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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 55 records · Page 3

Suppressed incommensurate order in swedenborgite Ca 0.5 Y 0.5 BaCo 4 O 7

Swedenborgite Ca 0.5 Y 0.5 BaCo 4 O 7 (CYBCO) with geometrically frustrated kagome and triangular lattices exhibits a disordered ground state in spite of strong antiferromagnetic couplings between the Co spins. The character of the disordered state has been debated due to ambiguous Co states in the triangular layers. Here, we perform single-crystal diffuse neutron scattering experiments to fully characterize the short-range spin correlations in CYBCO. Through reverse Monte Carlo and self-consistent Gaussian approximation analyses, we confirm that the Co ions in both the kagome and triangular layers are magnetic, and the interlayer couplings, together with the lattice distortion, promote an incommensurate magnetic order that is suppressed possibly by exchange disorder. Our work clarifies the short-range spin correlations in CYBCO and establishes a general correspondence between unequal interactions and incommensurate spin correlations on the swedenborgite lattice.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Europium diffusion in IG-110 nuclear graphite

Europium diffusion in graphite has been recognized to be of interest in high-temperature gas reactor safety analysis, particularly as an indicator of strontium diffusion. However, no measurements of europium diffusion coefficients have been reported in the literature. In this work, the effective diffusion coefficient of europium was measured using a time-release method. Natural europium was loaded into pre-milled unirradiated IG-110 graphite spheres using a pressurized acid digestion vessel. The time-release experiments were performed in the temperature range 1823 K – 1973 K using a SiC diffusion cell connected to an inductively-coupled plasma mass spectrometer (ICP-MS) via a He gas line. Finally, the results of this work are: D Eu, IG-110 = (1.5 x 10 -3 m 2 /s) exp $(\frac{-2.87\mathrm{x}10^{5} J/mol}{RT})$ This effective diffusion coefficient can be used to aid in predictive modelling of europium transport in HTGRs.

36 MATERIALS SCIENCE↗

Computational Material Processing in Microgravity

Working with Professor David Matthiesen at Case Western Reserve University (CWRU) a computer model of the DPIMS (Diffusion Processes in Molten Semiconductors) space experiment was developed that is able to predict the thermal field, flow field and concentration profile within a molten germanium capillary under both ground-based and microgravity conditions as illustrated. These models are coupled with a novel nonlinear statistical methodology for estimating the diffusion coefficient from measured concentration values after a given time that yields a more accurate estimate than traditional methods. This code was integrated into a web-based application that has become a standard tool used by engineers in the Materials Science Department at CWRU.

Source record↗

Convective and morphological instability in vapor crystal growth

Theoretical and experimental work on the fluid dynamics of physical vapor transport is reported. It is shown that diffusion in viscous interaction with container walls leads to concentration gradients normal to the main transport direction. Consequently any convection threshold is removed. This coupling with convective instabilities makes the theoretical interpretation of earthbound (anisotropic) morphological stability studies on vapor-solid interfaces intractable. Hence low-gravity experiments are suggested that will allow for the establishment of morphological stability criteria under diffusion controlled conditions.

Rosenberger, F.↗

Large-Scale Molecular Dynamics Simulation of the Dehydration of a Suspension of Smectite Clay Nanoparticles

Fine-grained sediments and sedimentary rocks play important roles in a variety of modern energy technologies from petroleum geology to geological carbon sequestration and radioactive waste management. However, despite their utility and ubiquity, many of their properties remain poorly understood. In particular, the ability to predict the permeability and mechanics of these media remains a persistent fundamental challenge in the geosciences. In the present work, we show how large-scale classical molecular dynamics (MD) simulations can help interpret the properties of fine-grained sedimentary material. All-atom simulations containing 30 discrete clay particles are utilized to understand the evolution of a clay nanoparticle suspension during its progressive dehydration. Microstructural (pore size distribution, tortuosity, anisotropy), thermodynamic (enthalpy and free energy of hydration, anion exclusion), mechanical (total suction), and transport properties (diffusion coefficient tensors of water and sodium) are calculated and compared to the experiment. Overall, our results provide new insight into the coupled chemistry, mechanics, and transport properties of disordered nanoparticle assemblages and shed light upon the important role of water films in controlling these properties.

