Short stack modeling of degradation in solid oxide fuel cells. Part II. Sensitivity and interaction analysis

NASA Astrophysics Data System (ADS)

Gazzarri, J. I.; Kesler, O.

In the first part of this two-paper series, we presented a numerical model of the impedance behaviour of a solid oxide fuel cell (SOFC) aimed at simulating the change in the impedance spectrum induced by contact degradation at the interconnect-electrode, and at the electrode-electrolyte interfaces. The purpose of that investigation was to develop a non-invasive diagnostic technique to identify degradation modes in situ. In the present paper, we appraise the predictive capabilities of the proposed method in terms of its robustness to uncertainties in the input parameters, many of which are very difficult to measure independently. We applied this technique to the degradation modes simulated in Part I, in addition to anode sulfur poisoning. Electrode delamination showed the highest robustness to input parameter variations, followed by interconnect oxidation and interconnect detachment. The most sensitive degradation mode was sulfur poisoning, due to strong parameter interactions. In addition, we simulate several simultaneous two-degradation-mode scenarios, assessing the method's capabilities and limitations for the prediction of electrochemical behaviour of SOFC's undergoing multiple simultaneous degradation modes.

Impact of Dynamic Specimen Shape Evolution on the Atom Probe Tomography Results of Doped Epitaxial Oxide Multilayers: Comparison of Experiment and Simulation

DOE PAGES

Madaan, Nitesh; Bao, Jie; Nandasiri, Manjula I.; ...

2015-08-31

The experimental atom probe tomography results from two different specimen orientations (top-down and side-ways) of a high oxygen ion conducting Samaria-doped-ceria/Scandia-stabilized-zirconia multilayer thin film solid oxide fuel cell electrolyte was correlated with level-set method based field evaporation simulations for the same specimen orientations. This experiment-theory correlation explains the dynamic specimen shape evolution and ion trajectory aberrations that can induce density artifacts in final reconstruction leading to inaccurate estimation of interfacial intermixing. This study highlights the need and importance of correlating experimental results with field evaporation simulations when using atom probe tomography for studying oxide heterostructure interfaces.

Modeling Manganese Silicate Inclusion Composition Changes during Ladle Treatment Using FactSage Macros

NASA Astrophysics Data System (ADS)

Piva, Stephano P. T.; Kumar, Deepoo; Pistorius, P. Chris

2017-02-01

This work investigated the use of FactSage macros to simulate steel-slag and steel-inclusion reaction kinetics in silicon-manganese killed steels, and predict oxide inclusion composition changes during ladle treatment. These changes were assessed experimentally using an induction furnace to simulate deoxidation and slag addition. The average steel mass transfer coefficient for the experimental setup was calculated from the analyzed aluminum pick-up by steel. Average oxide inclusion composition was measured using scanning electron microscopy and energy-dispersive X-ray spectroscopy. Confocal laser scanning microscopy was used to assess the physical state (solid or liquid) of oxide inclusions in selected samples. The changes in the chemical compositions of the oxide inclusions and the steel agreed with the FactSage macro simulations.

Three-dimensional three-phase model for simulation of hydrodynamics, oxygen mass transfer, carbon oxidation, nitrification and denitrification in an oxidation ditch.

PubMed

Lei, Li; Ni, Jinren

2014-04-15

A three-dimensional three-phase fluid model, supplemented by laboratory data, was developed to simulate the hydrodynamics, oxygen mass transfer, carbon oxidation, nitrification and denitrification processes in an oxidation ditch. The model provided detailed phase information on the liquid flow field, gas hold-up distribution and sludge sedimentation. The three-phase model described water-gas, water-sludge and gas-sludge interactions. Activated sludge was taken to be in a pseudo-solid phase, comprising an initially separated solid phase that was transported and later underwent biological reactions with the surrounding liquidmedia. Floc parameters were modified to improve the sludge viscosity, sludge density, oxygen mass transfer rate, and carbon substrate uptake due to adsorption onto the activated sludge. The validation test results were in very satisfactory agreement with laboratory data on the behavior of activated sludge in an oxidation ditch. By coupling species transport and biological process models, reasonable predictions are made of: (1) the biochemical kinetics of dissolved oxygen, chemical oxygen demand (COD) and nitrogen variation, and (2) the physical kinematics of sludge sedimentation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Dramatically different kinetics and mechanism at solid/liquid and solid/gas interfaces for catalytic isopropanol oxidation over size-controlled platinum nanoparticles.

PubMed

Wang, Hailiang; Sapi, Andras; Thompson, Christopher M; Liu, Fudong; Zherebetskyy, Danylo; Krier, James M; Carl, Lindsay M; Cai, Xiaojun; Wang, Lin-Wang; Somorjai, Gabor A

2014-07-23

We synthesize platinum nanoparticles with controlled average sizes of 2, 4, 6, and 8 nm and use them as model catalysts to study isopropanol oxidation to acetone in both the liquid and gas phases at 60 °C. The reaction at the solid/liquid interface is 2 orders of magnitude slower than that at the solid/gas interface, while catalytic activity increases with the size of platinum nanoparticles for both the liquid-phase and gas-phase reactions. The activation energy of the gas-phase reaction decreases with the platinum nanoparticle size and is in general much higher than that of the liquid-phase reaction which is largely insensitive to the size of catalyst nanoparticles. Water substantially promotes isopropanol oxidation in the liquid phase. However, it inhibits the reaction in the gas phase. The kinetic results suggest different mechanisms between the liquid-phase and gas-phase reactions, correlating well with different orientations of IPA species at the solid/liquid interface vs the solid/gas interface as probed by sum frequency generation vibrational spectroscopy under reaction conditions and simulated by computational calculations.

Zirconia ceramics for excess weapons plutonium waste

NASA Astrophysics Data System (ADS)

Gong, W. L.; Lutze, W.; Ewing, R. C.

2000-01-01

We synthesized a zirconia (ZrO 2)-based single-phase ceramic containing simulated excess weapons plutonium waste. ZrO 2 has large solubility for other metallic oxides. More than 20 binary systems A xO y-ZrO 2 have been reported in the literature, including PuO 2, rare-earth oxides, and oxides of metals contained in weapons plutonium wastes. We show that significant amounts of gadolinium (neutron absorber) and yttrium (additional stabilizer of the cubic modification) can be dissolved in ZrO 2, together with plutonium (simulated by Ce 4+, U 4+ or Th 4+) and impurities (e.g., Ca, Mg, Fe, Si). Sol-gel and powder methods were applied to make homogeneous, single-phase zirconia solid solutions. Pu waste impurities were completely dissolved in the solid solutions. In contrast to other phases, e.g., zirconolite and pyrochlore, zirconia is extremely radiation resistant and does not undergo amorphization. Baddeleyite (ZrO 2) is suggested as the natural analogue to study long-term radiation resistance and chemical durability of zirconia-based waste forms.

Direct oxidation of strong waste waters, simulating combined wastes in extended-mission space cabins

NASA Technical Reports Server (NTRS)

Ross, L. W.

1973-01-01

The applications of modern technology to the resolution of the problem of solid wastes in space cabin environments was studied with emphasis on the exploration of operating conditions that would permit lowering of process temperatures in wet oxidation of combined human wastes. It was found that the ultimate degree of degradation is not enhanced by use of a catalyst. However, the rate of oxidation is increased, and the temperature of oxidation is reduced to 400 F.

The calibration of a model for simulating the thermal and electrical performance of a 2.8 kW AC solid-oxide fuel cell micro-cogeneration device

NASA Astrophysics Data System (ADS)

Beausoleil-Morrison, Ian; Lombardi, Kathleen

The concurrent production of heat and electricity within residential buildings using solid-oxide fuel cell (SOFC) micro-cogeneration devices has the potential to reduce primary energy consumption, greenhouse gas emissions, and air pollutants. A realistic assessment of this emerging technology requires the accurate simulation of the thermal and electrical production of SOFC micro-cogeneration devices concurrent with the simulation of the building, its occupants, and coupled plant components. The calibration of such a model using empirical data gathered from experiments conducted with a 2.8 kW AC SOFC micro-cogeneration device is demonstrated. The experimental configuration, types of instrumentation employed, and the operating scenarios examined are treated. The propagation of measurement uncertainty into the derived quantities that are necessary for model calibration are demonstrated by focusing upon the SOFC micro-cogeneration system's gas-to-water heat exchanger. The calibration coefficients necessary to accurately simulate the thermal and electrical performance of this prototype device are presented and the types of analyses enabled to study the potential of the technology are demonstrated.

Fuzzy Logic Based Controller for a Grid-Connected Solid Oxide Fuel Cell Power Plant.

PubMed

Chatterjee, Kalyan; Shankar, Ravi; Kumar, Amit

2014-10-01

This paper describes a mathematical model of a solid oxide fuel cell (SOFC) power plant integrated in a multimachine power system. The utilization factor of a fuel stack maintains steady state by tuning the fuel valve in the fuel processor at a rate proportional to a current drawn from the fuel stack. A suitable fuzzy logic control is used for the overall system, its objective being controlling the current drawn by the power conditioning unit and meet a desirable output power demand. The proposed control scheme is verified through computer simulations.

A multi-level simulation platform of natural gas internal reforming solid oxide fuel cell-gas turbine hybrid generation system - Part II. Balancing units model library and system simulation

NASA Astrophysics Data System (ADS)

Bao, Cheng; Cai, Ningsheng; Croiset, Eric

2011-10-01

Following our integrated hierarchical modeling framework of natural gas internal reforming solid oxide fuel cell (IRSOFC), this paper firstly introduces the model libraries of main balancing units, including some state-of-the-art achievements and our specific work. Based on gPROMS programming code, flexible configuration and modular design are fully realized by specifying graphically all unit models in each level. Via comparison with the steady-state experimental data of Siemens-Westinghouse demonstration system, the in-house multi-level SOFC-gas turbine (GT) simulation platform is validated to be more accurate than the advanced power system analysis tool (APSAT). Moreover, some units of the demonstration system are designed reversely for analysis of a typically part-load transient process. The framework of distributed and dynamic modeling in most of units is significant for the development of control strategies in the future.

Complete oxidation of solid phase sulfides by manganese and bacteria in anoxic marine sediments

NASA Astrophysics Data System (ADS)

Aller, Robert C.; Rude, Peter D.

1988-03-01

During the physical or biological reworking of surficial marine sediments, metal oxides are often brought into contact with both solid and dissolved sulfides. Experiments simulating these mixing processes demonstrate that in natural sediments Mn-oxides can completely oxidize solid phase sulfides to SO 4- under anoxic conditions. The major source of sulfur is probably acid volatile sulfide. Minerals containing Mn +4 are apparently more effective than Mn +3 in driving the oxidation. There is slight or no evidence for complete sulfide oxidation by Fe-oxides under similar conditions. The reaction is inhibited by DNP (dinitrophenol) and azide, implying biological mediation by a group of chemolithotrophic bacteria such as the thiobacilli, having a well-organized cytochrome system, oxidative phosphorylation coupled with sulfide oxidation, and possibly aulolrophic CO 2 fixation. Lack of sensitivity to chlorate suggests that a No 3- reductase complex is not involved. Because of metal reduction and the overall stoichiometry of reaction, this sulfide oxidation causes a rise in pH in contrast to oxidation by O 2. Alkalinity is also simultaneously depeleted by Mn, Ca carbonate precipitation. Both manganoan kutnahorite and manganoan calcite are observed to form rapidly (days) during Mn reduction. The oxidation of sulfides by Mn-oxides is likely to be important, but highly variable, in organic-rich shelf sediments and environments such as hydrothermal vents where sulfidic plumes contact oxidized metals. A substantial Proportion of sedimentary sulfide may be oxidized and Mn reduced by this pathway, particularly in bioturbated sediments. The relative roles of lithotrophic (S) and heterotrophic (C) Mn-reduction in marine sediments are presently unknown.

