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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 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Microbeam analysis of four chondritic interplanetary dust particles for major elements, carbon and oxygen

Chemical compositions determined using electron excited X-rays are reported for four interplanetary dust particles collected in the stratosphere. These analyses include measurements of carbon and oxygen abundances which are important elements in these primitive materials. Spot analyses show very heterogeneous compositions on a micrometer scale although average composition approaches that of C1 carbonaceous chondrites. While the spot analyses show intermediate compositions between cometary dust and carbonaceous chondrites, the heterogeneity more closely resembles that of comet Halley dust particles.

Blanford, G. E.↗
NASA NTRS1991

Chemical studies of H chondrites. III - Regolith evolution of the Fayetteville chondrite parent

Radiochemical neutron concentration analysis was used to determine Ag, Au, Bi, Cd, Co, Cs, Ga, In, Rb, Sb, Se, Te, Tl, and Zn contents in consortium samples of solar gas and track-rich dark matrix. Data obtained confirmed that the matrix is chemically homogeneous. Most dark clasts had similar mean trace element concentrations as the matrix but were compositionally much more heterogeneous. It is concluded that material incorporated with soil and compacted to form the dark portion of Fayetteville included soil-melt, the odd C2M fragment, and dark and light clasts which escaped comminution.

Xiao, Xiaoyue↗
NASA NTRS1992

The Apollo 17 region: A compositional overview

Apollo 17 is located at a mare/highland boundary where the surface shows significant compositional heterogeneities. The composition of surface materials is estimated by analyzing their spectral/chemical correlations. Based on this spectral/chemical analysis, the chemical and normative mineralogical composition of two highland units and three mare units has been estimated.

Jaumann, R.↗
NASA NTRS1991

Styles of zoning in central Andean ignimbrites - Insights into magma chamber processes

Data are presented showing that calc-alkaline high-K ignimbrites from the Altiplano-Puna Volcanic Complex of the Central Volcanic Zone of the Andes, showing a variety of compositional zonations. The characteristics of the juvenile material from the zoned and heterogenous ignimbrites suggest that crystallization of the observed phenocrysts occurred in prezoned magma chambers consisting of two or more layers. It is suggested that the width/height ratio of a magma chamber plays a critical role in the control of the style of zonation that may develop in a closed magma chamber.

De Silva, S. L.↗
NASA NTRS1992

Shoot growth in aseptically cultivated daylily and haplopappus plantlets after a 5-day spaceflight

Plantlets of daylily (Hemerocallis cv. Autumn Blaze) regenerated from cell suspensions, and 4 clonal populations of Haplopappus gracilis were aseptically cultivated aboard the Shuttle "Discovery" during a 5-day mission within NASA's Plant Growth Unit (PGU) apparatus. Daylily was selected as a representative herbaceous perennial monocotyledon and the haplopappus clones represented an annual dicotyledon. The latter included 4 strains with different physiological and morphological characteristics: two aseptic seedling clones (each generated from a single seedling) and two tissue culture-derived lines. Mean daily growth rates for the primary shoots of all plantlets averaged 4.13 mm day-1 (SD = 2.20) for the flight experiment and 4.68 mm day-1 (SD = 2.59) for the ground control. Comparable growth rates calculated by summing both the primary and secondary shoots for all plantlets were 5.94 mm day-1 (SD = 2.89) for the flight experiment and 6.38 mm day-1 (SD = 3.71) for the control. Statistically significant differences existed between: (1) flight vs control primary shoot growth (the controls growing more than plantlets subjected to spaceflight conditions), (2) the different populations (the daylily gaining more shoot material than any of the haplopappus populations and the haplopappus seedling clones outperforming the tissue culture-derived haplopappus lines), and (3) the individual Plant Growth Chambers contained within the PGU. The data suggest that some spaceflight-associated factor(s) increased the tendency for primary shoot apices to degrade or senesce, resulting in the release of apical dominance and permitting the emergence of axillary branches, which subsequently partially compensated for the reduced primary axis growth. In addition to spaceflight-associated factors, the physiologically diverse nature of the experimental material as well as environmental heterogeneities within the culture apparatus contributed to the variation in growth results. The findings could explain some discrepancies reported from various plant culture experiments conducted in space.