02 PETROLEUM↗

A novel directly coupled gradostat

The original bidirectional compound chemostat (gradostat) described by Lovitt and Wimpenny has been simplified by making a more compact apparatus in which chemical gradients are established by diffusion between adjacent culture chambers. The experimental model (diffusion coupled (DC) gradostat) consisted of five chambers whose contents could be agitated by turbines rotating in the horizontal plane on a common shaft. Two biological experiments were designed to reveal the value of the DC gradostat. A methylotroph (Methylophilus methylotrophus) grown in a methanol gradient showed expected changes in cell viability as a function of position in the five vessel array. Cells of two species of photosynthetic bacteria (Rhodobacter capsulata and Rhodopseudomonas marina/agilis) with different salt sensitivities could be mixed and subsequently separated by the DC gradostat operating with a NaCl gradient of 0-3% w/v.

NASA Discipline Exobiology↗

Investigation of desorption of hydrogen gas from polymer matrix using thermal desorption analysis and finite element modeling

Polymer materials are used widely as sealing materials and liners in hydrogen storage and transportation infrastructure. During operating conditions, polymers are exposed to high pressure hydrogen gas periodically. When in contact, the hydrogen gas diffuses through the polymer material with ease due to its smaller sized molecules compared to the polymer molecules. In the event of rapid decompression of outside hydrogen gas, the hydrogen molecules within the polymer diffuse out. This process is known as the desorption of polymer and can cause blisters or cracking causing permanent damage to the polymer. Here, we used a combined experimental and modeling approach to investigate the desorption of the hydrogen gas in the polymer. Thermal desorption analysis (TDA) experiments were performed on the polymer sample exposed to the high-pressure hydrogen gas to measure the diffusion coefficient and equilibrium hydrogen concentration. Experiments also provided the quantity of hydrogen within the polymer during the desorption process which followed Fick’s law. However, for higher pressurization values, some anomaly was observed in the quantity of hydrogen remaining in the polymer sample. A continuum mechanics based coupled diffusion–deformation-damage model was deployed to simulate the gas desorption process in the material using the finite element method to understand its effect on the material. It was found that the anomaly in TDA results were due to the blister formation on the polymer surface which resulted in longer hydrogen retention. Simulations also showed that blister formation can be affected by multiple parameters such as the addition of filler particles, and pre-existing cavity size.

36 MATERIALS SCIENCE↗

Pattern selection in a boundary-layer model of dendritic growth in the presence of impurities

Presently analyzed, in the context of a boundary-layer model, is the problem of pattern selection in dendritic growth in a situation where impurities are present in the undercooled liquid. It is found that the tip-velocity selection criterion that has been proposed recently for the geometrical model and the boundary-layer model of a pure substance can be extended, in a nontrivial way, to this more complex situation where two coupled diffusion fields (temperature and solute) determine the interface dynamics. This model predicts a sharp enhancement of tip velocity in good qualitative agreement with experiment. This agreement is consistent with the conjecture that a solvability condition can be used to determine the operating point of the dendrite in the full nonlocal problem.

Karma, A.↗

Buoyancy Effects upon Vapor Flame and Explosion Processes

The objective of this microgravity project is to develop an experimental and theoretical analyses critical to the understanding of the coupling of buoyancy and turbulence generation and its effect on fuel-air mixing, flame intensity and flame propagation in jet diffusion flames. The experiment is designed to examine certain effects of buoyancy acting on a diffusion flame in which the flame is directed either upward or downward. This change from negative to positive g is observed to significantly alter the flame shape although all other operating conditions are the same for both configurations. However, to perform this experiment a significant coaxial secondary air flow is needed in order to prevent flow reversal when the flame is inverted. The theoretical analysis that has been developed handles the secondary air flow and the extreme change in gravity vector direction. Thus the data will provide a measure of credibility of the analysis which will then be used to assist in the design of the actual zero-g experiment.

