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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Applications of Kinetic Methods in Thermal Analysis: A Review

Determining kinetic parameters such as activation energy (Ea), pre-exponential factor (A), rate constants, and reaction order (n) via thermal analysis techniques is important to material synthesis and fabrication, industrial production, biomedicals, energy storage, catalysis, etc. Various kinetic methods based on the non-isothermal techniques have been developed to obtain the kinetic parameters. In this review, we focus on introducing various kinetic methods in non-isothermal analysis and their applications in different reactions, including thermal decomposition, solid-state phase transformation, crystallization, thermal ignition, curing process, etc.

Zhang, Xin↗
DOE OSTI2017

The Gaseous Phase as a Probe of the Astrophysical Solid Phase Chemistry

In support of space missions and spectroscopic observations, laboratory experiments on ice analogs enable a better understanding of organic matter formation and evolution in astrophysical environments. Herein, we report the monitoring of the gaseous phase of processed astrophysical ice analogs to determine if the gaseous phase can elucidate the chemical mechanisms and dominant reaction pathways occurring in the solid ice subjected to vacuum ultra-violet (VUV) irradiation at low temperature and subsequently warmed. Simple (CH{sub 3}OH), binary (H{sub 2}O:CH{sub 3}OH, CH{sub 3}OH:NH{sub 3}), and ternary ice analogs (H{sub 2}O:CH{sub 3}OH:NH{sub 3}) were VUV-processed and warmed. The evolution of volatile organic compounds in the gaseous phase shows a direct link between their relative abundances in the gaseous phase, and the radical and thermal chemistries modifying the initial ice composition. The correlation between the gaseous and solid phases may play a crucial role in deciphering the organic composition of astrophysical objects. As an example, possible solid compositions of the comet Lovejoy are suggested using the abundances of organics in its comae.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

A straightforward method for Vacuum-Ultraviolet flux measurements: The case of the hydrogen discharge lamp and implications for solid-phase actinometry

Vacuum-Ultraviolet (VUV) radiation is responsible for the photo-processing of simple and complex molecules in several terrestrial and extraterrestrial environments. In the laboratory such radiation is commonly simulated by inexpensive and easy-to-use microwave-powered hydrogen discharge lamps. However, VUV flux measurements are not trivial and the methods/devices typically used for this purpose, mainly actinometry and calibrated VUV silicon photodiodes, are not very accurate or expensive and lack of general suitability to experimental setups. Here, we present a straightforward method for measuring the VUV photon flux based on the photoelectric effect and using a gold photodetector. This method is easily applicable to most experimental setups, bypasses the major problems of the other methods, and provides reliable flux measurements. As a case study, the method is applied to a microwave-powered hydrogen discharge lamp. In addition, the comparison of these flux measurements to those obtained by O{sub 2} actinometry experiments allow us to estimate the quantum yield (QY) values QY{sub 122} = 0.44 ± 0.16 and QY{sub 160} = 0.87 ± 0.30 for solid-phase O{sub 2} actinometry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

A Low-Cost Fabrication Technique for the Growth of Single-Domain GdBCO Bulk Superconductor from Raw Metal Oxides

A single-domain GdBCO bulk superconductor is usually fabricated using a mixture of pre-reacted precursor powders (including GdBa{sub 2}Cu{sub 3}O{sub 7−δ} and Gd{sub 2}BaCuO{sub 5}) by the top-seeded melt texture growth (TSMTG) process. However, the synthesis of pure-phase precursor powder by the solid-state sintering reaction can not only consume time for weeks but also prolong the fabrication process and can lead to a low-efficiency and high-cost process. In this paper, we reported the successful growth of single-domain GdBCO bulk superconductors by the top-seeded metallic oxide melt growth (TS-MOMG) process in which the raw materials of Gd{sub 2}O{sub 3}, BaO, and CuO, the three different metallic oxides, are just involved to fabricate the single-domain GdBCO bulk superconductors. After detailed investigations in the morphology, levitation force, trapped magnetic field, and critical temperature of the grown samples with different ratios, it was found that the simplified precursor-phase source can be used to fabricate the single-domain GdBCO bulk superconductors more efficiently, which can combine the crystal growth procedure and greatly economize the preparation cost and the time to the most extent.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Compositions and morphologies of TiAlSi intermetallics in different diffusion couples

