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At least 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Electrochemical Sodiation Mechanism in Magnetite Nanoparticle-Based Anodes: Understanding of Nanoionics-Based Sodium Ion Storage Behavior of Fe 3 O 4

We report electrochemical ion storage behaviors of Fe 3 O 4 nanoparticles, as a representative transition metal oxide for an environmentally benign and low-cost anode for a sodium-ion battery, are thoroughly investigated through a combination of electrochemical analysis and diagnostics of Fe 3 O 4 electrode cells, X-ray-based and spectroscopic analysis of material structure evolution as functions of depth of discharge (DoD) and state of charge (SoC), and first principle modeling. The gravimetric capacity is found to be 50 mA h/g for bulk Fe 3 O 4 (50 nm average crystallite size) and 100 mA h/g--about a tenth of the theoretical prediction for complete conversion--for Fe 3 O 4 nanoparticles (8.7 nm average particle size), respectively. A fundamental and mechanistic study of material evolution as functions of DoD and SoC shows that Fe 3 O 4 does not allow electrochemical incorporation of Na + ions into the empty cation positions of the inverse spinel structure, leading to our assertion that electrochemical intercalation of Na + ions to conversion of the Fe 3 O 4 anode in sodium-ion batteries is nonviable. A density functional theory investigation points to the impracticality of the intercalation of Na + ions into Fe 3 O 4 and further validates our experimental findings. We propose several possible mechanisms corresponding to the observed low capacity, including formation of solid electrolyte interphases with unfavorable properties and adsorption of Na + ions onto surfaces of nanoparticles and/or at heterointerfaces in Fe 3 O 4 composite electrodes in a NaPF 6 -based electrolyte system.

25 ENERGY STORAGE↗
NASA NTRS1999

Enhanced Boiling on Micro-Configured Composite Surfaces Under Microgravity Conditions

In order to accommodate the growing thermal management needs of future space platforms, several two-phase active thermal control systems (ATCSs) have evolved and were included in the designs of space stations. Compared to the pumped single-phase liquid loops used in the conventional Space Transportation System and Spacelab, ATCSs offer significant benefits that may be realized by adopting a two-phase fluid-loop system. Alternately, dynamic power systems (DPSs), based on the Rankine cycle, seem inevitably to be required to supply the electrical power requirements of expanding space activities. Boiling heat transfer is one of the key technologies for both ATCSs and DPSs. Nucleate boiling near critical heat flux (CHF) can transport very large thermal loads with much smaller device size and much lower pumping power. However, boiling performance deteriorates in a reduced gravity environment and operation in the CHF regime is precarious because any slight overload will cause the heat transfer to suddenly move to the film boiling regime, which in turn, will result in burnout of the heat transfer surfaces. New materials, such as micro-configured metal-graphite composites, can provide a solution for boiling enhancement. It has been shown experimentally that this type of material manifests outstanding boiling heat transfer performance and their CHF is also extended to higher values. Due to the high thermal conductivity of graphite fiber (up to 1,200 W/m-K in the fiber direction), the composite surfaces are non-isothermal during the boiling process. The composite surfaces are believed to have a much wider safe operating region (a more uniform boiling curve in the CHF regime) because non-isothermal surfaces have been found to be less sensitive to variations of wall superheat in the CHF regime. The thermocapillary forces formed by the temperature difference between the fiber tips and the metal matrix play a more important role than the buoyancy in the bubble detachment, for the bubble detachment manifests itself by a necking process which should not be weakened by reduced gravity. In addition, the composite surfaces introduce no extra pressure drop, no fouling and do not impose significant primary or maintenance costs. All of these suggest that this type of composite is an ideal material for the challenge of accounting for both reliability and economy of the relevant components applied in the ATCSs, the DPSs and other devices in future space missions. The aim of the proposed work is to experimentally investigate high nucleate pool boiling performance on a micro-configured metal-graphite composite surface and to determine the mechanisms of the nucleate boiling heat transfer both experimentally and theoretically. Freon-113 and water will be used as the test liquids to investigate wettability effects on boiling characteristics. The Cu-Gr and Al-Gr composites with various volume fractions of graphite fibers will be tested to obtain the heat transfer characteristic data in the nucleate boiling region and in the CHF regime. In the experiments, the bubble emission and coalescence processes will be recorded by a video camera with a magnifying borescope probe immersed in the working fluid. The temperature profile in the thermal boundary layer on the composite surfaces will be measured by a group of micro thermocouples consisting of four ultra fine micro thermocouples. This instrument was developed and successfully used to measure the temperature profile of evaporating liquid thin layers by the proposers in a study performed at the NASA/Lewis Research Center. A two tier model to explain the nucleate boiling process and the performance enhancement on the composite surfaces has been suggested by the authors. According to the model, the thicknesses of the microlayer and the macrolayer underneath the bubbles and mushrooms, can be estimated by the geometry of the composite surface. The experimental results will be compared to the predictions from the model, and in turn, to revise and improve it.