Edelman, R. B.↗

The internal reference source (IRS) for diffuse infrared background experiment (DIRBE)

A means is described for providing internal calibration for the detectors for DIRBE, which is the Diffuse Infrared Background Experiment (a part of the Cosmic Background Explorer). The internal reference source (IRS) that is used consists of four thermal graybody sources coupled to an integrating sphere. The relative insensitivity of the DIRBE bolometers and the linear temperature dependence of the Rayleigh-Jeans law made bolometer stimulation over five orders of magnitude difficult, so four different sources were used with emitting areas varying by a factor of 10 to the 8th. A low heat capacity design with the necessary stability appears to be thin nichrome films on a sapphire substrate. Voltage stability to 0.01 percent is required for those near infrared bands that required stimulation on the Wien portion of the blackbody curve.

Silverglate, P.↗

Selective One-Dimensional 13 C– 13 C Spin-Diffusion Solid-State Nuclear Magnetic Resonance Methods to Probe Spatial Arrangements in Biopolymers Including Plant Cell Walls, Peptides, and Spider Silk

Two-dimensional (2D) and 3D through-space 13 C– 13 C homonuclear spin-diffusion techniques are powerful solid-state nuclear magnetic resonance (NMR) tools for extracting structural information from 13 C-enriched biomolecules, but necessarily long acquisition times restrict their applications. In this work, we explore the broad utility and underutilized power of a chemical shift-selective one-dimensional (1D) version of a 2D 13 C– 13 C spin-diffusion solid-state NMR technique. The method, which is called 1D dipolar-assisted rotational resonance (DARR) difference, is applied to a variety of biomaterials including lignocellulosic plant cell walls, microcrystalline peptide fMLF, and black widow dragline spider silk. 1D 13 C– 13 C spin-diffusion methods described here apply in select cases in which the 1D 13 C solid-state NMR spectrum displays chemical shift-resolved moieties. Furthermore, this is analogous to the selective 1D nuclear Overhauser effect spectroscopy (NOESY) experiment utilized in liquid-state NMR as a faster (1D instead of 2D) and often less ambiguous (direct sampling of the time domain data, coupled with increased signal averaging) alternative to 2D NOESY. Selective 1D 13 C– 13 C spin-diffusion methods are more time-efficient than their 2D counterparts such as proton-driven spin diffusion (PDSD) and dipolar-assisted rotational resonance. The additional time gained enables measurements of 13 C– 13 C spin-diffusion buildup curves and extraction of spin-diffusion time constants TSD, yielding detailed structural information. Specifically, selective 1D DARR difference buildup curves applied to 13 C-enriched hybrid poplar woody stems confirm strong spatial interaction between lignin and acetylated xylan polymers within poplar plant secondary cell walls, and an interpolymer distance of ~0.45–0.5 nm was estimated. Additionally, Tyr/Gly long-range correlations were observed on isotopically enriched black widow spider dragline silks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling Interdiffusion Phenomena and the Role of Nanoscale Diffusion Barriers in the Copper–Gold System

Diffusion is one of the most fundamental concepts in materials science, playing a pivotal role in materials synthesis, forming, and degradation. Of particular importance is solid state interdiffusion of metals which defines the usable parameter space for material combinations in the form of alloys. This parameter space can be explored on the macroscopic scale by using diffusion couples. However, this method reaches its limit when going to low temperatures, small scales, and when testing ultrathin diffusion barriers. Therefore, this work transfers the principle of the diffusion couples to small scales by using core–shell nanowires and in situ heating. This allows us to delve into the interdiffusion dynamics of copper and gold, revealing the interplay between diffusion and the disorder–order phase transition. Our in situ TEM experiments in combination with chemical mapping reveal the interdiffusion coefficients of Cu and Au at low temperatures and highlight the impact of ordering processes on the diffusion behavior. The formation of ordered domains within the solid-solution is examined using high-resolution imaging and nanodiffraction including strain mapping. In addition, we examine the effectiveness of ultrathin Al 2 O 3 barrier layers to control interdiffusion of the diffusion couple. Our findings indicate that a 5 nm thick layer serves as an efficient diffusion barrier. Furthermore, this research provides valuable insights into the interdiffusion behavior of Cu and Au on the nanoscale, offering potential applications in the development of miniaturized integrated circuits and nanodevices.