Two kinds of diffusion couples were designed to investigate the formation of ternary TiAlSi phases in Al–Si–Ti alloys. It was found that different diffusion processes result in various compositions and morphologies of TiAlSi intermetallics. The melted Al, Si and Ti atoms in the diffusion couple leads to the formation of flake-like TiAlSi phase through liquid–liquid reaction. Besides, unidirectional diffusion of Al and Si atoms into blocky TiAl{sub 3} particles or Ti powders via a liquid–solid diffusion process also results in the formation of TiAlSi, while keeping the block-like morphology. This kind of diffusion is a gradual process, driven by the concentration gradient. The reactions in the diffusion couples are helpful to understand the compositional and morphological evolutions of TiAlSi as reported in previous work. - Highlights: • Two diffusion couples were designed to investigate the formation of TiAlSi phases. • Compositions and morphologies of TiAlSi are influenced by the diffusion process. • Liquid–liquid and liquid–solid diffusions were detected. • The corresponding mechanisms were discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Polycrystalline Crusts in Accreting Neutron Stars

The crust of accreting neutron stars plays a central role in many different observational phenomena. In these stars, heavy elements produced by H–He burning in the rapid proton capture (rp-) process continually freeze to form new crust. Here, we investigate the expected composition of the solid phase. We first demonstrate using molecular dynamics that two distinct types of chemical separations occur, depending on the composition of the rp-process ashes. We then calculate phase diagrams for three-component mixtures and use them to determine the allowed crust compositions. We show that, for the large range of atomic numbers produced in the rp-process (Z ~ 10–50), the solid that forms has only a small number of available compositions. We conclude that accreting neutron star crusts should be polycrystalline, with domains of distinct composition. Our findings motivate further work on the size of the compositional domains and have implications for crust physics and accreting neutron star phenomenology.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

The effect of B{sub 2}O{sub 3} flux on growth NLBCO superconductor by solid state reaction and wet-mixing methods

The synthesis of B{sub 2}O{sub 3} flux substituted NLBCO superconductor NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂} has been done using solid state reaction and wet-mixing methods in order to obtain homogeneous crystals and single phase. From DTA/TGA characteritations showed the synthesis process by wet-mixing requires a lower temperature than the solid state reaction in growing the superconductor NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂}. Therefore, in this research NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂} sample calcinated at 650°C for wet-mixing method and 820°C for solid state reaction methods. The all samples was sintered at 950°C for ten hours. Crystallinity of the sample was confirmed using X-ray techniques and generally obtained sharp peaks that indicates the sample already well crystallized. Search match analyses for diffraction data gave weight fractions of impurity phase of the solid state reaction method higher than wet-mixing method. In this research showed decreasing the price of the lattice parameter about 1% with the addition of B{sub 2}O{sub 3} flux for the both synthesis process and 2% of wet mixing process for all samples. Characterization using scanning electron microscopy (SEM) showed the distribution of crystal zise for wet-mixing method more homogeneous than solid state reaction method, with he grain size of samples is around 150–250 nm. The results of vibrating sample magnetometer (VSM) showed the paramagnetic properties for all samples.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Groundwater Remediation in a Flood plain Aquifer at Shiprock, New Mexico - 16097