Zhang, Nengli↗
NASA NTRS1993

Hot corrosion of the B2 nickel aluminides

The hot corrosion behavior of the B2 nickel aluminides was studied to determine the inherent hot corrosion resistance of the beta nickel aluminides and to develop a mechanism for the hot corrosion of the beta nickel aluminides. The effects of the prior processing of the material, small additions of zirconium, stoichiometry of the materials, and preoxidation of the samples were also examined. Additions of 2, 5, and 15 w/o chromium were used to determine the effect of chromium on the hot corrosion of the beta nickel aluminides and the minimum amount of chromium necessary for good hot corrosion resistance. The results indicate that the beta nickel aluminides have inferior inherent hot corrosion resistance despite their excellent oxidation resistance. Prior processing and zirconium additions had no discernible effect on the hot corrosion resistance of the alloys. Preoxidation extended the incubation period of the alloys only a few hours and was not considered to be an effective means of stopping hot corrosion. Stoichiometry was a major factor in determining the hot corrosion resistance of the alloys with the higher aluminum alloys having a definitely superior hot corrosion resistance. The addition of chromium to the alloys stopped the hot corrosion attack in the alloys tested. From a variety of experimental results, a complex hot corrosion mechanism was proposed. During the early stages of the hot corrosion of these alloys the corrosion is dominated by a local sulphidation/oxidation form of attack. During the intermediate stages of the hot corrosion, the aluminum depletion at the surface leads to a change in the oxidation mechanism from a protective external alumina layer to a mixed nickel-aluminum spinel and nickel oxide that can occur both externally and internally. The material undergoes extensive cracking during the later portions of the hot corrosion.

Ellis, David L.↗
NASA NTRS1990

An experimental study of compression failure of fibrous laminated composites in the presence of stress gradients

Mechanisms of failure in laminates in the presence of a stress raiser were experimentally studied. The damage initiation and propagation throughout the entire load history were examined via real-time holographic interferometry and photomicrography of the hole surface. Multilayered composite flat plates made of T300/BP907 and IM7/8551-7 were tested. It is shown that the failure is initiated as a localized instability in the 0-deg plies at the hole surface approximately at right angles to the loading direction. A series of events is described which culminates in the complete loss of flexural stiffness of each of the delaminated portions, leading to catastrophic failure of the plate.

Waas, A. M.↗
NASA NTRS1983

Polyfunctional epoxies - Different molecular weights of brominated polymeric additives as flame retardants in graphite composites

The imparting of flame retardancy to graphite-reinforced composites without incurring mechanical property deterioration is investigated for the case of an experimental, trifunctional epoxy resin incorporating brominated polymeric additives (BPAs) of the diglycidyl type. Such mechanical properties as flexural strength and modulus, and short beam shear strength, were measured in dry and in hot/wet conditions, and the glass transition temperature, flammability, and water absorption were measured and compared with nonbromilated systems. Another comparison was made with a tetrafunctional epoxy system. The results obtained are explained in terms of differences in the polymeric backbone length of the bromine carrier polymer. BPAs are found to be a reliable bromine source for fire inhibition in carbon-reinforced composites without compromise of mechanical properties.