Yttria-stabilized zirconia solid oxide electrolyte fuel cells: Monolithic solid oxide fuel cells

NASA Astrophysics Data System (ADS)

1990-10-01

The monolithic solid oxide fuel cell (MSOFC) is currently under development for a variety of applications including coal-based power generation. The MSOFC is a design concept that places the thin components of a solid oxide fuel cell in lightweight, compact, corrugated structure, and so achieves high efficiency and excellent performance simultaneously with high power density. The MSOFC can be integrated with coal gasification plants and is expected to have high overall efficiency in the conversion of the chemical energy of coal to electrical energy. This report describes work aimed at: (1) assessing manufacturing costs for the MSOFC and system costs for a coal-based plant; (2) modifying electrodes and electrode/electrolyte interfaces to improve the electrochemical performance of the MSOFC; and (3) testing the performance of the MSOFC on hydrogen and simulated coal gas. Manufacturing costs for both the coflow and crossflow MSOFC's were assessed based on the fabrication flow charts developed by direct scaleup of tape calendering and other laboratory processes. Integrated coal-based MSOFC systems were investigated to determine capital costs and costs of electricity. Design criteria were established for a coal-fueled 200-Mw power plant. Four plant arrangements were evaluated, and plant performance was analyzed. Interfacial modification involved modification of electrodes and electrode/electrolyte interfaces to improve the MSOFC electrochemical performance. Work in the cathode and cathode/electrolyte interface was concentrated on modification of electrode porosity, electrode morphology, electrode material, and interfacial bonding. Modifications of the anode and anode/electrolyte interface included the use of additives and improvement of nickel distribution. Single cells have been tested for their electrochemical performance. Performance data were typically obtained with humidified H2 or simulated coal gas and air or oxygen.

A study on production of biodiesel using a novel solid oxide catalyst derived from waste.

PubMed

Majhi, Samrat; Ray, Srimanta

2016-05-01

The issues of energy security, dwindling supply and inflating price of fossil fuel have shifted the global focus towards fuel of renewable origin. Biodiesel, having renewable origin, has exhibited great potential as substitute for fossil fuels. The most common route of biodiesel production is through transesterification of vegetable oil in presence of homogeneous acid or base or solid oxide catalyst. But, the economics of biodiesel is not competitive with respect to fossil fuel due to high cost of production. The vegetable oil waste is a potential alternative for biodiesel production, particularly when disposal of used vegetable oil has been restricted in several countries. The present study evaluates the efficacy of a low-cost solid oxide catalyst derived from eggshell (a food waste) in transesterification of vegetable oil and simulated waste vegetable oil (SWVO). The impact of thermal treatment of vegetable oil (to simulate frying operation) on transesterification using eggshell-derived solid oxide catalyst (ESSO catalyst) was also evaluated along with the effect of varying reaction parameters. The study reported that around 90 % biodiesel yield was obtained with vegetable oil at methanol/oil molar ratio of 18:1 in 3 h reaction time using 10 % ESSO catalyst. The biodiesel produced with ESSO catalyst from SWVO, thermally treated at 150 °C for 24 h, was found to conform with the biodiesel standard, but the yield was 5 % lower compared to that of the untreated oil. The utilization of waste vegetable oil along with waste eggshell as catalyst is significant for improving the overall economics of the biodiesel in the current market. The utilization of waste for societal benefit with the essence of sustainable development is the novelty of this work.

Fully printable transparent monolithic solid-state dye-sensitized solar cell with mesoscopic indium tin oxide counter electrode.

PubMed

Yang, Ying; Ri, Kwangho; Rong, Yaoguang; Liu, Linfeng; Liu, Tongfa; Hu, Min; Li, Xiong; Han, Hongwei

2014-09-07

We present a new transparent monolithic mesoscopic solid-state dye-sensitized solar cell based on trilamellar films of mesoscopic TiO2 nanocrystalline photoanode, a ZrO2 insulating layer and an indium tin oxide counter electrode (ITO-CE), which were screen-printed layer by layer on a single substrate. When the thickness of the ITO-CE was optimized to 2.1 μm, this very simple and fully printable solid-state DSSC with D102 dye and spiro-OMeTAD hole transport materials presents efficiencies of 1.73% when irradiated from the front side and 1.06% when irradiated from the rear side under a standard simulated sunlight condition (AM 1.5 Global, 100 mW cm(-2)). Higher parameters could be expected with a better transparent mesoscopic counter electrode and hole conductor for the printable monolithic mesoscopic solid-state DSSC.

Modeling of Water-Breathing Propulsion Systems Utilizing the Aluminum-Seawater Reaction and Solid-Oxide Fuel Cells

DTIC Science & Technology

2011-01-01

ABSTRACT Title of Document: MODELING OF WATER-BREATHING PROPULSION SYSTEMS UTILIZING THE ALUMINUM-SEAWATER REACTION AND SOLID...Hybrid Aluminum Combustor (HAC): a novel underwater power system based on the exothermic reaction of aluminum with seawater. The system is modeled ...using a NASA-developed framework called Numerical Propulsion System Simulation (NPSS) by assembling thermodynamic models developed for each component

Simulation of pyrite oxidation in fresh mine tailings under near-neutral conditions.

PubMed

Alakangas, Lena; Lundberg, Angela; Nason, Peter

2012-08-01

Sulphidic residual products from ore processing may produce acid rock drainage, when exposed to oxygen and water. Predictions of the magnitude of ARD and sulphide oxidation rates are of great importance in mine planning because they can be used to minimize or eliminate ARD and the associated economic and environmental costs. To address the lack of field data of sulphide oxidation rate in fresh sulphide-rich tailings under near-neutral conditions, determination and simulation of the rate was performed in pilot-scale at Kristineberg, northern Sweden. The quality of the drainage water was monitored, along with oxygen and carbon dioxide concentrations. The chemical composition of the solid tailings was also determined. The field data were compared to predictions from simulations of pyrite oxidation using a 1-D numerical model. The simulations' estimates of the amount of Fe and S released over a seven year period (52 kg and 178 kg, respectively) were in reasonably good agreement with those obtained by analysing the tailings (34 kg and 155 kg, respectively). The discrepancy is probably due to the formation of secondary precipitates such as iron hydroxides and gypsum; which are not accounted for in the model. The observed mass transport of Fe and S (0.05 and 1.0 kg per year, respectively) was much lower than expected on the basis of the simulations and the core data. Neutralization reactions involving carbonates in the tailings result in a near-neutral pH at all depths except at the oxidation front (pH < 5), indicating that the dissolution of carbonates was too slow for the acid to be neutralized, which instead neutralized deeper down in the tailings. This was also indicated by the reduced abundance of solid Ca at greater depths and the high levels of carbon dioxide both of which are consistent with the dissolution of carbonates. It could be concluded that the near-neutral pH in the tailings has no decreasing effect on the rate of sulphide oxidation, but does reduce the concentrations of dissolved elements in the drainage water due to the formation of secondary minerals. This means that sulphide oxidation rates may be underestimated if determined from drainage alone.

High temperature oxidation behavior of interconnect coated with LSCF and LSM for solid oxide fuel cell by screen printing

NASA Astrophysics Data System (ADS)

Lee, Shyong; Chu, Chun-Lin; Tsai, Ming-Jui; Lee, Jye

2010-01-01

The current study examined the effect of La 0.6Sr 0.4Co 0.2Fe 0.8O 3 (LSCF) and La 0.7Sr 0.3MnO 3 (LSM) coatings on the electrical properties and oxidation resistance of Crofer22 APU at 800 °C hot air. LSCF and LSM were coated on Crofer22 APU by screen printing and sintered over temperatures ranging from 1000 to 1100 °C in N 2. The coated alloy was first checked for compositions, morphology and interface conditions and then treated in a simulated oxidizing environment at 800 °C for 200 h. After measuring the long-term electrical resistance, the area specific resistance (ASR) at 800 °C for the alloy coated with LSCF was less than its counterpart coated with LSM. This work used LSCF coating as a metallic interconnect to reduce working temperature for the solid oxide fuel cell.

Three dimensional electrochemical simulation of solid oxide fuel cell cathode based on microstructure reconstructed by marching cubes method

NASA Astrophysics Data System (ADS)

He, An; Gong, Jiaming; Shikazono, Naoki

2018-05-01

In the present study, a model is introduced to correlate the electrochemical performance of solid oxide fuel cell (SOFC) with the 3D microstructure reconstructed by focused ion beam scanning electron microscopy (FIB-SEM) in which the solid surface is modeled by the marching cubes (MC) method. Lattice Boltzmann method (LBM) is used to solve the governing equations. In order to maintain the geometries reconstructed by the MC method, local effective diffusivities and conductivities computed based on the MC geometries are applied in each grid, and partial bounce-back scheme is applied according to the boundary predicted by the MC method. From the tortuosity factor and overpotential calculation results, it is concluded that the MC geometry drastically improves the computational accuracy by giving more precise topology information.

Simulating the Stability of Colloidal Amorphous Iron Oxide in Natural Water

EPA Science Inventory

Considerable uncertainty exists as to whether existing thermodynamic equilibrium solid/water partitioning paradigms can be used to assess the mobility of insoluble manufactured nanomaterials in the aquatic environment. In this work, the traditional Derjaguin–Landau–Verwey–Overbee...