The Shiprock, New Mexico, Disposal Site is the location of a former uranium and vanadium ore-processing mill that operated from 1954 to 1968. During milling years, tailings leachate and other mill-related liquids migrated into underlying sediments, resulting in the contamination of groundwater beneath the river terrace containing the mill and a nearby flood plain alluvial aquifer adjacent to the San Juan River. The US DOE Office of Legacy Management manages the site and is implementing the current groundwater remedy for the flood plain area, consisting of natural flushing supplemented by extraction of alluvial groundwater to accelerate reduction in contaminant concentrations. The alluvial aquifer contains elevated concentrations of sulfate, uranium, and nitrate derived largely from the historical eastward migration of groundwater through terrace alluvium and underlying bedrock to the flood plain. The bedrock formation beneath the entire Shiprock site is Mancos shale, which forms an escarpment that separates the terrace from the flood plain. Contamination in the flood plain alluvial aquifer is influenced by a dynamic flow system that changes seasonally and from year to year. Simulations with a flood plain flow model based on monitored groundwater levels and coincident river-surface elevations show that background groundwater flow, unaffected by remediation pumping, is characterized by distinct hydraulic conditions for three separate periods each year. During months of low river flow in winter and early spring, river losses to the aquifer create a large hypo-rheic zone in the south half of the flood plain. Simultaneously, recharge of continually flowing surface water emptying onto the north half of the flood plain from Bob Lee Wash creates divergent, radial flow from the wash outlet and diverts northwestward-migrating contaminant plumes to the northeast where they discharge to the river. Subsequent bank storage processes in May and June from high snow melt runoff change background flow directions, increasing the spread of contamination in the alluvium. From mid-summer through fall, river flows are typically similar in value to those observed prior to the onset of snow melt, but groundwater elevations in the aquifer are noticeably lower than water levels observed in winter and early spring and may induce river losses to the aquifer. Several different contaminant sources have impacted the alluvial aquifer. Much of the contamination originated as tailings leachate and raffinate wastewater that infiltrated the terrace subsurface and eventually reached the flood plain at the escarpment. Additional sources of contamination in the aquifer included discharge of mill effluent to Bob Lee Wash and a pond at the base of the escarpment, and aqueous mobilization of solid-phase contamination in the form of windblown deposits and contaminants adsorbed to alluvial sediments. The degree to which remnant, secondary-source processes, such as leaching of solid-phase deposits and discharge of terrace groundwater across the escarpment, contribute to existing contaminant plumes is uncertain. The flood plain remediation system consists of two groundwater extraction wells, pumping from two horizontal wells placed in trenches near the base of the escarpment, a sump collecting discharges from seeps in the escarpment wall, and discharge of collected water to an evaporation pond on the terrace. Flow-model simulations indicate that most contaminated areas are captured by remediation pumping, resulting in several zones of freshwater between the river and the escarpment. Despite the highly transient nature of groundwater flow beneath the flood plain and the varied contaminant sources, initiation of remediation pumping in 2003 and coordinated operation of the system's various components have successfully removed large amounts of contaminant mass and helped prevent discharge of contaminated groundwater to the river. The percentage reductions of dissolved sulfate, uranium, and nitrate mass in the aquifer estimated for the first 9 years of remediation range from 40% to 72%. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Microstructure evolution and mechanical properties of Cu/Sn/Ag TLP-bonded joint during thermal aging

Highlights: • The thermal reliability of the Cu/Sn/Ag TLP-bonded joint was investigated through high-temperature storage. • A diffusion reaction occurred at the interface between Cu{sub 3}Sn and Ag{sub 3}Sn during thermal aging. • The mechanism of the Cu{sub 3}Sn/Ag{sub 3}Sn interfacial reaction was investigated from thermodynamics and kinetics. - Abstract: Low-temperature transient liquid phase (TLP) bonding is a promising joining technology for high-temperature electronic devices packaging. However, the effect of thermal aging on the joint microstructure and performance has been rarely studied so far. In this paper, the relationship between microstructural evolution and mechanical property was developed for the Cu/Sn/Ag TLP-bonded joint during 350 °C aging. Experimental results show that an interfacial reaction occurs between the intermetallic compounds (IMCs) of Cu{sub 3}Sn and Ag{sub 3}Sn, which induces that a great amount of Cu{sub 3}Sn particles or wedges embed into the Ag-Sn phase layer. The reaction process is controlled by a volume diffusion of Cu elements from the Cu substrate, and capable of promoting the transformation from Ag{sub 3}Sn into Ag(Sn) solid solution. Cu{sub 41}Sn{sub 11} phase can be formed at the expense of Cu{sub 3}Sn and Cu, of which transformation process is completely achieved after aging for 480 h, and the Cu(Sn) solid solution intimately contacts with the opposite Ag(Sn) solid solution in many areas after aging for 960 h. The joint mechanical property initially declines due to the formation of Cu{sub 41}Sn{sub 11} phase and Cu-Sn IMCs grain coarsening, and then increases because of the complete depletion of Cu{sub 3}Sn and substantial precipitation of Cu(Sn) solid solution. After aging for nearly 1000 h, the joint still maintains a high shear strength of >40 MPa, indicating an excellent thermal reliability.

36 MATERIALS SCIENCE↗
DOE OSTI2016

54 Mn Radiotracers Demonstrate Continuous Dissolution and Reprecipitation of Vernadite (δ-MnO 2 ) during Interaction with Aqueous Mn(II)