Nir, Z.↗
NASA NTRS2008

Application of an Elongated Kelvin Model to Space Shuttle Foams

Spray-on foam insulation is applied to the exterior of the Space Shuttle s External Tank to limit propellant boil-off and to prevent ice formation. The Space Shuttle foams are rigid closed-cell polyurethane foams. The two foams used most extensively on the Space Shuttle External Tank are BX-265 and NCFI24-124. Since the catastrophic loss of the Space Shuttle Columbia, numerous studies have been conducted to mitigate the likelihood and the severity of foam shedding during the Shuttle s ascent to space. Due to the foaming and rising process, the foam microstructures are elongated in the rise direction. As a result, these two foams exhibit a non-isotropic mechanical behavior. In this paper, a detailed microstructural characterization of the two foams is presented. The key features of the foam cells are summarized and the average cell dimensions in the two foams are compared. Experimental studies to measure the room temperature mechanical response of the two foams in the two principal material directions (parallel to the rise and perpendicular to the rise) are also reported. The measured elastic modulus, proportional limit stress, ultimate tensile stress and the Poisson s ratios for the two foams are compared. The generalized elongated Kelvin foam model previously developed by the authors is reviewed and the equations which result from this model are presented. The resulting equations show that the ratio of the elastic modulus in the rise direction to that in the perpendicular-to-rise direction as well as the ratio of the strengths in the two material directions is only a function of the microstructural dimensions. Using the measured microstructural dimensions and the measured stiffness ratio, the foam tensile strength ratio and Poisson s ratios are predicted for both foams. The predicted tensile strength ratio is in close agreement with the measured strength ratios for both BX-265 and NCFI24-124. The comparison between the predicted Poisson s ratios and the measured values is not as favorable.

Sullivan, Roy M.↗
DOE OSTI2021

Solution-Phase Growth of Cu Nanowires with Aspect Ratios Greater Than 1000: Multiscale Theory

Penta-twinned metal nanowires are finding widespread application in existing and emerging technologies. However, little is known about their growth mechanisms. Here, we probe the origins of chloride- and alkylamine-mediated, solution-phase growth of penta-twinned Cu nanowires from first principles using multi-scale theory. Using quantum density functional theory (DFT) calculations, we characterize the binding and surface diffusion of Cu atoms on chlorine-covered Cu(100) and Cu(111) surfaces. We find stronger binding and slower diffusion of Cu atoms on chlorinated Cu(111) than on chlorinated Cu(100) – a reversal of the trend for bare Cu surfaces. We also probe inter-facet diffusion and find this proceeds faster from Cu(100) to Cu(111) than the reverse. Using the DFT rates for hopping between individual sites at Ångstrom scales, we calculate coarse-grained, inter-facet rates for nanowires of various lengths – up to hundreds of μm – and diameters in the 10-nm range. We predict nanowires with aspect ratios around 100 based on surface diffusion, alone. We also account for the influence of a self-assembled alkylamine layer that covers most of the {100} facets, but is absent or thin and disordered on the {111} facets and in an “end zone” near the {100}-{111} boundary. With an end zone, we predict a wide range of nanowire aspect ratios in the experimental ranges. Our work reveals the mechanisms by which a halide – chloride – promotes the growth of high-aspect-ratio nanowires.

36 MATERIALS SCIENCE↗
NASA NTRS2015

Effects of Atomic-Scale Structure on the Fracture Properties of Amorphous Carbon - Carbon Nanotube Composites

The fracture of carbon materials is a complex process, the understanding of which is critical to the development of next generation high performance materials. While quantum mechanical (QM) calculations are the most accurate way to model fracture, the fracture behavior of many carbon-based composite engineering materials, such as carbon nanotube (CNT) composites, is a multi-scale process that occurs on time and length scales beyond the practical limitations of QM methods. The Reax Force Field (ReaxFF) is capable of predicting mechanical properties involving strong deformation, bond breaking and bond formation in the classical molecular dynamics framework. This has been achieved by adding to the potential energy function a bond-order term that varies continuously with distance. The use of an empirical bond order potential, such as ReaxFF, enables the simulation of failure in molecular systems that are several orders of magnitude larger than would be possible in QM techniques. In this work, the fracture behavior of an amorphous carbon (AC) matrix reinforced with CNTs was modeled using molecular dynamics with the ReaxFF reactive forcefield. Care was taken to select the appropriate simulation parameters, which can be different from those required when using traditional fixed-bond force fields. The effect of CNT arrangement was investigated with three systems: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. For each arrangement, covalent bonds are added between the CNTs and AC, with crosslink fractions ranging from 0-25% of the interfacial CNT atoms. The SWNT and MWNT array systems represent ideal cases with evenly spaced CNTs; the SWNT bundle system represents a more realistic case because, in practice, van der Waals interactions lead to the agglomeration of CNTs into bundles. The simulation results will serve as guidance in setting experimental processing conditions to optimize the mechanical properties of CNT composites.

