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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 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Valorization of bamboo biomass using combinatorial pretreatments

Current studies concerning liquid hot water pretreatment (LHWP) usually focus on cellulose saccharification or hemicellulose conversion, while the appropriate extraction and utilization of LHWP-induced lignin have not been addressed. To valorize whole biomass, here, in this study, a series of LHWP-based combinatorial pretreatments are proposed using advanced solvent systems. The first LHWP stage removed 73.74% of xylan at the optimized pretreatment severity (~4.0), at the same time preserving almost all the cellulose and lignin. As a result, 9.04 g L –1 xylo-oligosaccharides (XOSs) were obtained in the prehydrolyzate, representing 63.31% of the degraded xylan. The LHWP also caused the migration and partial degradation of the lignin which benefits the delignification in the second stage of pretreatment utilizing NaOH, deep eutectic solvent (DES) and 1,4-butanediol (BDO) under relatively mild conditions. The proposed combinatorial pretreatment significantly enhanced glucan conversion. The physiochemical structural properties of the untreated and pretreated substrates were investigated with XRD, FTIR, GPC, SEM, and Simons’ staining to understand the mechanisms of different combinatorial pretreatments for overcoming biomass recalcitrance and facilitating integrated biomass valorization. Finally, the physical and chemical properties of the regenerated lignins were analyzed. The results revealed that lignins from LHWP–NaOH pretreatment preserved most of the native β-O-4 structure (37.1%). Thus it could be used as an ideal method for the catalytic production of aromatic monomers. On the other hand, LHWP–DES pretreatment generated lignins with low molecular weight and high phenolic OH content, which is promising for synthesizing resins and antioxidants. In conclusion, the proposed combinatorial pretreatment established a reliable sequential pretreatment methodology for maximizing the output of bamboo biomass and may fit into different biorefinery configurations for various value-added products.

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

A high-solid DES pretreatment using never-dried biomass as the starting material: towards high-quality lignin fractionation

This study investigated a high-solid diol deep eutectic solvent (DES) pretreatment using a wet substrate as the starting material. This pretreatment led to a remarkable glucan saccharification of 94.8% with efficient lignin and xylan removal (as high as 63.1% and 73.0%, respectively). Here the chemical structures of the substrates were analyzed comprehensively to reveal the impact of the pretreatment. In addition, over 90% of the removed lignin was recovered from the pretreated liquid, which exhibited a well-preserved β-O-4 structure (46–56/100Ar). The protection mechanism of our DES was investigated by 2D HSQC NMR, GPC, and 31 P NMR analysis. This study emphasized that diol-based DES pretreatment of undried lignocellulosic biomass at a high-solid loading can significantly utilize both carbohydrates and lignin fractions with high saccharification yields and high-quality lignin as a co-product.

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

Recent advances in biomass pretreatment using biphasic solvent systems

The complexity and recalcitrance of lignocellulosic biomass seriously hinder its subsequent conversion to liquid fuels. To achieve high-value utilization of lignocellulosic biomass, the physical–chemical barrier should be overcome through appropriate pretreatment techniques to improve the accessibility of cellulose for efficient enzymatic hydrolysis. With the rapid emergence of novel pretreatment solvents, biphasic solvent pretreatments represent a nascent and green pretreatment method that has shown outstanding advantages and broad application prospects in the biorefinery of lignocellulosic substrates due to its ability to provide economically viable biomass upgrading, the separation process for products in the solvent phase, and the reutilization of solvents. Herein, different types of biphasic solvents (e.g., 2-methyltetrahydrofuran, methyl isobutyl ketone, 1-butanol, phenoxyethanol, ionic liquids, and deep eutectic solvents) were reviewed systematically, including the fundamental designs of biphasic solvents for biomass pretreatment, their effect on the fractionation of individual biomass components (e.g., carbohydrate and lignin) and the enzymatic hydrolysis performance, and the coproduction of furan and hydroxymethylfurfural. Finally, the main pros and cons of these different biphasic solvent systems are summarized, and the future development direction is also proposed. Finally, this review can provide a reference for designing and selecting effective biphasic pretreatment methods for various types of lignocellulosic biomass.

