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At least 91 records · Page 5

Failure analysis of solid oxide fuel cells nickel-yttria stabilized zirconia anode under siloxane contamination

In this study, the failure process of the solid oxide fuel cell (SOFC) Ni-yttria-stabilized zirconia (YSZ) anode is investigated with D4 siloxane (octamethylcyclotetrasiloxane) contamination. In order to evaluate the influence of the electrochemical reaction on the siloxane deposition process, the SOFC experiments were operated at open circuit voltage (OCV) and 50 mA cm -2 conditions at 800°C. During the failure process, electrochemical, morphology and exhaust gas component analysis testing are conducted at the critical points. An equivalent circuit model and corresponding microstructure parameter calculations for separated physicochemical processes were utilized for the quantitative analysis of the failure process. Further, the results confirm the siloxane chemical adsorption deposition mechanism proposed in previous work. As a result, the failure of the anode was attributed to the gas diffusion blockage by dense silicon dioxide layer formation. The anode failure process with siloxane contamination is faster when the anode is operated under polarization.

25 ENERGY STORAGE↗

3D Printed Carbon Aerogels for Polymer-Electrolyte Fuel Cells

Carbon aerogels (CA) are known for ultra-low density, very high surface area, fine porous structure, and excellent electrical conductivity. Recent advances in high resolution 3D printing at LLNL enable the manufacturing of complex structured CA electrodes which have been demonstrated in electrolysis, flow battery, and supercapacitor applications. Polymer-electrolyte fuel cells (PEFC) may be an excellent candidate for these materials/methods as designers seek to optimize membrane-electrode assemblies to achieve higher efficiencies. A major challenge to PEFC design is two-phase flow due to water production which causes pore flooding and leads to cell instability and degradation. To mitigate these effects, groups have investigated the creation of liquid specific pathways in the porous layers to alleviate liquid buildup and enhance gas diffusion. While some progress has been made, traditionally manufactured GDLs, which consist of randomly distributed carbon fibers, are limiting. 3D printed CAs are a promising solution as complex macroporous electrode structures can be manufactured out of micro and nano porous filaments with a high level of control. Additionally, the process may allow for the consolidation of multiple layers (MPL, GDL, & flow channels) into a single printed architecture. In this work various CA lattice structures were printed using a direct ink write (DIW) method and liquid breakthrough pressures were measured to demonstrate the ability to tune the water pathways to achieve specific pressure thresholds. Furthermore, a discussion of the prospects for printed CA electrodes in PEFC will focus on material properties, synthesis techniques, and current challenges.

36 MATERIALS SCIENCE↗

Study of Buoyancy Effects in Diffusion Flames Using Rainbow Schlieren Deflectometry

Diffusion flames are extensively encountered in many domestic and industrial processes. Even after many decades of research, a complete understanding of the diffusion flame structure is not available. The structure and properties of the flames are governed by the mixing (laminar or turbulent), chemical kinetics, radiation and soot processes. Another important phenomenon that affects flame structure in normal gravity is buoyancy. The presence of buoyancy has long hindered the rational understanding of many combustion processes. In gas jet diffusion flames, buoyancy affects the structure of the shear layer, the development of fluid instabilities, and formation of the coherent structures in the near nozzle region of the gas jets. The buoyancy driven instabilities generate vorticial structures outside the flame resulting in flame flicker. The vortices also strongly interact with the small-scale structures in the jet shear layer. This affects the transitional and turbulence characteristics of the flame. For a fundamental understanding of diffusion flames it is essential to isolate the effects of buoyancy. This is the primary goal of the experiments conducted in microgravity. Previous investigations, have shown dramatic differences between the jet flames in microgravity and normal gravity. It has been observed that flames in microgravity are taller and more sooty than in normal gravity. The fuels used in these experiments were primarily hydrocarbons. In the absence of buoyancy the soot resides near the flame region, which adversely affects the entrainment of reactants. It is very important to eliminate the interference of soot on flame characteristics in microgravity. The present work, therefore, focuses on the changes in the flame structure due to buoyancy without the added complexities of heterogeneous reactions. Clean burning hydrogen is used as the fuel to avoid soot formation and minimize radiative losses. Because of the low luminosity of hydrogen flames, we use rainbow schlieren deflectometry for visualization. The visualized images are digitized for quantification.The work reported here is divided into three sections; rainbow schlieren deflectometry (RSD), microgravity experiments and sub-atmospheric pressure experiments. The first section demonstrates the application of RSD for quantitative measurements in non-reacting and reacting flow systems. A computational effort to complement the experimental work is also included. In the second section, the experiments conducted at the 2.2s NASA Lewis Drop tower facility are described. The experiments were conducted to study the behavior of laminar, transitional and turbulent hydrogen flames in microgravity. The ability of RSD technique to provide quantitative data is highlighted. The final section deals with the sub-atmospheric pressure tests, which demonstrate that buoyancy in hydrogen diffusion flames can be scaled with pressure at normal gravity.