Solid oxide fuel cells fueled with reducible oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chuang, Steven S.; Fan, Liang Shih

A direct-electrochemical-oxidation fuel cell for generating electrical energy includes a cathode provided with an electrochemical-reduction catalyst that promotes formation of oxygen ions from an oxygen-containing source at the cathode, a solid-state reduced metal, a solid-state anode provided with an electrochemical-oxidation catalyst that promotes direct electrochemical oxidation of the solid-state reduced metal in the presence of the oxygen ions to produce electrical energy, and an electrolyte disposed to transmit the oxygen ions from the cathode to the solid-state anode. A method of operating a solid oxide fuel cell includes providing a direct-electrochemical-oxidation fuel cell comprising a solid-state reduced metal, oxidizing themore » solid-state reduced metal in the presence of oxygen ions through direct-electrochemical-oxidation to obtain a solid-state reducible metal oxide, and reducing the solid-state reducible metal oxide to obtain the solid-state reduced metal.« less

Hexavalent Chromium Generation within Naturally Structured Soils and Sediments

DOE PAGES

Hausladen, Debra M.; Fendorf, Scott

2017-01-13

Chromium(VI) produced from the oxidation of indigenous Cr(III) minerals is increasingly being recognized as a threat to groundwater quality. A critical determinant of Cr(VI) generation within soils and sediments is the necessary interaction of two low-solubility phases$-$Cr(III) silicates or (hydr)oxides and Mn(III/IV) oxides—that lead to its production. Here in this paper, we investigate the potential for Cr(III) oxidation by Mn oxides within fixed solid matrices common to soils and sediments. Artificial aggregates were constructed from Cr(OH) 3- and Cr 0.25Fe 0.75(OH) 3-coated quartz grains and either mixed with synthetic birnessite or inoculated with the Mn(II)-oxidizing bacterium Leptothrix cholodnii. In aggregatesmore » simulating low organic carbon environments, we observe Cr(VI) concentrations within advecting solutes at levels more than twenty-times the California drinking water standard. Chromium(VI) production is highly dependent on Cr-mineral solubility; increasing Fe-substitution (x = 0 to x = 0.75) decreases the solubility of the solid and concomitantly decreases total Cr(VI) generation by 37%. In environments with high organic carbon, reducing conditions within aggregate cores (microbially) generate sufficient Fe(II) to suppress Cr(VI) efflux. Our results illustrate Cr(VI) generation from reaction with Mn oxides within structured media simulating soils and sediments and provide insight into how fluctuating hydrologic and redox conditions impact coupled processes controlling Cr and Mn cycling.« less

Direct modeling of the electrochemistry in the three-phase boundary of solid oxide fuel cell anodes by density functional theory: a critical overview.

PubMed

Shishkin, M; Ziegler, T

2014-02-07

The first principles modeling of electrochemical reactions has proven useful for the development of efficient, durable and low cost solid oxide full cells (SOFCs). In this account we focus on recent advances in modeling of structural, electronic and catalytic properties of the SOFC anodes based on density functional theory (DFT) first principle calculations. As a starting point, we highlight that the adequate analysis of cell electrochemistry generally requires modeling of chemical reactions at the metal/oxide interface rather than on individual metal or oxide surfaces. The atomic models of Ni/YSZ and Ni/CeO2 interfaces, required for DFT simulations of reactions on SOFC anodes are discussed next, together with the analysis of the electronic structure of these interfaces. Then we proceed to DFT-based findings on charge transfer mechanisms during redox reactions on these two anodes. We provide a comparison of the electronic properties of Ni/YSZ and Ni/CeO2 interfaces and present an interpretation of their different chemical performances. Subsequently we discuss the computed energy pathways of fuel oxidation mechanisms, obtained by various groups to date. We also discuss the results of DFT studies combined with microkinetic modeling as well as the results of kinetic Monte Carlo simulations. In conclusion we summarize the key findings of DFT modeling of metal/oxide interfaces to date and highlight possible directions in the future modeling of SOFC anodes.

Hexavalent Chromium Generation within Naturally Structured Soils and Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hausladen, Debra M.; Fendorf, Scott

Chromium(VI) produced from the oxidation of indigenous Cr(III) minerals is increasingly being recognized as a threat to groundwater quality. A critical determinant of Cr(VI) generation within soils and sediments is the necessary interaction of two low-solubility phases$-$Cr(III) silicates or (hydr)oxides and Mn(III/IV) oxides—that lead to its production. Here in this paper, we investigate the potential for Cr(III) oxidation by Mn oxides within fixed solid matrices common to soils and sediments. Artificial aggregates were constructed from Cr(OH) 3- and Cr 0.25Fe 0.75(OH) 3-coated quartz grains and either mixed with synthetic birnessite or inoculated with the Mn(II)-oxidizing bacterium Leptothrix cholodnii. In aggregatesmore » simulating low organic carbon environments, we observe Cr(VI) concentrations within advecting solutes at levels more than twenty-times the California drinking water standard. Chromium(VI) production is highly dependent on Cr-mineral solubility; increasing Fe-substitution (x = 0 to x = 0.75) decreases the solubility of the solid and concomitantly decreases total Cr(VI) generation by 37%. In environments with high organic carbon, reducing conditions within aggregate cores (microbially) generate sufficient Fe(II) to suppress Cr(VI) efflux. Our results illustrate Cr(VI) generation from reaction with Mn oxides within structured media simulating soils and sediments and provide insight into how fluctuating hydrologic and redox conditions impact coupled processes controlling Cr and Mn cycling.« less

Molecular dynamics simulations of Li transport between cathode crystals

NASA Astrophysics Data System (ADS)

Garofalini, S. H.

The molecular dynamics (MD) computer simulation technique has been used to study the effect of an amorphous intergranular film (IGF) present in a polycrystalline cathode on Li transport. The solid electrolyte is a model lithium silicate glass while the cathode is a nanocrystalline vanadia with an amorphous V 2O 5 IGF separating the crystals. Thin (˜1 to a few nanometer thick) IGFs are known to be present in most polycrystalline oxide materials. However, the role of such a film on Li transport in oxide cathodes has not been addressed. Current scanning probe microscopy (SPM) studies have shown that the orientation of the layered nanocrystalline vanadia crystals near the cathode/solid electrolyte interface is not optimized for Li ion transport. While the precise structure of the material between the crystals has not been identified, initially it can be initially considered as likely to be a thin non-crystalline (amorphous) film. This is based on the ubiquitous presence of such a structure in other polycrystalline oxides. Also, and with more relevance to the materials used in thin film batteries, an amorphous film can be expected to form between nanocrystals that crystallized from an amorphous matrix, as would be the case in a deposited thin film cathode. Consistent with simulations of Li transport in amorphous vanadia, the current simulations show that Li ions diffuse more rapidly into the amorphous intergranular thin film than into the layered vanadia with the (0 0 1) planes parallel to the cathode/electrolyte interface.

Analysis of high mass resolution PTR-TOF mass spectra from 1,3,5-trimethylbenzene (TMB) environmental chamber experiments

NASA Astrophysics Data System (ADS)

Müller, M.; Graus, M.; Wisthaler, A.; Hansel, A.; Metzger, A.; Dommen, J.; Baltensperger, U.

2011-09-01

A series of 1,3,5-trimethylbenzene (TMB) photo-oxidation experiments was performed in the 27-m3 Paul Scherrer Institute environmental chamber under various NOx conditions. A University of Innsbruck prototype high resolution Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOF) was used for measurements of gas and particulate phase organics. The gas phase mass spectrum displayed ~200 ion signals during the TMB photo-oxidation experiments. Molecular formulas CNmHnNoOp were determined and ion signals were separated and grouped according to their C, O and N numbers. This allowed to determine the time evolution of the O:C ratio and of the average carbon oxidation state OSC of the reaction mixture. Both quantities were compared with master chemical mechanism (MCMv3.1) simulations. The O:C ratio in the particle phase was about twice the O:C ratio in the gas phase. Average carbon oxidation states of secondary organic aerosol (SOA) samples OSCSOA were in the range of -0.34 to -0.31, in agreement with expected average carbon oxidation states of fresh SOA (OSC = -0.5 - 0).

Analysis of high mass resolution PTR-TOF mass spectra from 1,3,5-trimethylbenzene (TMB) environmental chamber experiments

NASA Astrophysics Data System (ADS)

Müller, M.; Graus, M.; Wisthaler, A.; Hansel, A.; Metzger, A.; Dommen, J.; Baltensperger, U.

2012-01-01

A series of 1,3,5-trimethylbenzene (TMB) photo-oxidation experiments was performed in the 27-m3 Paul Scherrer Institute environmental chamber under various NOx conditions. A University of Innsbruck prototype high resolution Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOF) was used for measurements of gas and particulate phase organics. The gas phase mass spectrum displayed ~200 ion signals during the TMB photo-oxidation experiments. Molecular formulas CmHnNoOp were determined and ion signals were separated and grouped according to their C, O and N numbers. This allowed to determine the time evolution of the O:C ratio and of the average carbon oxidation state OSC of the reaction mixture. Both quantities were compared with master chemical mechanism (MCMv3.1) simulations. The O:C ratio in the particle phase was about twice the O:C ratio in the gas phase. Average carbon oxidation states of secondary organic aerosol (SOA) samples OSCSOA were in the range of -0.34 to -0.31, in agreement with expected average carbon oxidation states of fresh SOA (OSC = -0.5-0).

Monolith catalysts for closed-cycle carbon dioxide lasers

NASA Technical Reports Server (NTRS)

Herz, Richard K.

1994-01-01

The general subject area of the project involved the development of solid catalysts that have high activity at low temperature for the oxidation of gases such as CO. The original application considered was CO oxidation in closed-cycle CO2 lasers. The scope of the project was subsequently extended to include oxidation of gases in addition to CO and applications such as air purification and exhaust gas emission control. The primary objective of the final phase grant was to develop design criteria for the formulation of new low-temperature oxidation catalysts utilizing Monte Carlo simulations of reaction over NASA-developed catalysts.

Viscous properties of aluminum oxide nanotubes and aluminium oxide nanoparticles - silicone oil suspensions

NASA Astrophysics Data System (ADS)

Thapa, Ram; French, Steven; Delgado, Adrian; Ramos, Carlos; Gutierrez, Jose; Chipara, Mircea; Lozano, Karen

2010-03-01

Electrorheological (ER) fluids consisting of γ-aluminum oxide nanotubes and γ-aluminum oxide nanoparticles dispersed within silicone oil were prepared. The relationship between shear stress and shear rate was measured and theoretically simulated by using an extended Bingham model for both the rheological and electrorheological features of these systems. Shear stress and viscosity showed a sharp increase for the aluminum oxide nanotubes suspensions subjected to applied electric fields whereas aluminum oxide nanoparticles suspensions showed a moderate change. It was found that the transition from liquid to solid state (mediated by the applied electric field) can be described by a power law and that for low applied voltages the relationship is almost linear.

Heat resistant alloys as interconnect materials of reduced temperature SOFCs

NASA Astrophysics Data System (ADS)

Jian, Li; Jian, Pu; Guangyuan, Xie; Shunxu, Wang; Jianzhong, Xiao

Heat-resistant alloys, Haynes 230 and SS310, were exposed to air and humidified H 2 at 750 °C for up to 1000 h, respectively, simulating the environments in reduced temperature solid oxide fuel cells (SOFCs). The oxidized samples were characterized by using SEM, EDS and X-ray diffraction to obtain the morphology, thickness, composition and crystal structure of the oxide scales. A mechanism for the formation of metallic Ni-rich nodules on top of the oxide scale in Haynes 230 sample oxidized in humidified H 2 was established. Thermodynamic analysis confirmed that MnCr 2O 4 is the favored spinel phase, together with Cr 2O 3, in the oxide scales.

Ion irradiation of the native oxide/silicon surface increases the thermal boundary conductance across aluminum/silicon interfaces

NASA Astrophysics Data System (ADS)

Gorham, Caroline S.; Hattar, Khalid; Cheaito, Ramez; Duda, John C.; Gaskins, John T.; Beechem, Thomas E.; Ihlefeld, Jon F.; Biedermann, Laura B.; Piekos, Edward S.; Medlin, Douglas L.; Hopkins, Patrick E.