09 BIOMASS FUELS↗
DOE OSTI2024

Coordination of copper within a crystalline carbon nitride and its catalytic reduction of CO 2

Inherently disordered structures of carbon nitrides have hindered an atomic level tunability and understanding of their catalytic reactivity. Starting from a crystalline carbon nitride, poly(triazine imide) or PTI/LiCl, the coordination of copper cations to its intralayer N-triazine groups was investigated using molten salt reactions. The reaction of PTI/LiCl within CuCl or eutectic KCl/CuCl 2 molten salt mixtures at 280 to 450 °C could be used to yield three partially disordered and ordered structures, wherein the Cu cations are found to coordinate within the intralayer cavities. Local structural differences and the copper content, i.e., whether full or partial occupancy of the intralayer cavity occurs, were found to be dependent on the reaction temperature and Cu-containing salt. Crystallites of Cu-coordinated PTI were also found to electrophoretically deposit from aqueous particle suspensions onto either graphite or FTO electrodes. As a result, electrocatalytic current densities for the reduction of CO 2 and H 2 O reached as high as ∼10 to 50 mA cm −2 , and remained stable for >2 days. Selectivity for the reduction of CO 2 to CO vs. H 2 increases for thinner crystals as well as for when two Cu cations coordinate within the intralayer cavities of PTI. Mechanistic calculations have also revealed the electrocatalytic activity for CO 2 reduction requires a smaller thermodynamic driving force with two neighboring Cu atoms per cavity as compared to a single Cu atom. These results thus establish a useful synthetic pathway to metal-coordination in a crystalline carbon nitride and show great potential for mediating stable CO 2 reduction at sizable current densities.

Chemistry↗
DOE OSTI2014

Origin of the reverse optical-contrast change of Ga-Sb phase-change materials—An ab initio molecular-dynamics study

A large number of phase-change materials (PCMs) have been developed experimentally; however, only Ge{sub 2}Sb{sub 2}Te{sub 5}-based PCMs have been significantly explored using ab initio molecular-dynamics (AIMD) simulations. We present an AIMD study of the full melt/quench/anneal PC cycle for Ga-Sb materials, namely, the stoichiometric composition, GaSb, and the near-eutectic alloy, Ga{sub 16}Sb{sub 84}. The calculated electronic densities of states and optical reflectivities are compared between the amorphous and crystalline phases for both compositions, and it is shown that the contrasting opto-electronic properties of each crystalline material can be attributed to different structural transformations of Ga and Sb on crystallization from the amorphous state.

36 MATERIALS SCIENCE↗
DOE OSTI2014

The structural-phase state of iron-carbon coatings formed by the ultradispersed particles

The methods of nuclear gamma-resonance spectroscopy, elemental microanalysis, and X-ray diffraction were used to study nanoscale coatings. The samples were prepared by magnetron sputtering of carbon and iron particles. They alternately were deposited on monocrystalline silicon or polycrystalline corundum substrate moving relative to the plasma flows in the form of sublayers with a thickness of less than 0.6 nm up to the total thickness of 150-500 nm. Solid solutions with the carbon concentrations of up to 7.5, 12.0, 17.6, and 23.9 at% were produced by co-precipitation of ultradispersed particles of iron and carbon. Using method of conversion electron Mössbauer spectroscopy, we detected the anisotropy of orientation of magnetic moments of iron atoms due to texturing of the formed coatings. The deviation of the crystallite orientation from the average value depends on the degree of carbonization. At 550°C, the pearlite eutectic α‐Fe(C)+Fe{sub 3}C is formed from the amorphous structure without formation of intermediate carbides. The relative content of cementite correlates with the amount of carbon in the coating. The formation of the solid solutions-alloys directly during the deposition process confirms the theory of thermal-fluctuation melting of small particles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Thermal and galvanomagnetic properties of monocrystals CuInGa{sub 2}Te{sub 5}

By the methods of the physic-chemical analysis, determination of density and by measurement of micro hardness the character of chemical interaction in the In{sub 2}Te{sub 3}-Cu{sub 2}Ga{sub 4}Te{sub 7} system has been investigated and its faze diagram has been plotted. It is established that the system is quasibinary, of eutectic type. In the system the chemical combination of CuGa{sub 2}InTe{sub 5} composition melting congruently at 855°C is generated. There have been revealed solid solutions boundary of which based on In{sub 2}Te{sub 3} reach 5mol% at room temperatures. Temperature dependences of electric conductivity, the coefficient of thermo-emf, general heat conductivity, the Hall mobility of charge carriers.The mechanisms of electron-phonon diffusion in crystals of its compound have been revealed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Self-diffusion and microscopic dynamics in a gold-silicon liquid investigated with quasielastic neutron scattering