Jensen, Benjamin D.↗
NASA NTRS1997

The Effect of Gravity on the Combustion of Bulk Metals

In recent years, metal combustion studies at the University of Colorado have focused on the effects of gravity (g) on the ignition and burning behavior of bulk metals. The impetus behind this effort is the understanding of the ignition conditions and flammability properties of structural metals found in oxygen (O2) systems for space applications. Since spacecraft are subjected to higher-than-1g loads during launch and reentry and to a zero-gravity environment while in orbit, the study of ignition and combustion of bulk metals at different gravitational accelerations is of great practical concern. From the scientific standpoint, studies conducted under low gravity conditions provide simplified boundary conditions, since buoyancy is removed, and make possible the identification of fundamental ignition and combustion mechanisms. This investigation is intended to provide experimental verification of the influence of natural convection on the burning behavior of metals. In addition, the study offers the first findings of the influence of gravity on ignition of bulk metals and on the combustion mechanism and structure of metal-oxygen, vapor-phase diffusion flames in a buoyancy-free environment. Titanium (Ti) and magnesium (Mg) metals were chosen because of their importance as elements of structural materials and their simple chemical composition-pure metals instead of multicomponent alloys to simplify chemical and spectroscopic analyses. In addition, these elements present the two different combustion modes observed in metals: heterogeneous or surface burning (for Ti) and homogeneous or gas-phase reaction (for Mg). Finally, Mg, Ti, and their oxides exhibit a wide range of thermophysical and chemical properties. Metal surface temperature profiles, critical and ignition temperatures, propagation rates, burning times, and spectroscopic measurements are obtained under normal and reduced gravity. Visual evidence of all phenomena is provided by high-speed photography.

Branch, Melvyn C.↗
NASA NTRS2006

Autonomous Congestion Control in Delay-Tolerant Networks

Congestion control is an important feature that directly affects network performance. Network congestion may cause loss of data or long delays. Although this problem has been studied extensively in the Internet, the solutions for Internet congestion control do not apply readily to challenged network environments such as Delay Tolerant Networks (DTN) where end-to-end connectivity may not exist continuously and latency can be high. In DTN, end-to-end rate control is not feasible. This calls for congestion control mechanisms where the decisions can be made autonomously with local information only. We use an economic pricing model and propose a rule-based congestion control mechanism where each router can autonomously decide on whether to accept a bundle (data) based on local information such as available storage and the value and risk of accepting the bundle (derived from historical statistics). Preliminary experimental results show that this congestion control mechanism can protect routers from resource depletion without loss of data.

delay-tolerant networking↗
DOE OSTI2024

Computational modeling of coupled mechanical damage and electrochemistry in ternary oxide composite electrodes

Performance degradation of ternary layered oxide cathodes largely originates from their loss of structural integrity in cyclic usage. Mechanical damage, such as intergranular fracture of the active particles, is not only a mechanical cleavage process but also interferes with electrochemical kinetics such as infiltration of liquid electrolyte, surface corrosion of the constituent primary particles, and may eventually isolate the primary grains from the electron conducting network. Here, in this work, we develop a computational framework that integrates electrochemistry of a LiNi x Mn y Co 1−x−y O 2 (NMC) composite cathode with mechanical damage of the active particles. To fully examine the intricate chemomechanical behavior of the electrode, we evaluate the effects of the anisotropic material properties, the influence of mechanical potential on Li transport, and the concurrent intergranular fracture and electrolyte penetration along the grain boundaries upon multiple cycles. Electrolyte infiltration benefits capacity retention but aggravates further mechanical damage by corrosion. Structural failure mostly occurs in the first charging due to the anisotropic mechanical strain between the primary grains, while the resulting damage remains stable in the later few cycles. The results are consistent with experimental observations and the integration of electrochemistry and mechanical failure enables a step further understanding of the complex mechanism of battery degradation.

