strain in the metal rather than thermal expansion mismatch as a two-layer problem.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Interface velocity dependent solute trapping and phase selection during rapid solidification of laser melted hypo-eutectic Al-11at.%Cu alloy

Microstructure formation of a hypo-eutectic Al-11Cu (atom percent) alloy during solidification after laser melting has been studied by transmission electron microscopy (TEM). The evolution of the solid-liquid-interface velocity, V SL , during the solidification process has been determined from direct observation by in-situ TEM. This enabled correlating V SL with development of four distinct microstructure zones. Crystal growth mode transitions from planar to cellular, cellular to dendritic, dendritic to cellular, and cellular to planar, have been observed for the accelerating solid-liquid-interface. The transition from coupled two-phase growth to the single-phase growth occurred for V SL = V a = (0.80±0.05) m/s, where V a is the velocity of absolute stability, at the onset of banded morphology grain formation. The in-situ and post-mortem TEM uniquely permitted determination of the non-equilibrium solidus for the rapidly solidifying Al-11Cu alloy. Experimental evidence for solute clustering and chemical ordering tendencies at length scales on the order of ≤ 5nm has been detected in the single-phase regions of the banded grains. The structural features of the single-phase bands have been interpreted as signatures of ‘frozen in’ configurations present in the liquid boundary layer adjacent to the growing crystal, which has a width of about 3nm. Finally, the nano-scale spatiotemporal resolution experimental TEM studies performed here provided quantitative metrics, e.g. the solidification interface velocity dependent solute concentration of the α-Al phase and the near-atomic scale structure in the single-phase bands, that are uniquely suitable for comparison with theory and model predictions for solidification microstructure development in multicomponent alloys after laser melting.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Atomistic modeling of interface strengthening in Al-Si eutectic alloys

Al-Si cast alloys are usually composed of α-Al and Al-Si eutectic. Si flakes and Al matrix generally hold cube-on-cube orientation relationship with the primary interface (111) Al ∥(111) Si . Extensive experimental studies demonstrated that Si flakes cannot significantly improve mechanical properties of Al-Si cast alloys. We hypothesize that the weak strengthening effect associated with Si flakes might be attributed to thermomechanical properties of Al-Si interfaces besides their morphologies. To characterize Al-Si interfaces with a large lattice mismatch (> 30%), we proposed the quasi-coincident site lattice (Q-CSL) as reference lattice, and demonstrated that the Q-CSL Al-Si coherent interface has three characteristic coherent structures, one stable and low energy structure and two metastable and high energy structures. The translation vectors for the same type of coherent Q-CSL structures are consistent with three displacement shift complete (DSC) vectors. The two metastable structures can be obtained by shifting the low energy structure with three partial DSC vectors. Semi-coherent interface is composed of the low energy Q-CSL patches and three sets of interface misfit dislocations with Burgers vectors same as the DSC vectors. Atomistic simulations revealed that Al-Si interface exhibits low shear resistance. Ideal shear strength of the Q-CSL coherent interface is 110 MPa and semi-coherent interface is 20 MPa. The low shear resistance is attributed to the glide of interface misfit dislocations. Al-Si interface also exhibits low formation and migration energies of point defects. Owing to low shear strength and low formation and migration energies of point defects, interface sliding or shear readily happen under mechanical loading or during dislocation-interface interactions. Lattice dislocations can cross slip onto or climb along Al-Si interfaces. These reactions decrease the number of accumulated dislocation loops around Si flakes and promote nucleation and emission of lattice dislocations from Al-Si interfaces to matrix, consequently reduce the repulsive force on approaching dislocations and weaken Si flakes strengthening effect. In situ tension and compression tests in a scanning electron microscope reveal relatively weak strengthening effect due to Si flakes, consistent with the computed dislocation interaction with interfaces and shear behavior of interfaces.

36 MATERIALS SCIENCE↗