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At least 811 records · Page 45

(abstract) Alkali Metal Diffusion Through Porous Metal Electrodes in AMTEC Cells

The mechanisms of mass transport of an alkali metal through porous metal electrodes in alkali metal thermal-to-electric converter AMTEC cells is important in optimizing these high current density devices, but also affords the opportunity to investigate a variety of simple mass transport modes at high temperatures via electrochemical techniques. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes. Quantitative investigations of Na transport through WPt(sub 3.5) via surface or grain boundary diffusion, and K transport through porous Mo electrodes by free molecular flow, over large ranges of temperature have been performed. WPt(sub 3.5) has especially low transport impedance over the 950 to 1200K temperature range. New results are the Na through porous WPt(sub 3.5) and K through porous Mo diffusion rates and mechanisms.

alkali metal mass transport porous metal electrode↗

Characterization of Aerodynamic Performance of Boundary-Layer-Ingesting Inlet Under Crosswind

NASA has been studying future transport concepts, envisioned to be technically realizable in the timeframe of 2020-2030, to meet environmental and performance goals. One concept receiving considerable interest involves a propulsion system embedded into a hybrid wing-body aircraft. While offering significant advantages in fuel savings and noise reduction by this concept, there are several technical challenges that are not encountered in the current fleet and must be overcome so as to deliver target performance and operability. One of these challenges is associated with an inlet system that ingests a significantly thick boundary layer, developing along the wing-body surface, into a serpentine diffuser before the flow meeting fan blades. The flow is subject to considerable total pressure loss and distorted at the fan face, much more significantly than in the inlet system of conventional aircraft. In our previous studies [1, 2], we have shown that through innovative design changes on the airframe surface, it is possible to simultaneously increase total pressure recovery and decrease distortion in the flow, without resorting to conventional penalty-ridden flow control concepts, such as vortex generator or boundary layer bleeding/suction. In the current study, we are interested in understanding the following issues: how the embedded propulsion system performs under a crosswind condition by studying in detail the flow characteristics of two inlets, the baseline and another optimized previously under the cruise condition. With the insight, it is hoped that it can help in the follow-on study by devising effective strategies to minimize flow distortion arising from the integration of an embedded-engine system into an airframe to the level acceptable to the operation and fuel consumption before 2030. To achieve these demanding goals, non-conventional concepts are called for; but technology gap is too big that it requires evolutionary approach by focusing various concepts and technologies needed in the next three generations of aircraft, respectively named as N+1, N+2, and N+3. Noticeably, considerable reduction in each category of 1 is required in N+2 (relative to Boeing 777-200 and GE90 engines) and N+3 (relative to Boeing 737-800 and CFM56-7B engines). In this study, concepts for N+2 is our interest. A concept that has potential to achieve these metrics and has been under intensive study is the hybrid wing body (HWB) airframe with a tightly integrated propulsion system, see Fig. 1. The inlet is non-circular at the entrance and the entering flow, no longer uniform or free of disturbances, and is now carrying with it a boundary layer developing along the fuselage; the inlet is thus known as boundary-layer-ingesting (BLI) inlet.

Liou, Meng-Sing↗

Quantitative soil zymography: Mechanisms, processes of substrate and enzyme diffusion in porous media

Soil membrane zymography enables 2D mapping of enzyme activities on the surface of soil samples. The method is according to diffusion of components of enzymatically-mediated reactions to/from membrane, and, hence, reflects the distribution of enzyme activities at the intact soil surface. Zymography has been already successfully implemented in numerous soil ecology applications. Here we identify two methodological aspects for further improvement and expansion of the method at micro and macro scales: first, accounting for the area of contact between the soil surface and the zymography membranes and, second, accounting for diffusion effects during the zymography procedure. We tested three methods, namely, laser-scanning, staining with a fluorescent product (e.g. MUF: 4-methylumbelliferone), and X-ray computed micro-tomography, for assessing the area of the soil surface in contact with the membranes. We quantified diffusion of MUF, enzymes and substrate between the substrate-saturated membrane and soil as well as diffusion processes during membrane zymography via HP2 software. Diffusion of the substrate from the membrane and of the MUF-product to the membrane was detected, while there were no clear evidence of enzyme diffusion to/in the membrane. According to the model simulations, the enzyme activities detected via 2D zymography probably represent only a small portion, about 20%, of the actual reactions within the soil volume that is in both direct contact and in hydrological contact with zymography membranes. This is a result of omnidirectional diffusion of reaction products. The membrane contact with the soil surface estimated by three methods ranged from 3.4 to 36.5% further signifying that only a fraction of enzymes activity is detectable in a course of 2D soil zymography.