54 Mn radiotracers were used to assess Mn atom exchange between aqueous Mn(II) and vernadite (δ-MnO 2 ) at pH 5.0. Continuous solid–liquid redistribution of 54 Mn atoms occurred, and systems are near isotopic equilibrium after reaction for 3 months. Despite this extensive exchange, X-ray diffraction and X-ray absorption spectroscopy data showed no major changes in vernadite bulk mineralogy. These results demonstrate that the vernadite–Mn(II) interface is dynamic, with the substrate undergoing continuous dissolution and reprecipitation mediated by aqueous Mn(II) without observable impacts on its mineralogy. Interfacial redox reactions between adsorbed Mn(II) and solid-phase Mn(IV) and Mn(III) are proposed as the main drivers of this process. Interaction between aqueous Mn(II) and structural Mn(III) likely involves interfacial electron transfer coupled with Mn atom exchange. Here, the exchange of aqueous Mn(II) and solid-phase Mn(IV) is more complex and is proposed to result from coupled interfacial comproportionation–disproportionation reactions, where electron transfer from adsorbed Mn(II) to lattice Mn(IV) produces transient Mn(III) species that disproportionate to regenerate aqueous Mn(II) and structural Mn(IV). These findings provide further evidence of the importance of Mn(II) (aq) –MnO 2(s) interactions and the attendant production of transient Mn(III) intermediates to the geochemical functioning of phyllomanganates in environments undergoing Mn redox cycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Phase Transformations and Microstructural Evolution: Part II

The activities of the Phase Transformations Committee of the Materials Processing & Manufacturing Division (MPMD) of The Minerals, Metals & Materials Society (TMS) are oriented toward understanding the fundamental aspects of phase transformations. Emphasis is placed on the thermodynamic driving forces for phase transformations, the kinetics of nucleation and growth, interfacial structures and energies, transformation crystallography, surface reliefs, and, above all, the atomic mechanisms of phase transformations. Phase transformations and microstructural evolution are directly linked to materials processing, properties, and performance. In this issue, aspects of liquid–solid and solid-state phase transformations and microstructural evolution are highlighted. Many papers in this issue are highlighted by this paper, giving a brief summary of what they bring to the scientific community.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Direct observation of the kinetics of gas–solid reactions using in situ kinetic and spectroscopic techniques

Developing fundamental insight for reactions between gas phase H 2 S and solid phase CuO has the potential to lead to improved materials and processes for natural gas purification. However, this insight requires detailed knowledge of the atomistic characteristics of the solid and how these characteristics influence the reaction mechanism and kinetics. Herein, we use fixed bed reactors, X-ray absorption spectroscopy, and transmission X-ray microscopy to simultaneously probe the fundamental kinetics of the reaction of CuO with H 2 S to form CuS, and thereby probe spatial-temporal chemical and structural changes of copper during this reaction. H 2 S removal reaction kinetics show similar trends in fixed bed reactors as in 10-20 µm sized particles. However, reaction fronts proceed through the entire diameter of particles heterogeneously, indicating the presence of pore diffusion resistance even at very small length scales. In addition, CuO sorbent samples with similar characteristics exhibit 3 times different sulfidation conversion with reaction rate constants that differ by a factor of 1.5. Furthermore, these differences in reaction kinetics and conversion indicate the critical impact of possible atomic scale differences and the formation of different copper sulfide products.

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

Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites

Liquid-phase processing of molecules using heterogeneous catalysts – an important strategy for obtaining renewable chemicals sustainably from biomass – involves reactions that occur at solid-liquid interfaces. In glucose isomerization catalyzed by basic faujasite zeolites, the catalytic activity depends strongly on the solvent composition: initially, it declines precipitously when water is mixed with a small amount of the organic co-solvent γ-valerolactone (GVL), then recovers as the GVL content increases. Using solid-state 13C NMR spectroscopy, we observed glucose isomers located inside the zeolite pores directly, and followed their transformations into fructose and mannose in real time. At low GVL concentrations, glucose is depleted in the zeolite pores relative to the liquid phase, while higher GVL concentrations in solution drive glucose inside the pores, resulting in up to a 32 enhancement in the local glucose concentration. Although their populations exchange rapidly, molecules present at the reactive interface experience a significantly different environment from the bulk solution.

carbohydrate isomerization↗
DOE OSTI2023

Rational synthesis of high-performance Ni-rich layered oxide cathode enabled via probing solid-state lithiation evolution

Lithium (Li)-ion batteries using nickel (Ni)-rich layered oxide cathode have been pursued with interest due to high practical energy density. A fundamental understanding of the reaction pathways and structural evolution of the solid-phase synthesis of these materials is crucial for their rational design and process development for mass production. In this work, structural evolution during solid-state synthesis was traced via in situ technique, with a particular emphasis on the lithiation reaction and migration of transition metal (TM) ions. The sintering process is governed by the competitive relationship of decomposition and lithiation reactions, which can be regulated through temperature windows. Controlling the melting point of the Li sources, as well as their affinity to cathode precursors, is highly desired to maintain the layered ordering of TM ions throughout the whole synthesis process, which simplifies the manufacturing process and improves the quality of the manufactured cathode material.