short duration↗
DOE OSTI2024

Data Acquisition System Selection and Calibration of Resistive Moisture Content Measurements for Large-Scale Field Studies in Cold Climate Residential Building Envelope Performance

The residential building stock built before the energy codes were enforced has several significant inefficiency problems in terms of insulation and air leakage. To decrease these inefficiencies, building retrofits are necessary. However, if the envelope is not appropriately designed, excessive accumulation of moisture content and thus mold formation and decay inside the envelope layers can be a vital problem. This risk becomes higher, especially in extreme climate conditions such as cold winters and hot and humid summers as in some northern regions of the U.S. Field studies are essential to test the long-term hygrothermal performance of building envelopes. Although in-situ temperature, RH, and heat flux measurements are straightforward, moisture content measurements are cumbersome. Mainly, because of the heterogeneous nature of the wood materials, deviations and nonuniformities within the materials are unavoidable. Resistance measurements are one of the oldest methods used to measure the moisture content of wood and other building materials. In large-scale studies, it is commonly preferred to use multi-purpose data acquisition systems (DAQ) and custom-made or prefabricated moisture pins to measure the electrical resistance (and thus moisture content) of critical building materials. These multi-purpose DAQ systems generally provide lower costs and offer more flexibility. However, these systems require calibration and fine-tuning to achieve accurate moisture content measurements. A large-scale, two-year-long field study was conducted in northern Minnesota to monitor the hygrothermal performance of residential retrofit wall systems in cold climates. Two base case walls and sixteen different wall treatments were tested. Moisture contents were measured at various layers in each wall treatment using 85 sets of moisture pins. This paper focuses on the overall approach, fabrication, and calibration methodology for the combination of custom-made moisture pins and a multi-purpose DAQ. The aim is to directly use the low-excitation multi-purpose DAQ without any extra voltage regulator. A half-bridge circuit is used to measure wood resistance with 4V excitation voltage and 100 kΩ and 500 kΩ reference resistors. The system is calibrated for four different materials: Douglas fir, lodgepole pine, western red cedar, and oriented strand board (OSB). Calibration experiments were done under controlled conditions in 50% and 65% RH test chambers. Resistance-based moisture content calibration curves are obtained for each species. Results show that higher reference resistors provided better calibration curves for lower excitation voltages.

Desjarlais, Andre Omer↗
DOE OSTI2024

Supported Organochromium Ethylene Oligomerization Enabled by Surface Lithiation

Here, in this work, supported organochromium ethylene polymerization catalysts have been tuned to mediate ethylene oligomerization via surface lithiation, which provides a generalizable protocol to control stereoelectronics and redox states of surface organometallic active sites. The homoleptic chromium(IV) alkyl complex Cr(CH 2 SiMe 3 ) 4 was grafted on high-surface-area anatase titania (TiO 2 ) nanoparticles as well as on silica to produce Cr/TiO 2 and Cr/SiO 2 , respectively. Treatment of these materials with excess n-butyllithium led to the reduced chromium complexes Cr/Li x TiO 2 and Cr/Li/SiO 2 , each of which still retains one hydrocarbyl ligand on chromium. A set of heterogeneous complexes were studied by electron paramagnetic resonance and X-ray absorption spectroscopy, which indicate a reduction in the oxidation state of the major chromium species to Cr II upon lithiation. Cr/Li x TiO 2 converts ethylene to hexenes with a high selectivity (>80%), which was persistent over 10 days at 80 °C, achieving >950 turnovers. The exclusive formation of C 4 and C 6 olefins, preferring the trimerization product, without a statistical (Flory–Schulz) distribution is characteristic of the oxidative cyclization oligomerization mechanism rather than the traditional Cossee–Arlman mechanism, whereas Cr/Li/SiO 2 produced a mixture of trimerization and polymerization products, suggesting site heterogeneity in the silica-based material. On the other hand, the unreduced chromium(IV) materials as well as low lithium-containing Cr/Li x TiO 2 (x < 0.16) exclusively produced ultrahigh molecular weight polyethylene, determined by differential scanning calorimetry and gel permeation chromatography analysis, likely formed via a linear-insertion mechanism, with a crossover from the polymerization to oligomerization regime observed at ~16% Li intercalation.