alloys↗

Opposed-Flow Flame Spreading in Reduced Gravity

Experimental results obtained in drop towers and in Space Shuttle based experiments coupled with modelling efforts are beginning to provide information that is allowing an understanding to be developed of the physics of opposed-flow flame spread at reduced gravity where the spread rate and flow velocity are comparable and of the role played by radiative and diffusive processes in flame spreading in microgravity. Here we describe one Space Shuttle based experiment on flame spreading in a quiescent environment, the Solid Surface Combustion Experiment, SSCE, one planned microgravity experiment on flame spreading in a radiatively-controlled, forced opposing flow environment, the Diffusive and Radiative Transport in Fires Experiment, DARTFire, modelling efforts to support these experiments, and some results obtained to date.

Altenkirch, Robert A.↗

The second-moment climatology of the GATE rain rate data

The first part of this paper presents the description of the GARP (Global Atmospheric Research Program) Atlantic Tropical Experiment (GATE) 1 rain-rate data and its two-dimensional spectral and correlation characteristics, which has made it possible to accomplish the following: to show the concentration of a significant power along the frequency axis in the spatiotemporal spectra; to detect a diurnal cycle (which has a range of variation of about 3.4-5.4 mm/n) as one of the sources of bias in the rain statistics of satellite data; to study the distinction between the north-south and east-west transport of spatial rain-rate field and character of its anisotropy; to evaluate the scales of the distinction between second-moment estimates associated with ground and satellite samples; and to determine the appropriate spatial and temporal scales of simple linear stochastic models fitted to averaged rain-rate fields. The second part of this paper is devoted to an analysis of the diffusion of the rain rate by establishing a relationship between the parameters of the multivariate autoregressive model and the coefficients of a diffusion equation. This analysis led to the use of rain data to estimate the rain advection velocity as well as other coefficients of the diffusion equation of the corresponding field. The results obtained can be used for comparison with corresponding estimates of other sources of data (satellite, Tropical Oceans Global Atmosphere Coupled Ocean - Atmosphere Response Experiment (TOGA, COARE) or simulated by physical models), for generating multiple samples of any size, for solving the inverse problems of some of the hydrodynamic equations, and in some other areas of rain data analysis and modeling.

Polyak, Ilya↗

Diffusive isothermal partitioning in a layered medium with geologic applications

The diffusive isothermal partitioning of solute in a layered two-phase material has been analyzed to help elucidate the phenomenon of solute partitioning in multiphase lunar and terrestrial materials and to estimate the cooling history of samples. After reviewing the physical chemistry of partitioning and the case of an infinite one-dimensional diffusion couple, we solve in analytic form the case of a finite one-dimensional couple. The solution can be used to estimate cooling histories or to interpret laboratory experiments on partitioning. A sample calculation is included.

Hopper, R. W.↗

Particle Size Distribution Dynamics Can Help Constrain the Phase State of Secondary Organic Aerosol

Particle phase state is a property of atmospheric aerosols that has important implications for the formation, evolution, and gas/particle partitioning of secondary organic aerosol (SOA). In this work, we use a size-resolved chemistry and microphysics model (SOM-TOMAS), updated to include an explicit treatment of particle phase state, to constrain the bulk diffusion coefficient (Db) of SOA produced from ??- pinene ozonolysis. By leveraging data from laboratory experiments performed in the absence of a seed and under dry conditions, we find that the Db for SOA can be constrained (1-7 ×10-15 cm2 s-1 in these experiments) by simultaneously reproducing the time-varying SOA mass concentrations and the evolution of the particle size distribution. Another version of our model that used the predicted SOA composition to calculate the glass transition temperature, viscosity, and, ultimately, Db (~10-15 cm2 s-1) of the SOA was able to reproduce the mass and size distribution measurements when we included oligomer formation (oligomers accounted for about a fifth of the SOA mass). Our work highlights the potential of a size resolved SOA model to constrain the particle phase state of SOA by utilizing historical measurements of the evolution of the particle size distribution.