59 BASIC BIOLOGICAL SCIENCES↗

A Subgrid Approach for Modeling Microtopography Effects on Overland Flow

Microtopography, or heterogeneities in the elevation across scales much smaller than the domain of interest, plays a critical role in surface water retention, surface/subsurface interactions, and runoff. Resolving microtopographic influences on flow requires high–resolution simulations, which are computationally demanding even when considering the surface system in isolation and even more so when surface flow is one component in integrated simulations that couple surface flow with unsaturated subsurface flow. There is thus significant motivation for models that allow the effects of subgrid microtopography to be better represented. Subgrid models modify coarsened models to capture the microtopography–induced nonlinear effects on hydrologic processes. We present a subgrid model that alters the water storage and flow terms in the diffusion wave equation for surface flow. Stochastically generated microtopography with strongly contrasting spatial structure, high–resolution digital elevation maps from a polygonal tundra site on the North Slope of Alaska and a hummocky microtopography from a field site in Northern Minnesota are used to assess the accuracy and applicability of the subgrid model to disparate landscapes. Approaches for determining subgrid model parameters are tested and simulation results using the subgrid model are compared to benchmark fine–scale simulations and to coarse simulations that ignore microtopography. Our findings confirm that a properly parameterized subgrid model greatly improves the coarse–scale representation of hydrographs and total water content in the system. Furthermore, using the polygonal tundra example, we propose and test a strategy for moving to application–relevant spatial scales by combining microtopography classification and a few fine–scale simulations on small subdomains.

54 ENVIRONMENTAL SCIENCES↗

Rocket exhaust plume impingement on the Voyager spacecraft

In connection with the conduction of the long-duration Voyager missions to the outer planets and the sophisticated propulsion systems required, it was necessary to carry out an investigation to avoid exhaust plume impingement problems. The rarefied gas dynamics literature indicates that, for most engineering surfaces, the assumption of diffuse reemission and complete thermal accommodation is warranted in the free molecular flow regime. This assumption was applied to an analysis of a spacecraft plume impingement problem in the near-free molecular flow regime and yielded results to within a few percent of flight data. The importance of a correct treatment of the surface temperature was also demonstrated. Specular reflection, on the other hand, was shown to yield results which may be unconservative by a factor of 2 or 3. It is pointed out that one of the most difficult portions of an exhaust plume impingement analysis is the simulation of the impinged hardware. The geometry involved must be described as accurately and completely as possible.

Baerwald, R. K.↗

Absolute flux measurements for swift atoms

While a torsion balance in vacuum can easily measure the momentum transfer from a gas beam impinging on a surface attached to the balance, this measurement depends on the accommodation coefficients of the atoms with the surface and the distribution of the recoil. A torsion balance is described for making absolute flux measurements independent of recoil effects. The torsion balance is a conventional taut suspension wire design and the Young modulus of the wire determines the relationship between the displacement and the applied torque. A compensating magnetic field is applied to maintain zero displacement and provide critical damping. The unique feature is to couple the impinging gas beam to the torsion balance via a Wood's horn, i.e., a thin wall tube with a gradual 90 deg bend. Just as light is trapped in a Wood's horn by specular reflection from the curved surfaces, the gas beam diffuses through the tube. Instead of trapping the beam, the end of the tube is open so that the atoms exit the tube at 90 deg to their original direction. Therefore, all of the forward momentum of the gas beam is transferred to the torsion balance independent of the angle of reflection from the surfaces inside the tube.