2014-07-01

The thermal boundary conductance across solid-solid interfaces can be affected by the physical properties of the solid boundary. Atomic composition, disorder, and bonding between materials can result in large deviations in the phonon scattering mechanisms contributing to thermal boundary conductance. Theoretical and computational studies have suggested that the mixing of atoms around an interface can lead to an increase in thermal boundary conductance by creating a region with an average vibrational spectra of the two materials forming the interface. In this paper, we experimentally demonstrate that ion irradiation and subsequent modification of atoms at solid surfaces can increase the thermal boundary conductance across solid interfaces due to a change in the acoustic impedance of the surface. We measure the thermal boundary conductance between thin aluminum films and silicon substrates with native silicon dioxide layers that have been subjected to proton irradiation and post-irradiation surface cleaning procedures. The thermal boundary conductance across the Al/native oxide/Si interfacial region increases with an increase in proton dose. Supported with statistical simulations, we hypothesize that ion beam mixing of the native oxide and silicon substrate within ˜2.2nm of the silicon surface results in the observed increase in thermal boundary conductance. This ion mixing leads to the spatial gradation of the silicon native oxide into the silicon substrate, which alters the acoustic impedance and vibrational characteristics at the interface of the aluminum film and native oxide/silicon substrate. We confirm this assertion with picosecond acoustic analyses. Our results demonstrate that under specific conditions, a "more disordered and defected" interfacial region can have a lower resistance than a more "perfect" interface.

Fuel cell system modeling for solid oxide fuel cell/gas turbine hybrid power plants, Part I: Modeling and simulation framework

NASA Astrophysics Data System (ADS)

Leucht, Florian; Bessler, Wolfgang G.; Kallo, Josef; Friedrich, K. Andreas; Müller-Steinhagen, H.

A sustainable future power supply requires high fuel-to-electricity conversion efficiencies even in small-scale power plants. A promising technology to reach this goal is a hybrid power plant in which a gas turbine (GT) is coupled with a solid oxide fuel cell (SOFC). This paper presents a dynamic model of a pressurized SOFC system consisting of the fuel cell stack with combustion zone and balance-of-plant components such as desulphurization, humidification, reformer, ejector and heat exchangers. The model includes thermal coupling between the different components. A number of control loops for fuel and air flows as well as power management are integrated in order to keep the system within the desired operation window. Models and controls are implemented in a MATLAB/SIMULINK environment. Different hybrid cycles proposed earlier are discussed and a preferred cycle is developed. Simulation results show the prospects of the developed modeling and control system.

Solid oxide fuel cell hybrid system: Control strategy for stand-alone configurations

NASA Astrophysics Data System (ADS)

Ferrari, Mario L.

2011-03-01

The aim of this study is the development and testing of a control system for solid oxide fuel cell hybrid systems through dynamic simulations. Due to the complexity of these cycles, several parameters, such as the turbine rotational speed, the temperatures within the fuel cell, the differential pressure between the anodic and the cathodic side and the Steam-To-Carbon Ratio need to be monitored and kept within safe limits. Furthermore, in stand-alone conditions the system response to load variations is required to meet the global plant power demand at any time, supporting global load variations and avoiding dangerous or unstable conditions. The plant component models and their integration were carried out in previous studies. This paper focuses on the control strategy required for managing the net electrical power from the system, avoiding malfunctions or damage. Once the control system was developed and tuned, its performance was evaluated by simulating the transient behaviour of the whole hybrid cycle: the results for several operating conditions are presented and discussed.

Hybrids - Best of both worlds. [liquid and solid propellants mated for safe reliable and low cost launch vehicles

NASA Technical Reports Server (NTRS)

Goldberg, Ben E.; Wiley, Dan R.

1991-01-01

An overview is presented of hybrid rocket propulsion systems whereby combining solids and liquids for launch vehicles could produce a safe, reliable, and low-cost product. The primary subsystems of a hybrid system consist of the oxidizer tank and feed system, an injector system, a solid fuel grain enclosed in a pressure vessel case, a mixing chamber, and a nozzle. The hybrid rocket has an inert grain, which reduces costs of development, transportation, manufacturing, and launch by avoiding many safety measures that must be taken when operating with solids. Other than their use in launch vehicles, hybrids are excellent for simulating the exhaust of solid rocket motors for material development.

Multi scale modeling of ignition and combustion of micro and nano aluminum particles

NASA Astrophysics Data System (ADS)

Puri, Puneesh

With renewed interest in nano scale energetic materials like aluminum, many fundamental issues concerning the ignition and combustion characteristics at nano scales, remain to be clarified. The overall aim of the current study is the establishment of a unified theory accommodating the various processes and mechanisms involved in the combustion and ignition of aluminum particles at micro and nano scales. A comprehensive review on the ignition and combustion of aluminum particles at multi scales was first performed identifying various processes and mechanisms involved. Research focus was also placed on the establishment of a Molecular Dynamics (MD) simulation tool to investigate the characteristics of nano-particulate aluminum through three major studies. The general computational framework involved parallelized preprocessing, post-processing and main code with capability to simulate different ensembles using appropriate algorithms. Size dependence of melting temperature of pure aluminum particles was investigated in the first study. Phenomena like dynamic coexistence of solid and liquid phase and effect of surface charges on melting were explored. The second study involved the study of effect of defects in the form of voids on melting of bulk and particulate phase aluminum. The third MD study was used to analyze the thermo-mechanical behavior of nano-sized aluminum particles with total diameter of 5-10 nm and oxide thickness of 1-2.5 nm. The ensuing solid-solid and solid-liquid phase changes in the core and shell, stresses developed within the shell, and the diffusion of aluminum cations in the oxide layer, were explored in depth for amorphous and crystalline oxide layers. In the limiting case, the condition for pyrophoricity/explosivity of nano-particulate aluminum was analyzed and modified. The size dependence of thermodynamic properties at nano scales were considered and incorporated into the existing theories developed for micro and larger scales. Finally, a phenomenological theory for ignition and combustion of aluminum particles was proposed. The whole time history from ignition till particle burnout was divided into five stages. An attempt was made to explore different modes of ignition based on the effect of pressure, temperature, oxidizer, oxide thickness and particle diameter and was investigated using length and time scales involved during ignition and combustion.

Investigation into the effects of sulfur on syngas reforming inside a solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Li, Ting Shuai; Xu, Min; Gao, Chongxin; Wang, Baoqing; Liu, Xiyun; Li, Baihai; Wang, Wei Guo

2014-07-01

The electrochemical performance and long-term durability of a solid oxide fuel cell have been evaluated with a simulated coal syngas containing 2 ppm H2S as fuel. The resulting impedance spectra indicate that no observable power loss is caused by the addition of 2 ppm H2S, and the cell shows stability of nearly 500 h at 0.625 A cm-2. The composition of mixed gas is analyzed both at a current load of 0.625 A cm-2 and open circuit state. Hydrogen and carbon monoxide are directly consumed as fuels at the anode side, whereas methane stays unchanged during the operation. It seems the internal carbohydrate reforming and impurity poisoning interacts and weakens the poisoning effects. The oxidation of H2 and the water gas shift reaction take advantages over methane reforming at the cell operational conditions.

Enhanced photothermal effect in reduced graphene oxide in solid-state

NASA Astrophysics Data System (ADS)

Sahadev, Nishaina; Anappara, Aji A.

2017-11-01

We report on a giant photothermal effect in few-layer Reduced Graphene Oxide (RGO) in powder form. Graphite oxide synthesized following modified Hummer's method was thermally exfoliated and reduced to obtain RGO consisting of ˜8-10 layers. Upon irradiation with an incoherent, broad-band light source (wavelengths ranging from 250 to 450 nm), an enormous photothermal effect was observed. The heat generated by RGO determined from the isothermal differential photocalorimetric technique is as high as ˜319 W/g resulting from the dominant non-radiative de-excitation of photoexcited electrons due to the absence of a radiative pathway. A practical applicability was demonstrated using a commercial thermoelectric generator wherein upon illumination from a solar-simulator, an open voltage in the mV range was developed, giving a direct proof of the exothermic effect in powder RGO upon light illumination. Herewith, we have demonstrated a proof-of-concept of photothermal effects in solid-state RGO.

Solid state electrochemical current source

DOEpatents

Potanin, Alexander Arkadyevich; Vedeneev, Nikolai Ivanovich

2002-04-30

A cathode and a solid state electrochemical cell comprising said cathode, a solid anode and solid fluoride ion conducting electrolyte. The cathode comprises a metal oxide and a compound fluoride containing at least two metals with different valences. Representative compound fluorides include solid solutions of bismuth fluoride and potassium fluoride; and lead fluoride and potassium fluoride. Representative metal oxides include copper oxide, lead oxide, manganese oxide, vanadium oxide and silver oxide.

A coupled mechanical-chemical model for reflecting the influence of stress on oxidation reactions in thermal barrier coating

NASA Astrophysics Data System (ADS)

Chen, Lin; Yueming, Li

2018-06-01

In this paper, a coupled mechanical-chemical model is established based on the thermodynamic framework, in which the contribution of chemical expansion to free energy is introduced. The stress-dependent chemical potential equilibrium at the gas-solid interface and the stress gradient-dependent diffusion equation as well as a so-called generalized force which is conjugate to the oxidation rate are derived from the proposed model, which could reflect the influence of stresses on the oxidation reaction. Based on the proposed coupled mechanical-chemical model, a user element subroutine is developed in ABAQUS. The numerical simulation of the high temperature oxidation in the thermal barrier coating is carried out to verify the accuracy of the proposed model, and then the influence of stresses on the oxidation reaction is investigated. In thermally grown oxide, the considerable stresses would be induced by permanent volumetric swelling during the oxidation. The stresses play an important role in the chemical potential equilibrium at the gas-solid interface and strongly affect the oxidation reaction. The gradient of the stresses, however, only occurs in the extremely thin oxidation front layer, which plays a very limited role in the oxidation reaction. The generalized force could be divided into the stress-dependent and the stress-independent parts. Comparing with the stress-independent part, the stress-dependent part is smaller, which has little influence on oxidation reaction.

Ignition of Liquid Fuel Spray and Simulated Solid Rocket Fuel by Photoignition of Carbon Nanotube Utilizing a Camera Flash

DTIC Science & Technology

2011-12-01

10,11 There has been a recent report on the photoignition of graphene oxide for fuel ignition applications.12 In this report, we will describe the...slide Aluminum foil Glass petri dish Xe flash Camera Sample Black spray paint Figure 2- Schematic and photographs of the experimental setup...Gilje, Sergey Dubin, Alireza Badakhshan, Jabari Farrar, Stephen. A. Danczyk, Richard B. Kaner, “Photothermal Deoxygenation of Graphene Oxide for

A finite element analysis modeling tool for solid oxide fuel cell development: coupled electrochemistry, thermal and flow analysis in MARC®

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khaleel, Mohammad A.; Lin, Zijing; Singh, Prabhakar

2004-05-03

A 3D simulation tool for modeling solid oxide fuel cells is described. The tool combines the versatility and efficiency of a commercial finite element analysis code, MARC{reg_sign}, with an in-house developed robust and flexible electrochemical (EC) module. Based upon characteristic parameters obtained experimentally and assigned by the user, the EC module calculates the current density distribution, heat generation, and fuel and oxidant species concentration, taking the temperature profile provided by MARC{reg_sign} and operating conditions such as the fuel and oxidant flow rate and the total stack output voltage or current as the input. MARC{reg_sign} performs flow and thermal analyses basedmore » on the initial and boundary thermal and flow conditions and the heat generation calculated by the EC module. The main coupling between MARC{reg_sign} and EC is for MARC{reg_sign} to supply the temperature field to EC and for EC to give the heat generation profile to MARC{reg_sign}. The loosely coupled, iterative scheme is advantageous in terms of memory requirement, numerical stability and computational efficiency. The coupling is iterated to self-consistency for a steady-state solution. Sample results for steady states as well as the startup process for stacks with different flow designs are presented to illustrate the modeling capability and numerical performance characteristic of the simulation tool.« less

Modeling and experimental performance of an intermediate temperature reversible solid oxide cell for high-efficiency, distributed-scale electrical energy storage

NASA Astrophysics Data System (ADS)

Wendel, Christopher H.; Gao, Zhan; Barnett, Scott A.; Braun, Robert J.