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

Diffusion-limited hydrolysis in polymeric materials

Polymer degradation under aggressive environmental stressors often develops heterogeneities due to diffusion-limited reaction phenomena. This is well established for diffusion-limited oxidation (DLO), which is known to occur for most polymeric materials at elevated temperatures but has been less summarized for the conditions of diffusion-limited hydrolysis (DLH). Here, an overview of hydrolysis for several materials and a computational model, analogous to the underlying equations for DLO, able to define this diffusion-reaction system is presented. A systematic study of the influence of various parameters, such as water diffusivity, reaction rate and order, and a more in-depth focus on residual isocyanate hydrolysis in a polymeric methylene diphenyl diisocyanate (pMDI) based polyurethane (PU) foam is given. For this system, we present experimental data for model ‘input’ parameters and discuss predictions for different conditions. We conceptually compare the behavior of diffusion-limited oxidation to that of diffusion-limited hydrolysis (DLH). With the mathematical framework and key material properties presented herein, any DLH phenomena following Fickian diffusion behavior can be understood, modeled, and predicted.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Chemical redox of lithium-ion solid electroactive material in a packed bed flow reactor

Chemical redox reactions between solid electroactive materials and dissolved electroactive compounds are a necessary component of emerging technologies relevant to renewable energy including high energy density flow batteries and battery material recycling. In this work, an initial investigation of heterogeneous chemical redox for a packed bed reactor configuration between solid electroactive material and dissolved redox shuttles will be described. Experimental conditions including the height of the packed bed, the redox shuttle solution concentration, solution flow rate, and operating temperature were varied and their impact on the molar conversion of the solid electroactive material in the packed bed was quantified using electroanalytical techniques on the reactor effluent. The progression of the reaction and its dependence on the different variables explored will be discussed in the context of the limiting processes for porous packed aggregates of the solid electroactive material undergoing chemical oxidation.

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

Regularized machine learning on molecular graph model explains systematic error in DFT enthalpies

Abstract A major goal of materials research is the discovery of novel and efficient heterogeneous catalysts for various chemical processes. In such studies, the candidate catalyst material is modeled using tens to thousands of chemical species and elementary reactions. Density Functional Theory (DFT) is widely used to calculate the thermochemistry of these species which might be surface species or gas-phase molecules. The use of an approximate exchange correlation functional in the DFT framework introduces an important source of error in such models. This is especially true in the calculation of gas phase molecules whose thermochemistry is calculated using the same planewave basis set as the rest of the surface mechanism. Unfortunately, the nature and magnitude of these errors is unknown for most practical molecules. Here, we investigate the error in the enthalpy of formation for 1676 gaseous species using two different DFT levels of theory and the ‘ground truth values’ obtained from the NIST database. We featurize molecules using graph theory. We use a regularized algorithm to discover a sparse model of the error and identify important molecular fragments that drive this error. The model is robust to rigorous statistical tests and is used to correct DFT thermochemistry, achieving more than an order of magnitude improvement.