Fink, M.↗

Pulmonary diffusing capacity, capillary blood volume, and cardiac output during sustained microgravity

We measured pulmonary diffusing capacity (DL), diffusing capacity per unit lung volume, pulmonary capillary blood volume (Vc), membrane diffusing capacity (Dm), pulmonary capillary blood flow or cardiac output (Qc), and cardiac stroke volume (SV) in four subjects exposed to nine days of microgravity. DL in microgravity was elevated compared with preflight standing values and was higher than preflight supine because of the elevation of both Vc and Dm. The elevation in Vc was comparable to that measured supine in 1 G, but the increase in Dm was in sharp contrast to the supine value. We postulate that, in 0 G, pulmonary capillary blood is evenly distributed throughout the lung, providing for uniform capillary filling, leading to an increase in the surface area available for diffusion. By contrast, in the supine 1-G state, the capillaries are less evenly filled, and although a similar increase in blood volume is observed, the corresponding increase in surface area does not occur. DL and its subdivisions showed no adaptive changes from the first measurement 24 h after the start of 0 G to eight days later. Similarly, there were no trends in the postflight data, suggesting that the principal mechanism of these changes was gravitational. The increase in Dm suggests that subclinical pulmonary edema did not result from exposure to 0 G. Qc was modestly increased inflight and decreased postflight compared with preflight standing. Compared with preflight standing, SV was increased 46 percent inflight and decreased 14 percent in the 1st week postflight. There were temporal changes in Qc and SV during 0 G, with the highest values recorded at the first measurement, 24 h into the flight. The lowest values of Qc and SV occurred on the day of return.

Prisk, G. K.↗

A Computational-Experimental Development of Vortex Generator Use for a Transitioning S-Diffuser

The development of an effective design strategy for surface-mounted vortex generator arrays in a subsonic diffuser is described in this report. This strategy uses the strengths of both computational and experimental analyses to determine beneficial vortex generator locations and sizes. A parabolized Navier-Stokes solver, RNS3D, was used to establish proper placement of the vortex generators for reduction in circumferential total pressure distortion. Experimental measurements were used to determine proper vortex generator sizing to minimize total pressure recovery losses associated with vortex generator device drag. The best result achieved a 59% reduction in the distortion index DC60, with a 0.3% reduction in total pressure recovery.

Wendt, Bruce J.↗

High-Rate, Selective Electrosynthesis of Cyclohexanone Oxime via In Situ Generation and Release of Hydroxylamine on Bismuth

Oxime compounds are key industrial intermediates for nylon precursors and commodity chemicals. However, conventional routes rely on multistep reactions and hydroxylamine (NH 2 OH) salts, raising significant safety and sustainability concerns. Although electrosynthesis offers an alternative, oxime formation on d-block transition metals suffers from poor selectivity, as nitrogen oxyanion intermediates bind strongly to the surface and are readily over-reduced to ammonia. Here, we report morphology-controlled p-block bismuth rhombic dodecahedra (Bi RDs) that promote in situ NH 2 OH generation and its desorption into the electrolyte, enabling an electrochemical-chemical decoupled route for cyclohexanone oxime (CHO) synthesis. Bi RDs deliver nearly 100% Faradaic efficiency (FE) at −0.5 V vs. RHE and a yield of 1.4 mmol h –1 cm –2 at −0.9 V vs. RHE in an H-cell, while maintaining a CHO selectivity of nearly 100% at 100 mA cm –2 in a flow cell. Under identical conditions, d-block electrodes (Cu, Pd, Ag) show FE below 30%. Density functional theory calculations reveal that Bi 6p orbital-derived surface states weaken intermediate binding and facilitate NH 2 OH desorption, suppressing over-reduction. Kinetic analysis, post-addition trapping experiments, and in situ ATR-FTIR and Raman spectroscopy suggest the following reaction mechanism: NH 2 OH is selectively generated at the electrode surface, released as a freely diffusing intermediate, and undergoes homogeneous condensation with cyclohexanone in the bulk electrolyte, bypassing the surface-confined Langmuir–Hinshelwood pathway. These findings demonstrate that regulating intermediate desorption through p-block orbital chemistry provides a general strategy for achieving high selectivity in electro-organic nitrogen synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An in situ formed inorganic conductive network enables high stability and rate capability of single-crystalline nickel-rich cathodes