He, Yicong↗

Quantitative Species Measurements in Microgravity Combustion Flames using Near-Infrared Diode Lasers

Understanding the physical phenomena controlling the ignition and spread of flames in microgravity has importance for space safety as well as for characterizing dynamical and chemical combustion processes which are normally masked by buoyancy and other gravity-related effects. Unfortunately, combustion is highly complicated by fluid mechanical and chemical kinetic processes, requiring the use of numerical modeling to compare with carefully designed experiments. More sophisticated diagnostic methods are needed to provide the kind of quantitative data necessary to characterize the properties of microgravity combustion as well as provide accurate feedback to improve the predictive capabilities of the models. Diode lasers are a natural choice for use under the severe conditions of low gravity experiments. Reliable, simple solid state operation at low power satisfies the operational restrictions imposed by drop towers, aircraft and space-based studies. Modulation wavelength absorption spectroscopy (WMS) provides a means to make highly sensitive and quantitative measurements of local gas concentration and, in certain cases, temperature. With near-infrared diode lasers, detection of virtually all major combustion species with extremely rapid response time is possible in an inexpensive package. Advancements in near-infrared diode laser fabrication technology and concurrent development of optical fibers for these lasers led to their use in drop towers. Since near-infrared absorption line strengths for overtone and combination vibrational transitions are weaker than the mid-infrared fundamental bands, WMS techniques are applied to increase detection sensitivity and allow measurement of the major combustion gases. In the first microgravity species measurement, Silver et al. mounted a fiber-coupled laser at the top of the NASA 2.2-sec drop tower and piped the light through a single-mode fiber to the drop rig. A fiber splitter divided the light into eight channels that directed the laser beam across a methane or propane diffusion jet flame. The light beams were recaptured by a set of gradient index lenses, coupled back into separate fiber optic lines, and transmitted back to detectors and electronics in the instrument package. In these experiments a 6-mm od fiber cable (containing the nine optical fibers) fell with the drop rig. Using separate detection and demodulation channels, spatial and temporal (up to 20 Hz) maps of water vapor and methane concentrations were obtained at differing heights in the flames. While this apparatus was useful from a demonstration standpoint, several drawbacks needed attention before useful scientific measurements could be obtained. First, eight lines of sight are somewhat insufficient for detailing the spatial profiles of the gas. Second, multiple detection channels operating in parallel are both expensive and present a challenge for accurate calibration. As a result, a newer scanning system was developed in our first contract under this program. The primary characteristic of this system is that it contains a single detection channel and achieves "continuous" spatial resolution by scanning the laser beam across the flame region, then directing this beam onto a single detector. Thus spatial measurements are converted to a temporal series of data. The true spatial resolution is limited only by the beam diameter and width of the sweep. In these experiments the beam is focused to about 1-mm diameter and scans across a region up to 4-cm wide.

Silver, Joel A.↗

Unveiling the Origin of Morphological Instability in Topologically Complex Electrocatalytic Nanostructures

Coarsening and degradation phenomena in metals have largely focused on thermally driven processes, such as bulk and surface diffusion. However, dramatic coarsening has been reported in high-surface-area, nanometer-sized Pt-based catalysts during potential cycling in an electrolyte at room temperature─a temperature too low for the process to be explained purely by surface mobility values measured in both vacuum and electrolytes (∼10 –22 and ∼10 –18 cm 2 /s, respectively). This morphological evolution must be due to a different mechanism for mass transport that is sensitive to electrochemical conditions (e.g., electrolyte composition, potential limits, and scan rate). However, there have been no notable studies of electrochemically induced coarsening in nanometer-sized electrocatalysts. Here, we unveil the origins of coarsening in an electrolyte through coupled in situ experiments and atomistic kinetic Monte Carlo (kMC) simulations. Our work demonstrates electrochemical coarsening is driven by two concurrent mechanisms that can be explained at the atomistic level: (i) dissolution/redeposition during the reduction of an oxidized species and (ii) rapid surface diffusion of undercoordinated atoms.

gold↗