36 MATERIALS SCIENCE↗
NASA NTRS2001

Experiments Developed to Study Microgravity Smoldering Combustion

The overall objective of the Microgravity Smoldering Combustion (MSC) research program is to understand and predict smoldering combustion under normal and microgravity (near-zero-gravity) conditions to help prevent and control smolder-originated fires, in both environments. Smoldering is defined as a nonflaming, self-sustaining, propagating, exothermic surface reaction. If a material is sufficiently permeable, smoldering is not confined to its outer surface, but can propagate as a reaction wave through the interior of the material. The MSC program will accomplish its goals by conducting smolder experiments on the ground and in a space-based laboratory, and developing theoretical models of the process. Space-based experiments are necessary because smoldering is a very slow process and, consequently, its study in a microgravity environment requires extended periods of time that can only be achieved in space. Smoldering can occur in a variety of processes ranging from the smolder of porous insulating materials to underground coal combustion. Many materials can sustain smoldering, including wood, cloth, foams, tobacco, other dry organic materials, and charcoal. The ignition, propagation, transition to flaming, and extinction of the smolder reaction are controlled by complex, thermochemical mechanisms that are not well understood. As with many forms of combustion, gravity affects the availability of the oxidizer and the transport of heat, and therefore, the rate of combustion. The smoldering combustion of porous materials has been studied both experimentally and theoretically, usually in the context of fire safety. Smoldering encompasses a number of fundamental processes, including heat and mass transfer in a porous media; endothermic pyrolysis of combustible material; ignition, propagation, and extinction of heterogeneous exothermic reactions at the solid-gas pore interface; and the onset of gas phase reactions (flaming) from existing surface reactions. Smoldering presents a serious fire risk because the combustion can propagate slowly in a material's interior and go undetected for long periods of time. It typically yields a substantially higher conversion of fuel to toxic compounds than does flaming (though more slowly), and may undergo a sudden transition to flaming.

Vergilii, Franklin↗
DOE OSTI2024

Scanning electrochemical probe microscopy investigation of two-dimensional materials

Research interests in two-dimensional (2D) materials have seen exponential growth owing to their unique and fascinating properties. The highly exposed lattice planes coupled with tunable electronic states of 2D materials have created manifold opportunities in the design of new platforms for energy conversion and sensing applications. Still, challenges in understanding the electrochemical (EC) characteristics of these materials arise from the complexity of both intrinsic and extrinsic heterogeneities that can obscure structure–activity correlations. Scanning EC probe microscopic investigations offer unique benefits in disclosing local EC reactivities at the nanoscale level that are otherwise inaccessible with macroscale methods. This review summarizes recent progress in applying techniques of scanning EC microscopy (SECM) and scanning EC cell microscopy (SECCM) to obtain distinctive insights into the fundamentals of 2D electrodes. We showcase the capabilities of EC microscopies in addressing the roles of defects, thickness, environments, strain, phase, stacking, and many other aspects in the heterogeneous electron transfer, ion transport, electrocatalysis, and photoelectrochemistry of representative 2D materials and their derivatives. Perspectives for the advantages, challenges, and future opportunities of scanning EC probe microscopy investigation of 2D structures are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Inverse methods for design of soft materials

Functional soft materials, comprising colloidal and molecular building blocks that self-organize into complex structures as a result of their tunable interactions, enable a wide array of technological applications. Inverse methods provide a systematic means for navigating their inherently high-dimensional design spaces to create materials with targeted properties. Furthermore, while multiple physically motivated inverse strategies have been successfully implemented in silico, their translation to guiding experimental materials discovery has thus far been limited to a handful of proof-of-concept studies. In this perspective, we discuss recent advances in inverse methods for design of soft materials that address two challenges: (1) methodological limitations that prevent such approaches from satisfying design constraints and (2) computational challenges that limit the size and complexity of systems that can be addressed. Strategies that leverage machine learning have proven particularly effective, including methods to discover order parameters that characterize complex structural motifs and schemes to efficiently compute macroscopic properties from the underlying structure. We also highlight promising opportunities to improve the experimental realizability of materials designed computationally, including discovery of materials with functionality at multiple thermodynamic states, design of externally directed assembly protocols that are simple to implement in experiments, and strategies to improve the accuracy and computational efficiency of experimentally relevant models.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Direct-bonded diamond membranes for heterogeneous quantum and electronic technologies