We use incoherent quasielastic neutron scattering to study the atomic dynamics of gold in a eutectic Au{sub 81}Si{sub 19} melt. Despite the glass-forming nature of this system, the gold self-diffusivity displays an Arrhenius behavior with a low activation energy characteristic of simple liquids. At high temperatures, long-range transport of gold atoms is well described by hydrodynamic theory with a simple exponential decay of the self-correlation function. On cooling towards the melting temperature, structural relaxation crosses over to a highly stretched exponential behavior. This suggests the onset of a heterogeneous dynamics, even in the equilibrium melt, and is indicative of a very fragile liquid.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Effect of process parameters on hardness, temperature profile and solidification of different layers processed by direct metal laser sintering (DMLS)

In DMLS process objects are fabricated layer by layer from powdered material by melting induced by a controlled laser beam. Metallic powder melts and solidifies to form a single layer. Solidification map during layer formation is an important route to characterize micro-structure and grain morphology of sintered layer. Generally, solidification leads to columnar, equiaxed or mixture of these two types grain morphology depending on solidification rate and thermal gradient. Eutectic or dendritic structure can be formed in fully equiaxed zone. This dendritic growth has a large effect on material properties. Smaller dendrites generally increase ductility of the layer. Thus, materials can be designed by creating desired grain morphology in certain regions using DMLS process. To accomplish this, hardness, temperature distribution, thermal gradient and solidification cooling rate in processed layers will be studied under change of process variables by using finite element analysis, with specific application to Ti-6Al-4V.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Ignition and self-propagating reactions in Al/Pt multilayers of varied design

The different rate-limiting processes underlying ignition and self-propagating reactions in Al/Pt multilayers are examined through experiments and analytical modeling. Freestanding, ~1.6 μm-thick Al/Pt multilayers of varied stoichiometries and nanometer-scale layer thicknesses ignite at temperatures below the melting point of both reactants (and eutectics) demonstrating that initiation occurs via solid-state mixing. Equimolar multilayers exhibit the lowest ignition temperatures when comparing structures having a specific bilayer thickness. An activation energy of 76.6 kJ/mol at. associated with solid state mass transport is determined from the model analysis of ignition. High speed videography shows that equimolar Al/Pt multilayers undergo the most rapid self-sustained reactions with wavefront speeds as large as 73 m/s. Al- and Pt-rich multilayers react at reduced rates (as low as 0.3 m/s), consistent with reduced heat of reaction and lower adiabatic temperatures. An analytical model that accounts for key thermodynamic properties, preliminary mixing along interfaces, thermal transport, and mass diffusion is used to predict the wavefront speed dependencies on bilayer thickness. Finally, good fits to experimental data provide estimates for activation energy (51 kJ/mol at.) associated with mass transport subject to high heating rates and thermal diffusion coefficient of premixed interfacial volumes (2.8 × 10 -6 m 2 /s). Pt dissolution into molten Al is identified as a rate-limiting step underlying high temperature propagating reactions in Al/Pt multilayers.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Experimental demonstration of hydraulic jump control in liquid metal channel flow using Lorentz force

Here in this paper, hydraulic jump control using electromagnetic force in a liquid metal flow is presented. The control methods used give insight into the hydraulic jump behavior in the presence of magnetic fields and electrical currents. Flowing liquid metals is a proposed solution to heat flux challenges posed in fusion reactors, specifically the tokamak. Unfortunately, thin, fast-flowing liquid metal divertor concepts for fusion reactors are susceptible to hydraulic jumps that drastically reduce the liquid metal flow speed, leading to potential problems such as excessive evaporation, unsteady power removal, and possible plasma disruption. Highly electrically conductive flows within the magnetic fields do not exhibit traditional hydraulic jump behavior. There is very little research investigating the use of externally injected electrical currents and magnetic fields to control liquid metal hydraulic jumps. By using externally injected electrical currents and a magnetic field, a Lorentz force (also referred to as j × B force) may be generated to control the liquid metal jump behavior. In this work, a free-surface liquid metal—GaInSn eutectic or “galinstan”$-$flow through an electrically insulating rectangular duct was investigated. It was shown that applying a Lorentz force has a repeatable and predictable impact on the hydraulic jump, which can be used for liquid metal control within next-generation fusion reactors.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Molten Chloride Technology Pathway to Meet the U.S. DOE SunShot Initiative with Gen3 CSP