2015-06-01

Electrical energy storage is expected to be a critical component of the future world energy system, performing load-leveling operations to enable increased penetration of renewable and distributed generation. Reversible solid oxide cells, operating sequentially between power-producing fuel cell mode and fuel-producing electrolysis mode, have the capability to provide highly efficient, scalable electricity storage. However, challenges ranging from cell performance and durability to system integration must be addressed before widespread adoption. One central challenge of the system design is establishing effective thermal management in the two distinct operating modes. This work leverages an operating strategy to use carbonaceous reactant species and operate at intermediate stack temperature (650 °C) to promote exothermic fuel-synthesis reactions that thermally self-sustain the electrolysis process. We present performance of a doped lanthanum-gallate (LSGM) electrolyte solid oxide cell that shows high efficiency in both operating modes at 650 °C. A physically based electrochemical model is calibrated to represent the cell performance and used to simulate roundtrip operation for conditions unique to these reversible systems. Design decisions related to system operation are evaluated using the cell model including current density, fuel and oxidant reactant compositions, and flow configuration. The analysis reveals tradeoffs between electrical efficiency, thermal management, energy density, and durability.

Nanocrystalline cerium oxide materials for solid fuel cell systems

DOEpatents

Brinkman, Kyle S

2015-05-05

Disclosed are solid fuel cells, including solid oxide fuel cells and PEM fuel cells that include nanocrystalline cerium oxide materials as a component of the fuel cells. A solid oxide fuel cell can include nanocrystalline cerium oxide as a cathode component and microcrystalline cerium oxide as an electrolyte component, which can prevent mechanical failure and interdiffusion common in other fuel cells. A solid oxide fuel cell can also include nanocrystalline cerium oxide in the anode. A PEM fuel cell can include cerium oxide as a catalyst support in the cathode and optionally also in the anode.

Enhanced Chemical Cleaning: A New Process for Chemically Cleaning Savannah River Waste Tanks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ketusky, Edward; Spires, Renee; Davis, Neil

2009-02-11

At the Savannah River Site (SRS) there are 49 High Level Waste (HLW) tanks that eventually must be emptied, cleaned, and closed. The current method of chemically cleaning SRS HLW tanks, commonly referred to as Bulk Oxalic Acid Cleaning (BOAC), requires about a half million liters (130,000 gallons) of 8 weight percent (wt%) oxalic acid to clean a single tank. During the cleaning, the oxalic acid acts as the solvent to digest sludge solids and insoluble salt solids, such that they can be suspended and pumped out of the tank. Because of the volume and concentration of acid used, amore » significant quantity of oxalate is added to the HLW process. This added oxalate significantly impacts downstream processing. In addition to the oxalate, the volume of liquid added competes for the limited available tank space. A search, therefore, was initiated for a new cleaning process. Using TRIZ (Teoriya Resheniya Izobretatelskikh Zadatch or roughly translated as the Theory of Inventive Problem Solving), Chemical Oxidation Reduction Decontamination with Ultraviolet Light (CORD-UV{reg_sign}), a mature technology used in the commercial nuclear power industry was identified as an alternate technology. Similar to BOAC, CORD-UV{reg_sign} also uses oxalic acid as the solvent to dissolve the metal (hydr)oxide solids. CORD-UV{reg_sign} is different, however, since it uses photo-oxidation (via peroxide/UV or ozone/UV to form hydroxyl radicals) to decompose the spent oxalate into carbon dioxide and water. Since the oxalate is decomposed and off-gassed, CORD-UV{reg_sign} would not have the negative downstream oxalate process impacts of BOAC. With the oxalate destruction occurring physically outside the HLW tank, re-precipitation and transfer of the solids, as well as regeneration of the cleaning solution can be performed without adding additional solids, or a significant volume of liquid to the process. With a draft of the pre-conceptual Enhanced Chemical Cleaning (ECC) flowsheet, taking full advantage of the many CORD-UV{reg_sign} benefits, performance demonstration testing was initiated using available SRS sludge simulant. The demonstration testing confirmed that ECC is a viable technology, as it can dissolve greater than 90% of the sludge simulant and destroy greater than 90% of the oxalates. Additional simulant and real waste testing are planned.« less

An Ultrastable Heterobimetallic Uranium(IV)/Vanadium(III) Solid Compound Protected by a Redox-Active Phosphite Ligand: Crystal Structure, Oxidative Dissolution, and First-Principles Simulation.

PubMed

Gui, Daxiang; Dai, Xing; Zheng, Tao; Wang, Xiangxiang; Silver, Mark A; Chen, Lanhua; Zhang, Chao; Diwu, Juan; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

2018-02-05

The first heterobimetallic uranium(IV)/vanadium(III) phosphite compound, Na 2 UV 2 (HPO 3 ) 6 (denoted as UVP), was synthesized via an in situ redox-active hydrothermal reaction. It exhibits superior hydrolytic and antioxidant stability compared to the majority of structures containing low-valent uranium or vanadium, further elucidated by first-principles simulations, and therefore shows potential applications in nuclear waste management.

SITE EMERGING TECHNOLOGY SUMMARY: INTEGRATION OF PHOTOCATALYTIC OXIDATION WITH AIR STRIPPING OF CONTAMINATED AQUIFERS

EPA Science Inventory

In a recently completed test program, bench-scale laboratory studies at Arizona State University (ASU) in Tempe, AZ, and pilot-scale studies in a simulated field test situation at Zentox Corp in Ocala, FL, were performed to evaluate the integration of gas-solid ultraviolet (UV) p...

LINKING SOLID PHASE SPECIATION OF PB SEQUESTERED TO BIRNESSITE TO ORAL PB BIOACCESSIBLITY: IMPLICATIONS FOR SOIL REMEDIATION

EPA Science Inventory

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of lead-contaminated soils. In this study, Pb was sorbed to a model soil mineral, birnessite, and was placed in a simulated gastrointestinal tract (in vitro) to simula...

Model-based development of a fault signature matrix to improve solid oxide fuel cell systems on-site diagnosis

NASA Astrophysics Data System (ADS)

Polverino, Pierpaolo; Pianese, Cesare; Sorrentino, Marco; Marra, Dario

2015-04-01

The paper focuses on the design of a procedure for the development of an on-field diagnostic algorithm for solid oxide fuel cell (SOFC) systems. The diagnosis design phase relies on an in-deep analysis of the mutual interactions among all system components by exploiting the physical knowledge of the SOFC system as a whole. This phase consists of the Fault Tree Analysis (FTA), which identifies the correlations among possible faults and their corresponding symptoms at system components level. The main outcome of the FTA is an inferential isolation tool (Fault Signature Matrix - FSM), which univocally links the faults to the symptoms detected during the system monitoring. In this work the FTA is considered as a starting point to develop an improved FSM. Making use of a model-based investigation, a fault-to-symptoms dependency study is performed. To this purpose a dynamic model, previously developed by the authors, is exploited to simulate the system under faulty conditions. Five faults are simulated, one for the stack and four occurring at BOP level. Moreover, the robustness of the FSM design is increased by exploiting symptom thresholds defined for the investigation of the quantitative effects of the simulated faults on the affected variables.

Adaptive control paradigm for photovoltaic and solid oxide fuel cell in a grid-integrated hybrid renewable energy system.

PubMed

Mumtaz, Sidra; Khan, Laiq

2017-01-01

The hybrid power system (HPS) is an emerging power generation scheme due to the plentiful availability of renewable energy sources. Renewable energy sources are characterized as highly intermittent in nature due to meteorological conditions, while the domestic load also behaves in a quite uncertain manner. In this scenario, to maintain the balance between generation and load, the development of an intelligent and adaptive control algorithm has preoccupied power engineers and researchers. This paper proposes a Hermite wavelet embedded NeuroFuzzy indirect adaptive MPPT (maximum power point tracking) control of photovoltaic (PV) systems to extract maximum power and a Hermite wavelet incorporated NeuroFuzzy indirect adaptive control of Solid Oxide Fuel Cells (SOFC) to obtain a swift response in a grid-connected hybrid power system. A comprehensive simulation testbed for a grid-connected hybrid power system (wind turbine, PV cells, SOFC, electrolyzer, battery storage system, supercapacitor (SC), micro-turbine (MT) and domestic load) is developed in Matlab/Simulink. The robustness and superiority of the proposed indirect adaptive control paradigm are evaluated through simulation results in a grid-connected hybrid power system testbed by comparison with a conventional PI (proportional and integral) control system. The simulation results verify the effectiveness of the proposed control paradigm.

Adaptive control paradigm for photovoltaic and solid oxide fuel cell in a grid-integrated hybrid renewable energy system

PubMed Central

Khan, Laiq

2017-01-01

The hybrid power system (HPS) is an emerging power generation scheme due to the plentiful availability of renewable energy sources. Renewable energy sources are characterized as highly intermittent in nature due to meteorological conditions, while the domestic load also behaves in a quite uncertain manner. In this scenario, to maintain the balance between generation and load, the development of an intelligent and adaptive control algorithm has preoccupied power engineers and researchers. This paper proposes a Hermite wavelet embedded NeuroFuzzy indirect adaptive MPPT (maximum power point tracking) control of photovoltaic (PV) systems to extract maximum power and a Hermite wavelet incorporated NeuroFuzzy indirect adaptive control of Solid Oxide Fuel Cells (SOFC) to obtain a swift response in a grid-connected hybrid power system. A comprehensive simulation testbed for a grid-connected hybrid power system (wind turbine, PV cells, SOFC, electrolyzer, battery storage system, supercapacitor (SC), micro-turbine (MT) and domestic load) is developed in Matlab/Simulink. The robustness and superiority of the proposed indirect adaptive control paradigm are evaluated through simulation results in a grid-connected hybrid power system testbed by comparison with a conventional PI (proportional and integral) control system. The simulation results verify the effectiveness of the proposed control paradigm. PMID:28329015

Characterization of deposits formed on diesel injectors in field test and from thermal oxidative degradation of n-hexadecane in a laboratory reactor

PubMed Central

Venkataraman, Ramya; Eser, Semih

2008-01-01

Solid deposits from commercially available high-pressure diesel injectors (HPDI) were analyzed to study the solid deposition from diesel fuel during engine operation. The structural and chemical properties of injector deposits were compared to those formed from the thermal oxidative stressing of a diesel fuel range model compound, n-hexadecane at 160°C and 450 psi for 2.5 h in a flow reactor. Both deposits consist of polyaromatic compounds (PAH) with oxygen moieties. The similarities in structure and composition of the injector deposits and n-hexadecane deposits suggest that laboratory experiments can simulate thermal oxidative degradation of diesel in commercial injectors. The formation of PAH from n-hexadecane showed that aromatization of straight chain alkanes and polycondensation of aromatic rings was possible at temperatures as low as 160°C in the presence of oxygen. A mechanism for an oxygen-assisted aromatization of cylcoalkanes is proposed. PMID:19091086

Study by AES, EELS Spectroscopy of electron Irradiation on InP and InPO4/InP in comparison with Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Lounis, Z.; Bouslama, M.; Hamaida, K.; Jardin, C.; Abdellaoui, A.; Ouerdane, A.; Ghaffour, M.; Berrouachedi, N.