25 ENERGY STORAGE↗
DOE OSTI2021

Kinetics of solid–liquid interface motion in molecular dynamics and phase-field models: crystallization of chromium and silicon

The results of molecular dynamics (MD) simulations of the crystallization process in one-component materials and solid solution alloys reveal a complex temperature dependence of the velocity of the crystal–liquid interface featuring an increase up to a maximum at 10–30% undercooling below the equilibrium melting temperature followed by a gradual decrease of the velocity at deeper levels of undercooling. At the qualitative level, such non-monotonous behaviour of the crystallization front velocity is consistent with the diffusion-controlled crystallization process described by the Wilson–Frenkel model, where the almost linear increase of the interface velocity in the vicinity of melting temperature is defined by the growth of the thermodynamic driving force for the phase transformation, while the decrease in atomic mobility with further increase of the undercooling drives the velocity through the maximum and into a gradual decrease at lower temperatures. At the quantitative level, however, the diffusional model fails to describe the results of MD simulations in the whole range of temperatures with a single set of parameters for some of the model materials. The limited ability of the existing theoretical models to adequately describe the MD results is illustrated in the present work for two materials, chromium and silicon. It is also demonstrated that the MD results can be well described by the solution following from the hodograph equation, previously found from the kinetic phase-field model (kinetic PFM) in the sharp interface limit. The ability of the hodograph equation to describe the predictions of MD simulation in the whole range of temperatures is related to the introduction of slow (phase field) and fast (gradient flow) variables into the original kinetic PFM from which the hodograph equation is obtained. The slow phase-field variable is responsible for the description of data at small undercoolings and the fast gradient flow variable accounts for local non-equilibrium effects at high undercoolings. The introduction of these two types of variables makes the solution of the hodograph equation sufficiently flexible for a reliable description of all nonlinearities of the kinetic curves predicted in MD simulations of Cr and Si. This article is part of the theme issue ‘Transport phenomena in complex systems (part 1)’.

Science & Technology - Other Topics↗
DOE OSTI2017

Multi-Stage Structural Transformations in Zero-Strain Lithium Titanate Unveiled by in Situ X-ray Absorption Fingerprints

Zero-strain electrodes, such as spinel lithium titanate (Li 4/3 Ti 5/3 O 4 ), are appealing for application in batteries due to their negligible volume change and extraordinary stability upon repeated charge/discharge cycles. On the other hand, this same property makes it challenging to probe their structural changes during the electrochemical reaction. In this paper, we report in situ studies of lithiation-driven structural transformations in Li 4/3 Ti 5/3 O 4 via a combination of X-ray absorption spectroscopy and ab initio calculations. Based on excellent agreement between computational and experimental spectra of Ti K-edge, we identified key spectral features as fingerprints for quantitative assessment of structural evolution at different length scales. Results from this study indicate that, despite the small variation in the crystal lattice during lithiation, pronounced structural transformations occur in Li 4/3 Ti 5/3 O 4 , both locally and globally, giving rise to a multi-stage kinetic process involving mixed quasi-solid solution/macroscopic two-phase transformations over a wide range of Li concentrations. Finally, this work highlights the unique capability of combining in situ core-level spectroscopy and first-principles calculations for probing Li-ion intercalation in zero-strain electrodes, which is crucial to designing high-performance electrode materials for long-life batteries.

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

Impact of hydrologic boundaries on microbial planktonic and biofilm communities in shallow terrestrial subsurface environments

Subsurface environments contain a large proportion of planetary microbial biomass and harbor diverse communities responsible for mediating biogeochemical cycles important to groundwater used by human society for consumption, irrigation, agriculture and industry. Within the saturated zone, capillary fringe and vadose zones, microorganisms can reside in two distinct phases (planktonic or biofilm), and significant differences in community composition, structure and activity between free-living and attached communities are commonly accepted. However, largely due to sampling constraints and the challenges of working with solid substrata, the contribution of each phase to subsurface processes is largely unresolved. Here, we synthesize current information on the diversity and activity of shallow freshwater subsurface habitats, discuss the challenges associated with sampling planktonic and biofilm communities across spatial, temporal and geological gradients, and discuss how biofilms may be constrained within shallow terrestrial subsurface aquifers. We suggest that merging traditional activity measurements and sequencing/-omics technologies with hydrological parameters important to sediment biofilm assembly and stability will help delineate key system parameters. Ultimately, integration will enhance our understanding of shallow subsurface ecophysiology in terms of bulk-flow through porous media and distinguish the respective activities of sessile microbial communities from more transient planktonic communities to ecosystem service and maintenance.

54 ENVIRONMENTAL SCIENCES↗