Single-crystalline Ni-rich cathodes are promising for the next generation of high-energy-density Li-ion batteries due to their better capacity retention than their polycrystalline counterparts. However, there is still much room for improving the electrochemical performances when considering their surface degradation and severe kinetic hindrance during cycling. Herein, we report a strategy to construct an in situ formed robust Li-conductive Li 3 PO 4 layer on the surface of cathode particles. This Li-conductive layer significantly increases the Li-ion diffusion coefficients and suppresses detrimental surface phase transformation. In situ XRD reveals that the improved kinetics alleviate the local stress at high voltage. The as-prepared single-crystalline LiNi 0.83 Co 0.12 Mn 0.05 O 2 delivers good durability (96.8% after 100 cycles at 1C) and excellent rate capability (177.08 mA h g -1 at 5C). Here, this work provides a facile and efficient strategy to improve the cycling performance and boost the rate capability of single-crystalline Ni-rich cathodes.

25 ENERGY STORAGE↗

Teflon, Kapton surface and bulk effects

Two samples of 2 mil aluminized/Kapton thermal blanket and two samples of Teflon were received for evaluation. Their location on the solar maximum is given. The Kapton top layer of the thermal blanket had been exposed to the LEO atomic oxygen environment and shows the surface degradation due to atomic oxygen attack resulting in a diffuse character over most of the surface. The backside Kapton layer which was unexposed appeared to the eye to be in virgin condition. Another sample exhibited similar properties, but was, in large part, covered with Kapton adhesive tape and it was not possible to obtain usable specimens for analysis. One of the Teflon samples which was exposed shows signs of heavy degradation including attack on the Ag/Inconel backside by ultraviolet and atomic oxygen. The other Teflon sample which was unexposed was only slightly fogged on the Teflon side and the Ag/Inconel appeared untouched. These samples were subjected to several chemical and physical analyses, the results of which are discussed.

J C Robinson↗

Experimental Investigation of Centrifugal Compressor Stabilization Techniques

Results from a series of experiments to investigate techniques for extending the stable flow range of a centrifugal compressor are reported. The research was conducted in a high-speed centrifugal compressor at the NASA Glenn Research Center. The stabilizing effect of steadily flowing air-streams injected into the vaneless region of a vane-island diffuser through the shroud surface is described. Parametric variations of injection angle, injection flow rate, number of injectors, injector spacing, and injection versus bleed were investigated for a range of impeller speeds and tip clearances. Both the compressor discharge and an external source were used for the injection air supply. The stabilizing effect of flow obstructions created by tubes that were inserted into the diffuser vaneless space through the shroud was also investigated. Tube immersion into the vaneless space was varied in the flow obstruction experiments. Results from testing done at impeller design speed and tip clearance are presented. Surge margin improved by 1.7 points using injection air that was supplied from within the compressor. Externally supplied injection air was used to return the compressor to stable operation after being throttled into surge. The tubes, which were capped to prevent mass flux, provided 9.3 points of additional surge margin over the baseline surge margin of 11.7 points.

Skoch, Gary J.↗

Experimental Studies of Hydrogenation and Other Reactions on Surfaces Under Astrophysically Relevant Conditions

The goal of our project is to study hydrogen recombination reactions on solid surfaces under conditions that are relevant in astrophysics. Laboratory experiments were conducted using low-flux, cold atomic H and D beams impinging on a sample kept under ultra high vacuum conditions. Realistic analogues of interstellar dust grains were used. Our results show that current models for hydrogen recombination reactions have to be modified to take into account the role of activated diffusion of H on surfaces even at low temperature.