2012-02-01

We give the great interest to characterise the InP and InPO4/InP submitted to electron beam irradiation owing to the Auger Electron Spectroscopy (AES) associated to both methods Electron Energy Loss Spectroscopy (EELS). The incident electron produces breaking of (In-P) chemical bonds. The electron beam even acts to stimulate oxidation of InP surface involving on the top layers. Other, the oxide InPO4 developed on InP does appear very sensitive to the irradiation due to electron beam shown by the monitoring of EELS spectra recorded versus the irradiated times of the surface. There appears a new oxide thought to be In2O3. We give the simulation methods Casino (Carlo simulation of electron trajectory in solids) for determination with accuracy the loss energy of backscattered electrons and compared with reports results have been obtained with EELS Spectroscopy. These techniques of spectroscopy alone do not be able to verify the affected depth during interaction process. So, using this simulation method, we determine the interaction of electrons in the matter.

Charge Behaviors around Oxide Device/Pseudo-Physiological Solution Interface with Molecular Dynamic Simulations

NASA Astrophysics Data System (ADS)

Maekawa, Yuki; Shibuta, Yasushi; Sakata, Toshiya

2013-12-01

In this study, we investigated the charge behaviors of ions and water molecules at the oxide device/pseudo-physiological solution interface by use of molecular dynamics (MD) simulations because the detection principle of semiconductor-based biosensors is based on the detection of charge density changes at the oxide sensing surface in physiological environments. In particular, we designed an alpha-quartz (100) surface with some charges corresponding to pH=5.5 so that the ionic behaviors for 500 mM each of Na+ and Cl- around the interface were calculated under the surface condition with charges, considering a real system. As a result of the simulation, we defined the region of Debye length from the calculated potential distribution, in which some parameters such as diffusion coefficient and the vibration of water molecules around the interface differed from those of the bulk solution. The elucidation of the solid/liquid interfacial behaviors by the simulation technique should deepen our understanding of the detection principle of semiconductor-based biosensors and will give guidelines for the design of a bio-interface in the field of biosensing technology, because they cannot be demonstrated experimentally.

Molecular dynamics simulations of oxide memory resistors (memristors).

PubMed

Savel'ev, S E; Alexandrov, A S; Bratkovsky, A M; Williams, R Stanley

2011-06-24

Reversible bipolar nanoswitches that can be set and read electronically in a solid-state two-terminal device are very promising for applications. We have performed molecular dynamics simulations that mimic systems with oxygen vacancies interacting via realistic potentials and driven by an external bias voltage. The competing short- and long-range interactions among charged mobile vacancies lead to density fluctuations and short-range ordering, while illustrating some aspects of observed experimental behavior, such as memristor polarity inversion. The simulations show that the 'localized conductive filaments' and 'uniform push/pull' models for memristive switching are actually two extremes of the one stochastic mechanism.

A novel structure photonic crystal fiber based on bismuth-oxide for optical parametric amplification

NASA Astrophysics Data System (ADS)

Jin, Cang; Yuan, Jinhui; Yu, Chongxiu

2010-11-01

The heavy metal oxide glasses containing bismuth such as bismuth sesquioxide show unique high refractive index. In addition, the bismuth-oxide based glass does not include toxic elements such as Pb, As, Se, Te, and exhibits well chemical, mechanical and thermal stability. Hence, it is used to fabricate high nonlinear fiber for nonlinear optical application. Although the bismuth-oxide based high nonlinear fiber can be fusion-spliced to conventional silica fibers and have above advantages, yet it suffers from large group velocity dispersion because of material chromatic dispersion which restricts its utility. In regard to this, the micro-structure was introduced to adjust the dispersion of bismuth-oxide high nonlinear fiber in the 1550nm wave-band. In this paper, a hexagonal solid-core micro-structure is developed to balance its dispersion and nonlinearity. Our simulation and calculation results show that the bismuth-oxide based photonic crystal fiber has near zero dispersion around 1550nm where the optical parametric amplification suitable wavelength is. Its dispersion slop in the communication wavelength range is also relatively flat. Moreover, both nonlinear coefficient and model filed distribution were simulated, respectively.

Effects of acid rain on grapevines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Forsline, P.L.; Musselman, R.C.; Dee, R.J.

1983-01-01

Mature vineyard-growing Concord grapevines (Vitis labrusca, Bailey) were sprayed with simulated acid rain solutions ranging from pH 2.5 to pH 5.5 both as acute treatments at anthesis and chronically throughout the season in 1980 and 1981. In 1981, eight additional varieties were also treated with simulated acid rain solutions at pH 2.75 and pH 3.25. With Concord in 1981, few foliar lesions on leaves were visible at pH 2.75. In contrast, many leaf lesions with decreased fruit soluble solids in the absence of acid rain leaf lesions at pH>2.5 remains unclear. Acute sprays (pH 2.75) at anthesis reduced pollen germinationmore » in four grape cultivars. However, fruit set was reduced in only one of these. Only the cultivars de Chaunac and Ives had reduced berry soluble solids with chronic weekly sprays at pH 2.75. Reduction in soluble solids was not associated with increased oxidant stipple (ozone injury) in Concord and de Chaunac cultivars, but this association was observed in Ives. There was no evidence that acid rain in combination with ozone increased oxidant stipple as occurs when ozone and SO/sub 2/ are combined. Grape yields were not influenced by acid rain treatments. There was no evidence that acid rain at ambient pH levels had negative effects on grape production or fruit quality.« less

Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

NASA Astrophysics Data System (ADS)

Dang-Long, T.; Quang-Tuyen, T.; Shiratori, Y.

2016-06-01

Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH4 and CO2 and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidate for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO2 reforming of CH4 and electrochemical oxidation of the produced syngas (H2-CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH4-CO2 mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO2 had strong influences on both reaction processes. The increase in CO2 partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH4-CO2 mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

Enzyme activity in terrestrial soil in relation to exploration of the Martian surface

NASA Technical Reports Server (NTRS)

Mclaren, A. D.

1974-01-01

Sensitive tests for the detection of extracellular enzyme activity in Martian soil was investigated using simulated Martian soil. Enzyme action at solid-liquid water interfaces and at low humidity were studied, and a kinetic scheme was devised and tested based on the growth of microorganisms and the oxidation of ammonium nitrite.

46 CFR 194.05-11 - Flammable solids and oxidizing materials-Detail requirements.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 46 Shipping 7 2011-10-01 2011-10-01 false Flammable solids and oxidizing materials-Detail... and Marking § 194.05-11 Flammable solids and oxidizing materials—Detail requirements. (a) Flammable solids and oxidizing materials used as chemical stores and reagents are governed by subparts 194.15 and...

46 CFR 194.05-11 - Flammable solids and oxidizing materials-Detail requirements.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Flammable solids and oxidizing materials-Detail... and Marking § 194.05-11 Flammable solids and oxidizing materials—Detail requirements. (a) Flammable solids and oxidizing materials used as chemical stores and reagents are governed by subparts 194.15 and...

Regenerative process and system for the simultaneous removal of particulates and the oxides of sulfur and nitrogen from a gas stream

DOEpatents

Cohen, M.R.; Gal, E.

1993-04-13

A process and system are described for simultaneously removing from a gaseous mixture, sulfur oxides by means of a solid sulfur oxide acceptor on a porous carrier, nitrogen oxides by means of ammonia gas and particulate matter by means of filtration and for the regeneration of loaded solid sulfur oxide acceptor. Finely-divided solid sulfur oxide acceptor is entrained in a gaseous mixture to deplete sulfur oxides from the gaseous mixture, the finely-divided solid sulfur oxide acceptor being dispersed on a porous carrier material having a particle size up to about 200 microns. In the process, the gaseous mixture is optionally pre-filtered to remove particulate matter and thereafter finely-divided solid sulfur oxide acceptor is injected into the gaseous mixture.

A study of pyrolysis of oil shale of the Leningrad deposit by solid heat carrier

NASA Astrophysics Data System (ADS)

Gerasimov, G. Ya; Khaskhachikh, V. V.; Potapov, O. P.

2017-11-01

The investigation of the oil shale pyrolysis with a solid heat carrier was carried out using the experimental retorting system that simulates the Galoter industrial process. This system allows verifying both fractional composition of the oil shale and solid heat carrier, and their ratio and temperature. The oil shale of the Leningradsky deposit was used in the work, and quartz sand was used as the solid heat carrier. It is shown that the yield of the shale oil under the pyrolysis with solid heat carrier exceeds by more than 20% the results received in the standard Fisher retort. Using ash as the solid heat carrier results in a decrease in the yield of oil and gas with simultaneous increase in the amount of the solid residue. This is due to the chemical interaction of the acid components of the vapor-gas mixture with the oxides of alkaline-earth metals that are part of the ash.

PEP Integrated Test D Run Report Caustic and Oxidative Leaching in UFP-VSL-T02A

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sevigny, Gary J.; Bredt, Ofelia P.; Burns, Carolyn A.

2009-12-11

Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed, constructed and operated as part of a plan to respond to issue M12, "Undemonstrated Leaching Processes" of the External Flowsheet Review Team (EFRT) issue response plan. The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. Themore » PEP replicates the WTP leaching processes using prototypic equipment and control strategies. The PEP also includes non-prototypic ancillary equipment to support the core processing. Two operating scenarios are currently being evaluated for the ultrafiltration process (UFP) and leaching operations. The first scenario (Test B and D) has caustic leaching performed in the UFP-2 ultrafiltration feed vessels (i.e., vessel UFP-VSL-T02A in the PEP and vessels UFP-VSL-00002A and B in the WTP PTF). The second scenario (Test A) has caustic leaching conducted in the UFP-1 ultrafiltration feed preparation vessels (i.e., vessels UFP-VSL-T01A and B in the PEP and vessels UFP VSL-00001A and B in the WTP PTF). In Test D, 19M sodium hydroxide (NaOH, caustic) was added to the waste slurry in the UFP VSL T02 vessel after the solids were concentrated to ~20% undissolved solids. The NaOH was added to leach solid aluminum compounds (e.g., gibbsite, boehmite). Caustic addition is followed by heating to 85°C using direct injection of steam to accelerate the leach process. The main difference of Test D compared to Test B is that the leach temperature is 85°C for 24 hrs as compared to 100°C for 12 hours. The other difference is the Test D simulant had Cr in the simulant from the start of processing and Test B had Cr added to adjust the simulant composition after aluminum leaching. Following the caustic leach, the UFP-VSL-T02A vessel contents are cooled using the vessel cooling jacket. The slurry was then concentrated to 17 wt% undissolved solids and washed with inhibited water to remove NaOH and other soluble salts. Next, the slurry was oxidatively leached using sodium permanganate to solubilize chrome. The slurry was then washed to remove the dissolved chrome and concentrated.« less

Simulation and optimization of ammonia removal at low temperature for a double channel oxidation ditch based on fully coupled activated sludge model (FCASM): a full-scale study.