Diamond has superlative material properties for a broad range of quantum and electronic technologies. However, heteroepitaxial growth of single crystal diamond remains limited, impeding integration and evolution of diamond-based technologies. Here, we directly bond single-crystal diamond membranes to a wide variety of materials including silicon, fused silica, sapphire, thermal oxide, and lithium niobate. Our bonding process combines customized membrane synthesis, transfer, and dry surface functionalization, allowing for minimal contamination while providing pathways for near unity yield and scalability. We generate bonded crystalline membranes with thickness as low as 10 nm, sub-nm interfacial regions, and nanometer-scale thickness variability over 200 by 200 μm 2 areas. We measure spin coherence times T 2 for nitrogen vacancy centers in 150 nm-thick bonded membranes of up to 623 ± 21 μs, suitable for advanced quantum applications. We demonstrate multiple methods for integrating high quality factor nanophotonic cavities with the diamond heterostructures, highlighting the platform versatility in quantum photonic applications. Furthermore, we show that our ultra-thin diamond membranes are compatible with total internal reflection fluorescence (TIRF) microscopy, which enables interfacing coherent diamond quantum sensors with living cells while rejecting unwanted background luminescence. The processes demonstrated herein provide a full toolkit to synthesize heterogeneous diamond-based hybrid systems for quantum and electronic technologies.

color center↗
DOE OSTI2024

Influence of zwitterionic amphiphilic copolymers on heterogeneous gypsum formation: A promising approach for scaling resistance

Here, this study aims to investigate the influence of zwitterionic amphiphilic copolymers (ZACs) in the nucleation and growth of heterogeneous CaSO4 at the zwitterion-water interface, which is crucial for the prevention of mineral scaling and consequent downtime or suboptimal performance in industries like membrane desalination, heat exchangers, and pipeline transportation. In situ grazing incidence small angle X-ray Scattering (GISAXS), and quartz crystal microbalance with dissipation (QCM-D) techniques were used to analyze the evolution of CaSO 4 particles on two new ZAC coatings: poly-(trifluoroethyl methacrylate-random-sulfobetaine methacrylate) (PTFEMA-r-SBMA, or PT:SBMA) and poly(trifluoroethyl methacrylate-random-2-methacryloyloxyethyl phosphorylcholine) (PTFEMA-r-MPC, or PT:MPC). The results showed that PT:MPC coatings promoted nucleation but inhibited crystal growth, resulting in slower overall reaction kinetics on PT:MPC coatings compared to PT:SBMA coatings. Interfacial interactions involving the substrates, sulfate minerals, and ions were examined, revealing that calcium ion adsorption, primarily governed by electrostatic attraction, played a crucial role in the nucleation and growth processes on both ZAC coatings. The crystal characterization revealed a phase transition from bassanite to gypsum on both ZAC coatings, suggesting that these zwitterionic materials can influence the mineral phase of heterogeneously formed CaSO 4 crystals. These findings enhance our understanding of the fundamental mechanisms underlying heterogeneous CaSO 4 scaling in the presence of zwitterionic materials.

42 ENGINEERING↗
DOE OSTI2023

A Graph Dynamical neural network approach for decoding dynamical states in ferroelectrics.