Third-generation (Gen3) concentrating solar power (CSP) technologies require a thermally stable and inexpensive fluid to be used for heat transfer and thermal energy storage. For Gen3 CSP plants, a molten salt composed of MgCl2 - KCl - NaCl is a new candidate, but it is familiar enough to plants with existing molten-salt systems. To determine the best composition for the heat-transfer fluid, we mixed nine different ratios of the salts, dry/purified them following strict protocols, and tested them with a differential scanning calorimeter and a thermogravimetric analyzer. Our results showed that the lowest melting and solidification temperature of 385 degrees C +/- 1 degrees C was determined for the eutectic composition 44.7 MgCl2 - 25.8 KCl - 29.4 NaCl (mol.%). We determined that improper handling and preparation of the salt mixture highly affects its thermal properties because of moisture absorption. Preparation standards - particularly the dehydration of hydrous MgCl2 - merit further development.

14 SOLAR ENERGY↗
DOE OSTI2021

A high temperature cell for investigating interfacial structure on the molecular scale in molten salt/alloy systems

In this work, we describe the design and development of an in situ neutron reflectometry cell for high temperature investigations of structural changes occurring at the interface between inorganic salts, in their molten state up to 800 °C, and corrosion resistant alloys or other surfaces. In the cell, a molten salt is confined by an annular ring of single crystal sapphire constrained between the sample substrate and a sapphire plate using two gold O-rings, enclosing a liquid salt volume of 20 ml, along with a dynamic cell volume to accommodate expansion of the liquid with heating. Further, as a test case for the cell, we report on an in situ neutron reflectometry measurement of the interface between a eutectic salt mixture of MgCl 2 –KCl (32:68 molar ratio) and a single crystal sapphire substrate at 450 °C, resulting in the formation of a 60 Å layer having a scattering length density of 1.72 × 10 –6 Å –2 . While the origin of this layer is uncertain, it is likely to have resulted from the salt reacting with an existing impurity layer on the sapphire substrate.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

X-ray diffraction from shock driven Sn microjets

Here, in situ x-ray diffraction was performed on shock-generated microjets composed of Sn and Sn–4Ag. Under low pressure drives (~21 GPa), a significant fraction of the jet volume was found to be in the β-Sn phase, and these crystallites were much smaller than the initial grain size of the material. Significant quantities of amorphous (molten) material were observed for higher drive pressures (~25–35 GPa). The extent of melting at these pressures was greater than would be predicted for uniaxial shock loading. Diffraction patterns from the Sn–4Ag alloy showed a peak that is consistent with the expected Ag 3 Sn intermetallic phase. This peak remained evident under drive conditions where the sample was otherwise fully amorphous. This indicates a slushy or a mixed phase of liquid Sn and solid Ag 3 Sn. Given the eutectic character of this alloy, this observation is attributed to a kinetic limitation on the dissolution of Ag 3 Sn. This implies that a much broader range of drive conditions will lead to mixed phase jets and ejecta than would be predicted from the equilibrium melt boundary of such alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effects of a refractory metal protective barrier on uranium carbonitride ceramic–metallic composites exposed to a high temperature hydrogen environment

Uranium nitride has been under consideration at NASA and the Department of Energy for nuclear thermal propulsion applications intended for deep space exploration vehicles. It is critical to the success of the technology development that the behavior of the fuel system is properly characterized in operational environments. This body of work fabricated ceramic metal composites consisting of uranium ceramic fuel in a molybdenum and molybdenum–tungsten metal matrix, both with and without an exterior molybdenum barrier. Specimens were introduced to a high temperature hydrogen environment and characterized through x-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy to identify characteristic changes. A portion of the specimens was fabricated with a 1.27 mm thick molybdenum barrier in order to isolate the material from the hydrogen environment. Instability of the uranium nitride occurred as low as 2073 K, leading to aggressive instability approaching 2658 K. Carbon reactions with the metal matrix were observed as well as alloying between the uranium and metal matrix constituents. The liquid uranium resulting from the instability of the uranium nitride was observed to attack the grain boundaries of the refractory metal, resulting in the formation of a liquid uranium molybdenum eutectic melt. Specimens encased in a barrier experienced similar results. The authors conclude this is a significant challenge to applications of this cermet at these temperatures. Alternate configurations with resilient hermetic seals or lower temperature applications such as power reactors may have more success.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Origins of ultralow velocity zones through slab-derived metallic melt