Agrawal, Ajay K.↗

Influence of Coating Method on the Performance of Roll-to-Roll Coated PEM Fuel Cell Catalyst Layers

As production of fuel cell vehicles and power systems increases there is a need to understand the process science of fuel cell manufacturing. Industrial production of polymer electrolyte membrane fuel cell (PEMFC) electrodes will rely on continuous roll-to-roll (R2R) coating methods to meet the rates needed for mass production. There are a variety of coating methods that could be used to coat catalyst layers. The different physics of each method may result in different morphologies and performance. Here we present the results of a study comparing fuel cell catalyst layers coated using two R2R coating methods: slot-die and gravure. These two methods were selected because the physics of applying the liquid to the substrate is very different between the two cases. Pt/C catalysts layers were coated directly onto carbon-fiber gas diffusion media to create gas diffusion electrodes (GDEs), without the use of a decal transfer process. These GDEs were assembled into membrane electrode assemblies (MEAs) by hot pressing to Nafion membranes. In situ performance and other electrochemical diagnostics were used to determine the influence of coating method on catalyst layer electrochemical properties. Electron microscopy was utilized to understand the influence of coating method on electrode morphology and its influence on electrochemical properties. We also explored the influence of solvent ratio to understand the potential coupling between ink formulation and coating methodology.

DIRECT ENERGY CONVERSION,MATERIALS SCIENCE↗

Mechanistic calculation of the effective silver diffusion coefficient in polycrystalline silicon carbide: Application to silver release in AGR-1 TRISO particles

The silicon carbide (SiC) layer in tristructural isotropic (TRISO) fuel particles serves as a barrier to prevent the escape of fission products produced and not retained in the fuel kernel. The release of silver (Ag) is a concern due to the long half-life of the 110m Ag isotope. However, accurately determining the fission gas release rate requires knowing the diffusion coefficient through the SiC layer. In this study, we leverage atomistic calculations of Ag diffusivity in SiC bulk and grain boundaries (GBs) to develop a mesoscale effective Ag diffusion coefficient (D eff ) in SiC. Since GBs serve as pathways for Ag diffusion, D eff is defined as a function of temperature and microstructure variables. In particular, the size of SiC grains in the direction perpendicular to diffusion is shown to significantly affect Ag diffusion. The prediction of the mechanistic, mesoscale approach falls within one order of magnitude of empirical values. The temperature and microstructure-dependent effective Ag diffusivity in SiC is implemented in the fuel performance code Bison with a correction factor to predict Ag release from AGR-1 TRISO fuel particles. We hereby quantify the impact of SiC grain size on Ag release and improve Bison’s predictions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Mass transfer across combustion gas thermal boundary layers - Power production and materials processing implications

The effects of Soret diffusion (for vapors) and thermophoresis (for particles) are illustrated using recent optical experiments and boundary layer computations. Mass transfer rate augmentations of up to a factor of 1000 were observed and predicted for submicron-particle capture by cooled solid surfaces, while mass transfer suppressions of more than 10 to the -10th-fold were predicted for 'overheated' surfaces. It is noted that the results obtained are of interest in connection with such technological applications as fly-ash capture in power generation equipment and glass droplet deposition in optical-waveguide manufacture.

Rosner, D. E.↗

Rhenium-Oxygen Interactions at High Temperatures

The reaction of pure rhenium metal with dilute oxygen/argon mixtures was studied from 600 to 1400 C. Temperature, oxygen pressure, and flow rates were systematically varied to determine the rate-controlling steps. At lower temperatures the oxygen/rhenium chemical reaction is rate limiting; at higher temperatures gas-phase diffusion of oxygen through the static boundary layer is rate limiting. At all temperatures post-reaction microstructures indicate preferential attack along certain crystallographic planes and defects.

Jacobson, Nathan S.↗

Photometry and polarimetry of Jupiter at large phase angles. I - Analysis of imaging data of a prominent belt and a zone from Pioneer 10

Photopolarimetric observations of a prominent bright zone and a dark belt of Jupiter in red and blue light are analyzed which were performed by Pioneer 10 at phase angles of 12, 23, 34, 109, 120, 127, and 150 deg. Geometric and photometric reductions of the imaging data are described, the instrument sensitivity at various times is evaluated, and the data are referred to an absolute scale. The observations are analyzed in detail by comparing the data with results of radiative-transfer calculations for specific scattering models of Jupiter's atmosphere. These models include those with a vertical structure consisting of a layer of Rayleigh-scattering gas above a semiinfinite mixture of cloud particles and gas, those having a small quantity of aerosols in the gas above either the diffuse cloud in a reflecting-scattering model or the top cloud of a two-cloud-layer model, those in which a forward-scattering haze is mixed uniformly with gas, and those containing dust layers. It is found that in both the belt and the zone in red as well as blue light, cloud phase functions are required which provide both strong forward scattering and some backscattering.