Vidali, Gianfranco↗

Reshaping of Truncated Pd Nanocubes: Energetic and Kinetic Analysis Integrating Transmission Electron Microscopy with Atomistic-Level and Coarse-Grained Modeling

Stability against reshaping of metallic fcc nanocrystals synthesized with tailored far-from-equilibrium shapes is key to maintaining optimal properties for applications such as catalysis. Yet Arrhenius analysis of experimental reshaping kinetics, and appropriate theory and simulation, is lacking. As such, we use TEM to monitor the reshaping of Pd nanocubes of ~25 nm side length between 410 °C (over ~4.5 h) and 440 °C (over ~0.25 h), extracting a high effective energy barrier of E eff ≈ 4.6 eV. We also provide an analytic determination of the energy variation along the optimal pathway for reshaping that involves transfer of atoms across the nanocube surface from edges or corners to form new layers on side {100} facets. The effective barrier from this analysis is shown to increase strongly with the degree of truncation of edges and corners in the synthesized nanocube. Theory matches experiment for the appropriate degree of truncation. In addition, we perform simulations of a stochastic atomistic-level model incorporating a realistic description of diffusive hopping for undercoordinated surface atoms, thereby providing a visualization of the initial reshaping process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface Processes of Faceted Growth

Atomic force microscopy and high precision optical interferometry allow to analyze the processes that are in the core of our present understanding of faceted crystal growth. Some of these processes will be reviewed. Recent experiments suggest that the Gibbs-Thomson Law (GTL) may not be applicable to the weakly fluctuating strongly polygonized steps, with low kink density. Propagation rate of a straight short step segment changes with the segment length much steeper than predicted by GTL. If the step fluctuations are still well developed, the typical transition length may be determined just by the radius of rounded comers of the polygonized step. If fluctuations do not have enough time to develop, the kinetic effects may be essential. Indeed, 'communications' between comers of a short straight step segment may occur and, thus, the GTL may be implemented only via kink exchange. E.g., dissolutions of this short segment at macroscopic equilibrium occurs as follows: The kinks are split from one comer as a result of fluctuations, and annihilate with kinks of the opposite sign generated by another comer. Similarly, an exchange via chain of kinks on a rough step is the mechanism to implement the GT Law. If there is a supersaturation with respect to a large crystal, the kinks not only diffuse along the step, but move back the generating comers. This 'wind' prevents communication between the comers and places upper limit supersaturation only below which GTL is applicable. Steps replace kinks in the 3D case, though, of course, another dimensionality brings about another physics. Another specific problem to think about is if fluctuations are always fast enough to provide enough kinks for linear dependence of step rate on supersaturation. Increasing azimuthal polygonization of growth hillocks is a sign of insufficient fluctuation rate. Morphological stability of vicinal faces is usually considered on the basis of mutually parallel steps. Azimuthal anisotropy and interlacing of step bunches inducing the well known bunch splitting is another challenge. Among other challenging problems are: existence of surface diffusion on the crystal/so1ution interface, step interaction in solutions, achievement of step flow modes from liquids, impurity effects. New phenomena essential in biomacromolecular crystallization is another interesting area.