Understanding the ultralow velocity zones (ULVZs) places constraints on the chemical composition and thermal structure of deep Earth and provides critical information on the dynamics of large-scale mantle convection, but their origin has remained enigmatic for decades. Recent studies suggest that metallic iron and carbon are produced in subducted slabs when they sink beyond a depth of 250 km. Here we show that the eutectic melting curve of the iron-carbon system crosses the current geotherm near Earth’s core-mantle boundary, suggesting that dense metallic melt may form in the lowermost mantle. If concentrated into isolated patches, such melt could produce the seismically observed density and velocity features of ULVZs. Depending on the wetting behavior of the metallic melt, the resultant ULVZs may be short-lived domains that are replenished or regenerated through subduction, or long-lasting regions containing both metallic and silicate melts. Slab-derived metallic melt may produce another type of ULVZ that escapes core sequestration by reacting with the mantle to form iron-rich post-bridgmanite or ferropericlase. The hypotheses connect peculiar features near Earth’s core-mantle boundary to subduction of the oceanic lithosphere through the deep carbon cycle.

58 GEOSCIENCES↗
DOE OSTI2021

Pressure drop in a prototypical 3D magnetohydrodynamic flow across contraction of a fusion blanket manifold

Predicting 3D magnetohydrodynamic (MHD) pressure losses associated with liquid metal flows in complex geometry ducts is required to design breeding blankets for fusion reactors. Of such components, manifolds exhibit major pressure losses. Recent correlations [T. Rhodeset al. Magnetohydrodynamic pressure drop and flow balancing of liquid metal flow in a prototypic fusion blanket manifold. Phys. Fluids. 2018; 30: 057101.] demonstrate promise for predicting pressure drops in electrically insulated inlet manifolds. In the present work, the extend to which these correlations can be applied to outlet manifolds, which feature sudden contractions, is investigated in both viscous-electromagnetic (VE) and inertial-electromagnetic (IE) regimes for Reynolds numbers 50 < Re < 1500, Hartmann numbers 2500 < Ha < 5475, and expansion/contraction ratio 10. Numerical computations have shown that the MHD pressure drops in the eutectic lead-lithium (PbLi) flows in contractions are almost identical to those in the flows featuring expansion with slightly higher magnitudes in the contraction cases. The small discripancy in the MHD pressure drop between contractions and expansions (<8%) suggests that the earlier obtained correlations for the 3D MHD pressure drop in a duct flow with a sudden expansion can also be applied to flows with a sudden contraction.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Overview of the SAS4A Metallic Fuel Models and Extended Analysis of a Postulated Severe Accident in the Prototype Gen-IV Sodium-Cooled Fast Reactor

The SAS4A safety analysis code, originally developed for the analysis of postulated severe accidents in oxide fuel sodium-cooled fast reactors (SFRs), has been significantly extended to allow the mechanistic analysis of severe accidents in metallic fuel SFRs. The SAS4A metallic fuel models simulate the metallic fuel thermomechanical and chemical behavior and track the evolution and relocation of multiple fuel and cladding components during the pretransient irradiation and during the postulated accident, allowing an accurate description of the changes in the local fuel composition. The local fuel composition determines the fuel thermophysical properties, such as freezing and melting temperatures, which in turn affect the fuel relocation behavior and ultimately the core reactivity and power history during the postulated accidents. Models describing the fuel-cladding interaction and eutectic formation, the effects of the in-pin sodium on the in-pin fuel relocation, and the postfailure reentry of the molten fuel and fission gas from the pin plenum have also been added. This paper provides an overview of the SAS4A key metallic fuel models emphasizing the postfailure metallic fuel relocation models included in the LEVITATE-M module of SAS4A. The capabilities of the SAS4A metallic fuel models are illustrated through an extended SAS4A analysis of a postulated unprotected loss-of-flow and transient-overpower accident in the metallic fuel prototype Gen-IV sodium fast reactor. The results show that the maximum relative power reached during the postulated accident is 1.19 P 0 . The favorable characteristics of the metallic fuel cause a significant decrease in net reactivity and relative power due to prefailure in-pin fuel relocation. Furthermore, negative net reactivity values persist after cladding failure, and the postfailure fuel relocation events occur at low and decreasing power levels.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