Tomasko, M. G.↗

Mathematical model of diffusion-limited evolution of multiple gas bubbles in tissue

Models of gas bubble dynamics employed in probabilistic analyses of decompression sickness incidence in man must be theoretically consistent and simple, if they are to yield useful results without requiring excessive computations. They are generally formulated in terms of ordinary differential equations that describe diffusion-limited gas exchange between a gas bubble and the extravascular tissue surrounding it. In our previous model (Ann. Biomed. Eng. 30: 232-246, 2002), we showed that with appropriate representation of sink pressures to account for gas loss or gain due to heterogeneous blood perfusion in the unstirred diffusion region around the bubble, diffusion-limited bubble growth in a tissue of finite volume can be simulated without postulating a boundary layer across which gas flux is discontinuous. However, interactions between two or more bubbles caused by competition for available gas cannot be considered in this model, because the diffusion region has a fixed volume with zero gas flux at its outer boundary. The present work extends the previous model to accommodate interactions among multiple bubbles by allowing the diffusion region volume of each bubble to vary during bubble evolution. For given decompression and tissue volume, bubble growth is sustained only if the bubble number density is below a certain maximum.

Evaluation Studies↗

Environmental Protection Coating System for Refractory Metal Alloys (EPCS for RMAs)

As part of ARPA-E’s Ultra High Temperature Impervious Materials Advancing Turbine Efficiency (UITIMATE) program, this project aims to develop an environmental protection coating system (EPCS) for refractory metal alloys (RMAs) – which will provide radical improvement in long term protection for ultra-high temperature refractory metal components in harsh gas-turbine environments. The drive for higher fuel efficiency and higher core power of gas turbines used in electric power generation and in aircraft propulsion requires higher peak operation temperatures. The temperature capability of state-of-the-art materials cannot meet the new requirements. Refractory metal alloys have desirable capabilities for achieving the required peak temperatures, but most of them are subject to oxidation in the gas turbine environment. Thus, there is a strong need to develop novel environmental protective coatings that enable the refractory metals to operate in an ultra-high temperature engine environment. This project is composed of four major technical innovations that can provide a potentially transformational solution in providing environmental protection for refractory metal alloys over a wide range of temperature. 1) Multi-layer self-healing environmental barrier coating (EBC) that provides protection against combustion gas environment. 2) Oxidation resistant diffusion barrier (DB) on the alloy surface to enhance coating stability. 3) Synergistic integration of the multi-layer self-healing EBC with the diffusion barrier to extend coating life. 4) Guidance of physics-based modeling to accelerate coating development and optimization. Our team has successfully developed a multi-layer self-healing environmental protection coating system (EPCS) that can provide oxidation protection for commercially available molybdenum based refractory metal alloys over a wide temperature range of up to 1600 °C for fuel-efficient gas turbine applications. The team also developed a multi-layer high temperature coating design tool to accelerate coating development and optimization based on physics-based modeling. The team also engaged RTX business unite, notable Pratt and Whitney, for future commercialization of this technology. The successful completion of this Phase I effort led to the selection of performing Phase II of the program. In Phase II, the team plans to apply the EPCS in the protection of a newly discovered molybdenum-based metal alloy which has the potential of superior high temperature properties to the commercial products. Th coating will be evaluated under test conditions and environment that mimic gas turbine operation.

36 MATERIALS SCIENCE↗

Near-Limit Flamelet Phenomena in Buoyant Low Stretch Diffusion Flames Beneath a Solid Fuel

A unique near-limit low stretch multidimensional stable flamelet phenomena has been observed for the first time which extends the material flammability limit beyond the one-dimensional low stretch flammability limit to lower burning rates and higher relative heat losses than is possible with uniform flame coverage. During low stretch experiments burning the underside of very large radii (greater than or = 75 cm stretch rate less than or = 3/s) cylindrical cast PMMA samples, multidimensional flamelets were observed, in contrast with a one-dimensional flame that was found to blanket the surface for smaller radii samples ( higher stretch rate). Flamelets were observed by decreasing the stretch rate or by increasing the conductive heat loss from the flame. Flamelets are defined as flames that cover only part of the burning sample at any given time, but persist for many minutes. Flamelet phenomena is viewed as the flame's method of enhancing oxygen flow to the flame, through oxygen transport into the edges of the flamelet. Flamelets form as heat losses (surface radiation and solid-phase conduction) become large relative to the weakened heat release of the low stretch flame. While heat loss rates remain fairly constant, the limiting factor in the heat release of the flame is hypothesized to be the oxygen transport to the flame in this low stretch (low convective) environment. Flamelet extinction is frequently caused by encroachment of an adjacent flamelet. Large-scale whole-body flamelet oscillations at 1.2 - 1.95 Hz are noted prior to extinction of a flamelet. This oscillation is believed to be due a repeated process of excess fuel leakage through the dark channels between the flamelets, fuel premixing with slow incoming oxidizer, and subsequent rapid flame spread and retreat of the flamelet through the premixed layer. The oscillation frequency is driven by gas-phase diffusive time scales.