Battery degradation↗
DOE OSTI2026

Exploring the Photogenerated Charge Transfer Mechanism in Cu 2 O@MoS 2 Heterojunction Photocatalyst Using Transient Absorption Spectroscopy

Both heterojunction and core–shell photocatalysts have demonstrated promising performance in photocatalytic CO 2 conversions to fuels. However, fundamental knowledge of heterojunctions in core–shell structures is highly desired to facilitate the design of future photocatalysts. By combining advanced experimental characterizations and density functional theory (DFT) calculations, the role of the Cu 2 O@MoS 2 heterojunction in photocatalytic CO 2 conversions to fuels was investigated. We discovered that the charge dynamics and electron transfer properties of Cu2O@MoS 2 photocatalysts are altered by the heterojunction and Cu 2 O underlayer due to the electron transfer from Cu 2 O to MoS 2 and the change in CO 2 adsorption strength on the hybrid catalyst surface. Consequently, more electrons can travel to the surrounding liquid environment to be consumed by CO 2 reduction. This study provides experimental and theoretical investigations of the fundamental mechanisms of heterojunction core–shell photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Spatially Resolved Near Field Spectroscopy of Vibrational Polaritons at the Small N Limit

Vibrational polaritons, which have been primarily studied in Fabry–Pérot cavities with a large number of molecules (N ~ 10 6 –10 10 ) coupled to the resonator mode, exhibit various experimentally observed effects on chemical reactions. However, the exact mechanism is elusively understood from the theoretical side, as the large number of molecules involved in an experimental strong coupling condition cannot be represented completely in simulations. This discrepancy between theory and experiment arises from computational descriptions of polariton systems typically being limited to only a few molecules, thus failing to represent the experimental conditions adequately. To address this mismatch, we used surface phonon polariton (SPhP) resonators as an alternative platform for vibrational strong coupling. SPhPs exhibit strong electromagnetic confinement on the surface and thus allow for coupling to a small number of molecules. As a result, this platform can enhance nonlinearity and slow down relaxation to the dark modes. In this study, we fabricated a pillar-shaped quartz resonator and then coated it with a thin layer of cobalt phthalocyanine (CoPc). By employing scattering-type scanning near-field optical microscopy (s-SNOM), we spatially investigated the dependency of vibrational strong coupling on the spatially varying electromagnetic field strength and demonstrated strong coupling with 38,000 molecules only–reaching to the small N limit. Through s-SNOM analysis, we found that strong coupling was observed primarily on the edge of the quartz pillar and the apex of the s-SNOM tip, where the maximum field enhancement occurs. In contrast, a weak resonance signal and lack of coupling were observed closer to the center of the pillar. This work demonstrates the importance of spatially resolved polariton systems in nanophotonic platforms and lays a foundation to explore polariton chemistry and chemical dynamics at the small N limit–one step closer to reconcile with high-level quantum calculations.

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

Experimental investigation on the coolability of nuclear reactor debris beds using seawater

During the Fukushima nuclear reactor accident, seawater was injected into the reactor core to cool the decay heat from the heat generating porous debris bed. However, the impact of dissolved salts in water on the coolability of a debris bed is not well understood. This paper is one of the first works to investigate the cooling mechanisms for debris bed using seawater. An experimental system was built where the packed bed test section was volumetrically heated via a high frequency induction heater. The temperature along the axis of the test section was measured using a high resolution temperature sensor based on Optical Frequency Domain Reflectometry. Experimental results show that the dryout heat flux increases with an increase in concentration, with pure water having a dryout volumetric heat flux of 1.8 MW/m and salt water of concentration 7% having a dryout volumetric heat flux of 2.8 MW/m. However, this enhanced coolability using salt water is short term, as the crystallization fouling mechanism becomes significant over time and leads to gradual temperature excursion in the bed. The fouling mechanism eventually leads to a cross section of the debris bed to plug with the deposited salts, and this leads to a pressure build up in the lower regions of the debris bed.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
NASA NTRS1994