Chernov, A.↗

Scaling microstructural processes in the sintering of ionic ceramics

A multi-scale framework, combining a multiphase field formulation and large deformation mechanics, was developed as a stepping stone to perform the data analytics of the microstructural level kinetics of a sintering solid. Relevant microstructural information from this framework, such as grain, stress, and porosity statistics, was scaled up to describe the macroscopic level sintering kinetics. Here, the developed formulation was applied to describe the electric field assisted sintering of Y 2 O 3 . Microstructural inhomogeneities in a multi-granular solid result in the formation of a field of compressive stress networks, which interleave with low compression and weakly tensile regions, defining a scaffolding for sintering concentration regions to develop. A Poisson effect-induced lateral stress network is also naturally self-induced as a result of the mechanical constraints imposed by the sintering apparatus. For long sintering times, localized shear stresses enhancing mass flow along grain boundaries and internal surfaces develop. Three-sided pores are removed by either vacancy transport to the surrounding pores, or move towards the external surfaces through grain boundary diffusion. Four- and higher order-sided pores stabilize because an equal amount of vacancies are gained and lost through the connecting grain boundaries. Grain dewetting contributes to pore coalescence, suggesting that pore kinetics and grain growth are coupled and should be analyzed in concert. The combined sintering and grain growth kinetics define six regimes of sintering behavior: (1) T, the transient regime; (2) E$_Υ$, the surface energy dominated, early sintering regime, where the grain growth exponent, p = 1, and the stress concentration factor, $f$ ~ $1/\hat{ρ}^{4.6}$; (3) E S , the stress dominated, early sintering regime, where p = 1 and $f$ ~ $1/\hat{ρ}^{4}$; (4) I$_Υ$, the surface energy dominated, intermediate sintering regime, where p = 2 and $f$ ~ $1/\hat{ρ}^{4.6}$; (5) I S , the stress dominated, intermediate sintering regime, where p = 2 and $f$ ~ $1/\hat{ρ}^{4}$; and (6) L, the late sintering regime, where p = 3 and $f$ ~ 1. At the macroscopic level, the rapid densification and suppression of grain growth observed in the electric field assisted sintering process is a consequence of the compounding effects of the underlying stress-, transport-, and interfacial-energy-induced energy minimization kinetics, as predicted by the multi-scale framework.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Heat transfer, diffusion, and evaporation

Although it has long been known that the differential equations of the heat-transfer and diffusion processes are identical, application to technical problems has only recently been made. In 1916 it was shown that the speed of oxidation of the carbon in iron ore depends upon the speed with which the oxygen of the combustion air diffuses through the core of gas surrounding the carbon surface. The identity previously referred to was then used to calculate the amount of oxygen diffusing to the carbon surface on the basis of the heat transfer between the gas stream and the carbon surface. Then in 1921, H. Thoma reversed that procedure; he used diffusion experiments to determine heat-transfer coefficients. Recently Lohrisch has extended this work by experiment. A technically very important application of the identity of heat transfer and diffusion is that of the cooling tower, since in this case both processes occur simultaneously.

GASES - DIFFUSION↗

A Generalized Grain-Scale Model for the Non-Plasma and Plasma-Assisted Hydrogen Direct Reduction of Iron Ore

Direct Reduction of Iron ore using hydrogen (H-DRI) is a promising pathway towards efficient steelmaking and accurate predictive models are a necessity for scale-up and optimization of this technology. However, accurate models of this process remain limited because existing models oversimplify grain-scale phenomena, such as nonlinearity inside grain, self-sufficient porosity, surface reactions, and the role of plasma species. These phenomena are important for flash steelmaking and plasma-assisted H-DRI processes. To address this need, we present a phenomenological model for simulating H-DRI at the scale of a single micron-sized grain of the iron ore. We call this the Transient Reactive Grain Model (TRGM). TRGM incorporates key physical process: gas species transport, a chemical kinetics of material conversion, nanopore structural evolution and, adsorption-desorption surface kinetics at the reactive nanopore surface. The important contribution of this work is that the model provides a dependence on different reductant species, specifically hydrogen atoms versus molecules, so that role of hydrogen plasma reduction can be clarified compared to the use of pure hydrogen gas reduction. TRGM predictions agree well with experimental data for both molecular H2 reduction of Fe2O3 and plasma hydrogen reduction of Fe3O4. Results reveal species concentration gradients with a diffuse reaction zone, and enhanced hydrogen diffusion at the grain outer surface due to evolving porosity. These findings challenge common assumptions in existing models, including sharp reaction fronts, quasi-steady diffusion and kinetics, and the neglect of surface chemistry. As a generalized grain-scale model for H-DRI processes, TRGM has practical applications in flash steelmaking and in-flight reduction using both molecular and plasma hydrogen.

08 HYDROGEN↗