Olson, S. L.↗

The distribution of warm ionized gas in NGC 891

Narrow-band imaging is presented of the edge-on spiral NGC 891 in the H-alpha and S II 6716, 6731 A forbidden lines. Emission from H II regions confined to the plane of the galaxy and from diffuse gas up to about 4 kpc off the plane is readily detected. The full radial extent of the diffuse emission in the plane is about 30 kpc. NGC 891 is found to have a surface density of diffuse ionized gas twice the Galactic value, a thicker ionized gas layer, and a larger surface density of ionized gas relative to neutral gas. These are interpreted as consequences of a relatively high level of star formation in this galaxy. Other star formation tracers indicate the same conclusion. Many vertical H-alpha filaments, or 'worms,' extending to over 2 kpc off the plane of the galaxy are seen. These worms are interpreted in terms of chimney models for the interstellar media of spirals.

Rand, Richard J.↗

Engineered Thin Diffusion Layers for Anion-Exchange Membrane Electrolyzer Cells with Outstanding Performance

Anion-exchange membrane electrolyzer cells (AEMECs) are one of the most promising technologies for carbon-neutral hydrogen production. Over the past few years, the performance and durability of AEMECs have substantially improved. Herein, we report an engineered liquid/gas diffusion layer (LGDL) with tunable pore morphologies that enables the high performance of AEMECs. The comparison with a commercial titanium foam in the electrolyzer indicated that the engineered LGDL with thin-flat and straight-pore structures significantly improved the interfacial contacts, mass transport, and activation of more reaction sites, leading to outstanding performance. We obtained a current density of 2.0 A/cm 2 at 1.80 V with an efficiency of up to 81.9% at 60 °C under 0.1 M NaOH-fed conditions. The as-achieved high performance in this study provides insight to design advanced LGDLs for the production of low-cost and high-efficiency AEMECs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diffusion Driven Combustion Waves in Porous Media

Filtration of gas containing oxidizer, to the reaction zone in a porous medium, due, e.g., to a buoyancy force or to an external pressure gradient, leads to the propagation of Filtration combustion (FC) waves. The exothermic reaction occurs between the fuel component of the solid matrix and the oxidizer. In this paper, we analyze the ability of a reaction wave to propagate in a porous medium without the aid of filtration. We find that one possible mechanism of propagation is that the wave is driven by diffusion of oxidizer from the environment. The solution of the combustion problem describing diffusion driven waves is similar to the solution of the Stefan problem describing the propagation of phase transition waves, in that the temperature on the interface between the burned and unburned regions is constant, the combustion wave is described by a similarity solution which is a function of the similarity variable x/square root of(t) and the wave velocity decays as 1/square root of(t). The difference between the two problems is that in the combustion problem the temperature is not prescribed, but rather, is determined as part of the solution. We will show that the length of samples in which such self-sustained combustion waves can occur, must exceed a critical value which strongly depends on the combustion temperature T(sub b). Smaller values of T(sub b) require longer sample lengths for diffusion driven combustion waves to exist. Because of their relatively small velocity, diffusion driven waves are considered to be relevant for the case of low heat losses, which occur for large diameter samples or in microgravity conditions, Another possible mechanism of porous medium combustion describes waves which propagate by consuming the oxidizer initially stored in the pores of the sample. This occurs for abnormally high pressure and gas density. In this case, uniformly propagating planar waves, which are kinetically controlled, can propagate, Diffusion of oxidizer decreases the wave velocity. In addition to the reaction and diffusion layers, the uniformly propagating wave structure includes a layer with a pressure gradient, where the gas motion is induced by the production or consumption of the gas in the reaction as well as by thermal expansion of the gas. The width of this zone determines the scale of the combustion wave in the porous medium.

Aldushin, A. P.↗

Analysis of gas flow through a multilayer insulation system.

A theoretical investigation of gas flow inside a multilayer insulation system has been made for the case of the broadside pumping process. A set of simultaneous first-order differential equations for the temperature and pressure of the gas mixture was obtained by considering the diffusion mechanism of the gas molecules through the perforations on the insulation layers. A modified Runge-Kutta method was used for numerical experiment. The numerical stability problem was investigated. It has been shown that when the relaxation time is small compared with the time period over which the gas properties change appreciably, the set of differential equations can be replaced by a set of algebraic equations for solution. Numerical examples were given and comparison with experimental data was made.

Lin, J. T.↗