Ferroelectric materials such as BaTiO 3 show tremendous potential for emerging advances in memory devices, particular neuromorphic type devices. High density of memory can be obtained by stabilising polar domain walls at the nanoscale, regions of discontinuity between the well-defined polarization order parameter, but little is known about what controls their structure and dynamics in real nanoscale materials. Indeed, chiral polar domain walls have been observed in heterogeneous ferroelectrics, such as oxygen-deficient BaTiO 3 , but very little is known about how such polar-domains walls interact with defects. Indeed, a critical understanding of how dynamics of domain-walls depend on point-defects is crucial to create engineered ferroelectric memory devices. For this work, we perform large-scale simulations of nansocale domain-wall dynamics in pristine and defective BaTiO 3 using reactive force-field developed by us earlier (Phys. Chem. Chem. Phys., 2019, 21, 18240–18249), and capture their dynamical dependence on point defects using a graph dynamical neural-network approach, which we adapted to interrogate solids with well-defined order-parameters, and implemented using Pytorch based libraries. Our machine learning (ML) approach goes beyond the traditional post-processing methods to capture both spatial and temporal heterogeneities of large-scale molecular dynamics simulations of complex defective ferroelectric oxide materials. We crucially find that isolated oxygen vacancies introduce very localized spatial regions (~1–2 unit-cell in length) that show slow dipole relaxation due to formation of defect-dipoles, and that these defect-dipoles in turn slow the intrinsic dynamics of domain walls. Further, the roughness of domain walls, also influenced by vacancies, introduce dynamic heterogeneity along the domain-wall. As such we find a novel mechanism by which quenched disorder due to defects introduce dynamic heterogeneity thereby influencing response to external fields (particularly time varying fields) in a ferroelectric. Our study also emphasizes the need for creating digital twins of dynamical quantities to achieve autonomous in operando control of nanoscale switching.

42 ENGINEERING↗
DOE OSTI2021

Precise Identification and Characterization of Catalytically Active Sites on the Surface of γ‐Alumina**

Abstract γ‐alumina is one of the oldest and most important commercial catalytic materials with high surface area and stability. These attributes enabled its use as the first commercial large‐scale heterogeneous catalyst for ethanol dehydration. Despite progress in materials characterization the nature of the specific sites on the surface of γ‐alumina that are responsible for its unique catalytic properties has remained obscure and controversial. By using combined infrared spectroscopy, electron microscopy and solid‐state nuclear magnetic resonance measurements we identify the octahedral, amphoteric (O) 5 Al(VI)‐OH sites on the (100) segments of massively restructured (110) facets on typical rhombus‐platelet γ‐alumina as well as the (100) segments of irrational surfaces (invariably always present in all γ‐alumina samples) responsible for its unique catalytic activity. Such (O) 5 Al(VI)‐OH sites are also present on the macroscopically defined (100) facets of γ‐alumina with elongated/rod‐like geometry. The mechanism by which these sites lose ‐OH groups upon thermal dehydroxylation resulting in coordinatively unsaturated penta‐coordinate Al +3 O 5 sites is clarified. These coordinatively unsaturated penta‐coordinate Al sites produce well‐defined thermally stable Al‐carbonyl complexes. Our findings contribute to the understanding of the nature of coordinatively unsaturated Al sites on the surface of γ‐alumina and their role as catalytically active sites.

Khivantsev, Konstantin↗
DOE OSTI2023

High reactivity of mesoporous CeO 2 to dissociate chemical warfare agent sarin

We perform spectroscopic surface characterization on mesoporous ceria (CeO 2 ) under exposure of sarin gas, also known as GB. We find mesoporous CeO 2 displays extraordinary reactivity towards GB dissociation under high vacuum. The spectroscopic results combined with density functional theory (DFT) calculations suggest that the cleavage of the P–F and P–OR bonds are both possible pathways for GB to dissociate on the CeO 2 surfaces. The modeling reveals differences in dissociation pathways of GB on the crystallographic (111)- and (110)-surfaces of ceria. Here we also report some dissociation of GB on mesoporous CeO 2 under ambient conditions. The finding that mesoporous CeO 2 can degrade GB under mild conditions is encouraging and implies the strong potential of ceria-based materials to be applied in combating chemical warfare agents related to the GB series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