Influence of convection on microstructure

The primary motivation for this research was to determine the cause for space processing altering the microstructure of some eutectics, especially the MnBi-Bi eutectic. Four primary hypotheses were to be tested under this current grant: (1) A fibrous microstructure is much more sensitive to convection than a lamellar microstructure, which was assumed in our prior theoretical treatment. (2) An interface with one phase projecting out into the melt is much more sensitive to convection than a planar interface, which was assumed in our prior theoretical treatment. (3) The Soret effect is much more important in the absence of convection and has a sufficiently large influence on microstructure that its action can explain the flight results. (4) The microstructure is much more sensitive to convection when the composition of the bulk melt is off eutectic. These hypotheses were tested. It was concluded that none of these can explain the Grumman flight results. Experiments also were performed on the influence of current pulses on MnBi-Bi microstructure. A thorough review was made of all experimental results on the influence of convection on the fiber spacing in rod eutectics, including results from solidification in space or at high gravity, and use of mechanical stirring or a magnetic field. Contradictory results were noted. The predictions of models for convective influences were compared with the experimental results. Vigorous mechanical stirring appears to coarsen the microstructure by altering the concentration field in front of the freezing interface. Gentle convection is believed to alter the microstructure of a fibrous eutectic only when it causes a fluctuating freezing rate with a system for which the kinetics of fiber branching differs from that for fiber termination. These fluctuations may cause the microstructure to coarsen or to become finer, depending on the relative kinetics of these processes. The microstructure of lamellar eutectics is less sensitive to freezing rate fluctuations and to gentle convection.

Wilcox, William R.↗
DOE OSTI2021

A crystal plasticity model with an atomistically informed description of grain boundary sliding for improved predictions of deformation fields

Crystal plasticity (CP) is a powerful meso-scale technique for deformation modeling in polycrystalline materials. Crystal plasticity models typically do not include an explicit description of grain boundary (GB) sliding, which could lead to inaccurate predictions of strain distributions, especially in the vicinity of GBs. In the present study, a CP model is developed that includes GB sliding as an additional deformation mechanism and models the interaction between slip and GB sliding. Atomistic simulations are used to formulate the constitutive model for GB sliding and its interaction with incident slip. The deformation fields and structure of the GBs are obtained directly from experimental characterization and are faithfully reproduced as bicrystal systems for molecular dynamics simulations. The GBs are modeled as random-type (non-coincidence, asymmetrical) boundaries as observed from experimental data. The underlying atomistic-scale mechanism for pure sliding of random GBs was found to be analogous to fluid-flow. The interaction between incident slip and a sliding GB caused local increases in stress concentration, which further led to a momentary increase in the local sliding rate. The displacement profiles at the sliding GBs computed from the CP model with sliding accommodation are 38% more accurate than the baseline CP model as quantified by the mean squared error between the simulations and experiment. Here these results help improve the sophistication and accuracy of deformation modeling by including physics-based descriptions for GB sliding and its interaction with slip, eventually leading to more reliable predictions of micromechanical quantities.

36 MATERIALS SCIENCE↗
NASA NTRS1975

Physiological mechanisms of the effect of weightlessness on the body

Experimental data show that physiological reactions observed under weightlessness conditions are caused by: (1) The direct effect of weightlessness, as a consequence of decrease (""disappearance'') of the weight of body tissues and organs; and (2) the mediated effect of weightlessness, as a result of changes in the functional state of the central nervous system and the cooperative work of the analyzers. The human body adopts to weightless conditions under the prolonged effects of it. In this case, four periods can be distinguished: The first period, a transitional process lasting from 1 to 24 hours; second period, initial adaptation to conditions of weightlessness and readjustment of all functional systems of the body; the third period, adaptation to the unusual mechanical conditions of the external environment, lasting from 3 to 8 days and more; and the fourth period, the stage of possible imbalance of the functions and the systems of some astronauts, as a result of the prolonged effect of weightlessness.

Kasyan, I. I.↗