PubMed

Yang, Min; Sun, Peide; Wang, Ruyi; Han, Jingyi; Wang, Jianqiao; Song, Yingqi; Cai, Jing; Tang, Xiudi

2013-09-01

An optimal operating condition for ammonia removal at low temperature, based on fully coupled activated sludge model (FCASM), was determined in a full-scale oxidation ditch process wastewater treatment plant (WWTP). The FCASM-based mechanisms model was calibrated and validated with the data measured on site. Several important kinetic parameters of the modified model were tested through respirometry experiment. Validated model was used to evaluate the relationship between ammonia removal and operating parameters, such as temperature (T), dissolved oxygen (DO), solid retention time (SRT) and hydraulic retention time of oxidation ditch (HRT). The simulated results showed that low temperature have a negative effect on the ammonia removal. Through orthogonal simulation tests of the last three factors and combination with the analysis of variance, the optimal operating mode acquired of DO, SRT, HRT for the WWTP at low temperature were 3.5 mg L(-1), 15 d and 14 h, respectively. Copyright © 2013 Elsevier Ltd. All rights reserved.

Engineered glass seals for solid-oxide fuel cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Surdoval, Wayne; Lara-Curzio, Edgar; Stevenson, Jeffry

2017-02-07

A seal for a solid oxide fuel cell includes a glass matrix having glass percolation therethrough and having a glass transition temperature below 650.degree. C. A deformable second phase material is dispersed in the glass matrix. The second phase material can be a compliant material. The second phase material can be a crushable material. A solid oxide fuel cell, a precursor for forming a seal for a solid oxide fuel cell, and a method of making a seal for a solid oxide fuel cell are also disclosed.

Electrochemical enhancement of nitric oxide removal from simulated lean-burn engine exhaust via solid oxide fuel cells.

PubMed

Huang, Ta-Jen; Wu, Chung-Ying; Lin, Yu-Hsien

2011-07-01

A solid oxide fuel cell (SOFC) unit is constructed with Ni-YSZ as the anode, YSZ as the electrolyte, and La(0.6)Sr(0.4)CoO(3)-Ce(0.9)Gd(0.1)O(1.95) as the cathode. The SOFC operation is performed at 600 °C with a cathode gas simulating the lean-burn engine exhaust and at various fixed voltage, at open-circuit voltage, and with an inert gas flowing over the anode side, respectively. Electrochemical enhancement of NO decomposition occurs when an operating voltage is generated; higher O(2) concentration leads to higher enhancement. Smaller NO concentration results in larger NO conversion. Higher operating voltage and higher O(2) concentration can lead to both higher NO conversion and lower fuel consumption. The molar rate of the consumption of the anode fuel can be very much smaller than that of NO to N(2) conversion. This makes the anode fuel consumed in the SOFC-DeNO(x) process to be much less than the equivalent amount of ammonia consumed in the urea-based selective catalytic reduction process. Additionally, the NO conversion increases with the addition of propylene and SO(2) into the cathode gas. These are beneficial for the application of the SOFC-DeNO(x) technology on treating diesel and other lean-burn engine exhausts.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K; Daniel, Claus

2013-05-28

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K.; Daniel, Claus

2015-11-19

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Improving Tribological Properties of Multialkylated Cyclopentanes under Simulated Space Environment: Two Feasible Approaches.

PubMed

Fan, Xiaoqiang; Wang, Liping; Li, Wen; Wan, Shanhong

2015-07-08

Space mechanisms require multialkylated cyclopentanes (MACs) more lubricious, more reliable, more durable, and better adaptive to harsh space environments. In this study, two kinds of additives were added into MACs for improving the tribological properties under simulated space environments: (a) solid nanoparticles (tungsten disulfide (WS2), tungsten trioxide (WO3), lanthanum oxide (La2O3), and lanthanum trifluoride (LaF3)) for steel/steel contacts; (b) liquid additives like zinc dialkyldithiophosphate (ZDDP) and molybdenum dialkyldithiocarbamate (MoDTC) for steel/steel and steel/diamond-like carbon (DLC) contacts. The results show that, under harsh simulated space environments, addition of the solid nanoparticles into MACs allows the wear to be reduced by up to one order magnitude, while liquid additives simultaneously reduce friction and wear by 80% and 93%, respectively. Friction mechanisms were proposed according to surface/interface analysis techniques, such as X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS). The role of solid nanoparticles in reducing friction and wear mainly depends on their surface enhancement effect, and the liquid additives are attributed to the formation of tribochemical reaction film derived from ZDDP and MoDTC on the sliding surfaces.

Li + transport in poly(ethylene oxide) based electrolyte: A combined study of neutron scattering, dielectric spectroscopy, and MD simulation

NASA Astrophysics Data System (ADS)

Do, Changwoo; Lunkenheimer, Peter; Diddens, Diddo; Götz, Marion; Weiß, Matthias; Loidl, Alois; Sun, Xiao-Guang; Allgaier, Jürgen; Ohl, Michael

2013-03-01

Dynamics of Li + transport in polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imde (LiTFSI) mixtures are investigated by combining various experimental techniques (neutron spin-echo and dielectric spectroscopy) with molecular dynamics (MD) simulations. Our results suggest that the characteristic live times within the cages formed by oxygens are mainly determined by the alpha-relaxation which corresponds to local segmental motions of polymers, to a much lesser extent by the main chain relaxation, and not at all by the beta-relaxation or any other faster processes. The significant contribution of Li + hopping process to the ion conductivity is also identified. Subsequently, detailed characteristic length and time scales of various Li + transport processes in solid polymer electrolytes are presented and interpreted.

Electrode design for low temperature direct-hydrocarbon solid oxide fuel cells

DOEpatents

Chen, Fanglin; Zhao, Fei; Liu, Qiang

2015-10-06

In certain embodiments of the present disclosure, a solid oxide fuel cell is described. The solid oxide fuel cell includes a hierarchically porous cathode support having an impregnated cobaltite cathode deposited thereon, an electrolyte, and an anode support. The anode support includes hydrocarbon oxidation catalyst deposited thereon, wherein the cathode support, electrolyte, and anode support are joined together and wherein the solid oxide fuel cell operates a temperature of 600.degree. C. or less.

Electrode Design for Low Temperature Direct-Hydrocarbon Solid Oxide Fuel Cells

NASA Technical Reports Server (NTRS)

Liu, Qiang (Inventor); Chen, Fanglin (Inventor); Zhao, Fei (Inventor)

2015-01-01

In certain embodiments of the present disclosure, a solid oxide fuel cell is described. The solid oxide fuel cell includes a hierarchically porous cathode support having an impregnated cobaltite cathode deposited thereon, an electrolyte, and an anode support. The anode support includes hydrocarbon oxidation catalyst deposited thereon, wherein the cathode support, electrolyte, and anode support are joined together and wherein the solid oxide fuel cell operates a temperature of 600.degree. C. or less.

Partial oxidation of methane (POM) assisted solid oxide co-electrolysis

DOEpatents

Chen, Fanglin; Wang, Yao

2017-02-21

Methods for simultaneous syngas generation by opposite sides of a solid oxide co-electrolysis cell are provided. The method can comprise exposing a cathode side of the solid oxide co-electrolysis cell to a cathode-side feed stream; supplying electricity to the solid oxide co-electrolysis cell such that the cathode side produces a product stream comprising hydrogen gas and carbon monoxide gas while supplying oxygen ions to an anode side of the solid oxide co-electrolysis cell; and exposing the anode side of the solid oxide co-electrolysis cell to an anode-side feed stream. The cathode-side feed stream comprises water and carbon dioxide, and the anode-side feed stream comprises methane gas such that the methane gas reacts with the oxygen ions to produce hydrogen and carbon monoxide. The cathode-side feed stream can further comprise nitrogen, hydrogen, or a mixture thereof.

Mixed oxide solid solutions

DOEpatents

Magno, Scott; Wang, Ruiping; Derouane, Eric

2003-01-01

The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

Phase field modeling of microstructure evolution and concomitant effective conductivity change in solid oxide fuel cell electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lei, Yinkai; Cheng, Tian -Le; Wen, You -Hai

Microstructure evolution plays an important role in the performance degradation of SOFC electrodes. In this work, we propose a much improved phase field model to simulate the microstructure evolution in the electrodes of solid oxide fuel cell. We demonstrate that the tunability of the interfacial energy in this model has been significantly enhanced. Parameters are set to fit for the interfacial energies of a typical Ni-YSZ anode, an LSM-YSZ cathode and an artificial reference electrode, respectively. The contact angles at various triple junctions and the microstructure evolutions in two dimensions are calibrated to verify the model. As a demonstration ofmore » the capabilities of the model, three dimensional microstructure evolutions are simulated applying the model to the three different electrodes. The time evolutions of grain size and triple phase boundary density are analyzed. In addition, a recently proposed bound charge successive approximation algorithm is employed to calculate the effective conductivity of the electrodes during microstructure evolution. Furthermore, the effective conductivity of all electrodes are found to decrease during the microstructure evolution, which is attributed to the increased tortuosity and the loss of percolated volume fraction of the electrode phase.« less

Phase field modeling of microstructure evolution and concomitant effective conductivity change in solid oxide fuel cell electrodes

DOE PAGES

Lei, Yinkai; Cheng, Tian -Le; Wen, You -Hai

2017-02-13

Microstructure evolution plays an important role in the performance degradation of SOFC electrodes. In this work, we propose a much improved phase field model to simulate the microstructure evolution in the electrodes of solid oxide fuel cell. We demonstrate that the tunability of the interfacial energy in this model has been significantly enhanced. Parameters are set to fit for the interfacial energies of a typical Ni-YSZ anode, an LSM-YSZ cathode and an artificial reference electrode, respectively. The contact angles at various triple junctions and the microstructure evolutions in two dimensions are calibrated to verify the model. As a demonstration ofmore » the capabilities of the model, three dimensional microstructure evolutions are simulated applying the model to the three different electrodes. The time evolutions of grain size and triple phase boundary density are analyzed. In addition, a recently proposed bound charge successive approximation algorithm is employed to calculate the effective conductivity of the electrodes during microstructure evolution. Furthermore, the effective conductivity of all electrodes are found to decrease during the microstructure evolution, which is attributed to the increased tortuosity and the loss of percolated volume fraction of the electrode phase.« less

Modeling and optimization of proton-conducting solid oxide electrolysis cell: Conversion of CO2 into value-added products

NASA Astrophysics Data System (ADS)

Namwong, Lawit; Authayanun, Suthida; Saebea, Dang; Patcharavorachot, Yaneeporn; Arpornwichanop, Amornchai

2016-11-01

Proton-conducting solid oxide electrolysis cells (SOEC-H+) are a promising technology that can utilize carbon dioxide to produce syngas. In this work, a detailed electrochemical model was developed to predict the behavior of SOEC-H+ and to prove the assumption that the syngas is produced through a reversible water gas-shift (RWGS) reaction. The simulation results obtained from the model, which took into account all of the cell voltage losses (i.e., ohmic, activation, and concentration losses), were validated using experimental data to evaluate the unknown parameters. The developed model was employed to examine the structural and operational parameters. It is found that the cathode-supported SOEC-H+ is the best configuration because it requires the lowest cell potential. SOEC-H+ operated favorably at high temperatures and low pressures. Furthermore, the simulation results revealed that the optimal S/C molar ratio for syngas production, which can be used for methanol synthesis, is approximately 3.9 (at a constant temperature and pressure). The SOEC-H+ was optimized using a response surface methodology, which was used to determine the optimal operating conditions to minimize the cell potential and maximize the carbon dioxide flow rate.

Influence of the charge double layer on solid oxide fuel cell stack behavior

NASA Astrophysics Data System (ADS)

Whiston, Michael M.; Bilec, Melissa M.; Schaefer, Laura A.

2015-10-01

While the charge double layer effect has traditionally been characterized as a millisecond phenomenon, longer timescales may be possible under certain operating conditions. This study simulates the dynamic response of a previously developed solid oxide fuel cell (SOFC) stack model that incorporates the charge double layer via an equivalent circuit. The model is simulated under step load changes. Baseline conditions are first defined, followed by consideration of minor and major deviations from the baseline case. This study also investigates the behavior of the SOFC stack with a relatively large double layer capacitance value, as well as operation of the SOFC stack under proportional-integral (PI) control. Results indicate that the presence of the charge double layer influences the SOFC stack's settling time significantly under the following conditions: (i) activation and concentration polarizations are significantly increased, or (ii) a large value of the double layer capacitance is assumed. Under normal (baseline) operation, on the other hand, the charge double layer effect diminishes within milliseconds, as expected. It seems reasonable, then, to neglect the charge double layer under normal operation. However, careful consideration should be given to potential variations in operation or material properties that may give rise to longer electrochemical settling times.

Web-Based Toxic Gas Dispersion Model for Shuttle Launch Operations

NASA Technical Reports Server (NTRS)

Bardina, Jorge; Thirumalainambi, Rajkumar

2004-01-01

During the launch of the Space Shuttle vehicle, the burning of liquid hydrogen fuel with liquid oxygen at extreme high temperatures inside the three space shuttle main engines, and the burning of the solid propellant mixture of ammonium perchlorate oxidizer, aluminum fuel, iron oxide catalyst, polymer binder, and epoxy curing agent in the two solid rocket boosters result in the formation of a large cloud of hot, buoyant toxic exhaust gases near the ground level which subsequently rises and entrains into ambient air until the temperature and density of the cloud reaches an approximate equilibrium with ambient conditions. In this paper, toxic gas dispersion for various gases are simulated over the web for varying environmental conditions which is provided by rawinsonde data. The model simulates chemical concentration at ground level up to 10 miles (1 KM grids) in downrange up to an hour after launch. The ambient concentration of the gas dispersion and the deposition of toxic particles are used as inputs for a human health risk assessment model. The advantage of the present model is the accessibility and dissemination of model results to other NASA centers over the web. The model can be remotely operated and various scenarios can be analyzed.

Staged heating by oxidation of carbonaceous material

DOEpatents

Knell, Everett W.; Green, Norman W.

1978-01-31

A carbonaceous material is pyrolyzed in the presence of a particulate source of heat obtained by the partial oxidation of a carbon containing solid residue of the carbonaceous material. The heat obtained from the oxidation of the carbon containing solid residue is maximized by preheating the carbon containing solid residue with a hot gas stream obtained by oxidizing the gaseous combustion products of the carbon containing solid residue.

Solid-state rechargeable magnesium battery

DOEpatents

Shao, Yuyan; Liu, Jun; Liu, Tianbiao; Li, Guosheng

2016-09-06

Embodiments of a solid-state electrolyte comprising magnesium borohydride, polyethylene oxide, and optionally a Group IIA or transition metal oxide are disclosed. The solid-state electrolyte may be a thin film comprising a dispersion of magnesium borohydride and magnesium oxide nanoparticles in polyethylene oxide. Rechargeable magnesium batteries including the disclosed solid-state electrolyte may have a coulombic efficiency .gtoreq.95% and exhibit cycling stability for at least 50 cycles.

Theoretical Design and Experimental Evaluation of Molten Carbonate Modified LSM Cathode for Low Temperature Solid Oxide Fuel Cells

DTIC Science & Technology

2015-01-07

Min Lee, Kevin Huang. Mixed Oxide-Ion and Carbonate-Ion Conductors (MOCCs) as Electrolyte Materials for Solid Oxide Fuel Cells, 218th ECS Meeting... Solid Oxide Fuel Cells The views, opinions and/or findings contained in this report are those of the author(s) and should not contrued as an official...ES) U.S. Army Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 Solid Oxide Fuel Cell, Oxygen Reduction, Molten Carbonate

New ambuic acid derivatives from the solid culture of Pestalotiopsis neglecta and their nitric oxide inhibitory activity

PubMed Central

Qi, Qiu-Yue; Li, Er-Wei; Han, Jun-Jie; Pei, Yun-Fei; Ma, Ke; Bao, Li; Huang, Ying; Zhao, Feng; Liu, Hong-Wei

2015-01-01

Four new ambuic acid derivatives (1–4), and four known derivatives (5–8), were isolated from the solid culture of a plant pathogenic fungus Pestalotiopsis neglecta. Their structures were elucidated by extensive NMR experiments. The absolute configuration of the C-16 secondary alcohol in 1 was deduced via the CD data of the in situ formed [Rh2(OCOCF3)4] complex with the acetonide derivative of 1. The absolute configuration in 3 was assigned by comparison of the experimental and simulated electronic circular dichroism (ECD) spectrum. The NMR data of compound 5 was reported for the first time. In the nitric oxide (NO) inhibition assay, compounds 4, 6 and 7 showed inhibitory activity against the NO production in the lipopolysaccharide (LPS)-induced macrophage with IC50 values of 88.66, 11.20, and 20.80 µM, respectively. PMID:25989228

New ambuic acid derivatives from the solid culture of Pestalotiopsis neglecta and their nitric oxide inhibitory activity.

PubMed

Qi, Qiu-Yue; Li, Er-Wei; Han, Jun-Jie; Pei, Yun-Fei; Ma, Ke; Bao, Li; Huang, Ying; Zhao, Feng; Liu, Hong-Wei

2015-05-19

Four new ambuic acid derivatives (1-4), and four known derivatives (5-8), were isolated from the solid culture of a plant pathogenic fungus Pestalotiopsis neglecta. Their structures were elucidated by extensive NMR experiments. The absolute configuration of the C-16 secondary alcohol in 1 was deduced via the CD data of the in situ formed [Rh2(OCOCF3)4] complex with the acetonide derivative of 1. The absolute configuration in 3 was assigned by comparison of the experimental and simulated electronic circular dichroism (ECD) spectrum. The NMR data of compound 5 was reported for the first time. In the nitric oxide (NO) inhibition assay, compounds 4, 6 and 7 showed inhibitory activity against the NO production in the lipopolysaccharide (LPS)-induced macrophage with IC50 values of 88.66, 11.20, and 20.80 µM, respectively.

Modeling Methodologies for Design and Control of Solid Oxide Fuel Cell APUs

NASA Astrophysics Data System (ADS)

Pianese, C.; Sorrentino, M.

2009-08-01

Among the existing fuel cell technologies, Solid Oxide Fuel Cells (SOFC) are particularly suitable for both stationary and mobile applications, due to their high energy conversion efficiencies, modularity, high fuel flexibility, low emissions and noise. Moreover, the high working temperatures enable their use for efficient cogeneration applications. SOFCs are entering in a pre-industrial era and a strong interest for designing tools has growth in the last years. Optimal system configuration, components sizing, control and diagnostic system design require computational tools that meet the conflicting needs of accuracy, affordable computational time, limited experimental efforts and flexibility. The paper gives an overview on control-oriented modeling of SOFC at both single cell and stack level. Such an approach provides useful simulation tools for designing and controlling SOFC-APUs destined to a wide application area, ranging from automotive to marine and airplane APUs.

Modelling and control of solid oxide fuel cell generation system in microgrid

NASA Astrophysics Data System (ADS)

Zhou, Niancheng; Li, Chunyan; Sun, Fangqing; Wang, Qianggang

2017-11-01

Compared with other kinds of fuel cells, solid oxide fuel cell (SOFC) has been widely used in microgrids because of its higher efficiency and longer operation life. The weakness of SOFC lies in its slow response speed when grid disturbance occurs. This paper presents a control strategy that can promote the response speed and limit the fault current impulse for SOFC systems integrated into microgrids. First, the hysteretic control of the bidirectional DC-DC converter, which joins the SOFC and DC bus together, is explored. In addition, an improved droop control with limited current protection is applied in the DC-AC inverter, and the active synchronization control is applied to ensure a smooth transition of the microgrid between the grid-connected mode and the islanded mode. To validate the effectiveness of this control strategy, the control model was built and simulated in PSCAD/EMTDC.

Reactivating the Ni-YSZ electrode in solid oxide cells and stacks by infiltration

NASA Astrophysics Data System (ADS)

Skafte, Theis Løye; Hjelm, Johan; Blennow, Peter; Graves, Christopher

2018-02-01

The solid oxide cell (SOC) could play a vital role in energy storage when the share of intermittent electricity production is high. However, large-scale commercialization of the technology is still hindered by the limited lifetime. Here, we address this issue by examining the potential for repairing various failure and degradation mechanisms occurring in the fuel electrode, thereby extending the potential lifetime of a SOC system. We successfully infiltrated the nickel and yttria-stabilized zirconia cermet electrode in commercial cells with Gd-doped ceria after operation. By this method we fully reactivated the fuel electrode after simulated reactant starvation and after carbon formation. Furthermore, by infiltrating after 900 h of operation, the degradation of the fuel electrode was reduced by a factor of two over the course of 2300 h. Lastly, the scalability of the concept is demonstrated by reactivating an 8-cell stack based on a commercial design.

Real-time electrochemical impedance spectroscopy diagnosis of the solid oxide fuel cell for marine power applications

NASA Astrophysics Data System (ADS)

Nakajima, Hironori; Kitahara, Tatsumi

2017-11-01

We have investigated the behavior of an operating solid oxide fuel cell (SOFC) with supplying a simulated syngas to develop diagnosis method of the SOFC for marine power applications fueled with liquefied natural gas (LNG). We analyze the characteristics of a syngas-fueled intermediate temperature microtubular SOFC at 500 ∘C for accelerated deterioration by carbon deposition as a model case by electrochemical impedance spectroscopy (EIS) to in-situ find parameters useful for the real-time diagnosis. EIS analyses are performed by complex nonlinear least squares (CNLS) curve fitting to measured impedance spectra with an equivalent electric circuit model consisting of several resistances and capacitances attributed to the anode and cathode processes as well as Ohmic resistance of the cell. The characteristic changes of those circuit parameters by internal reforming and anode degradation are extracted, showing that they can be used for the real-time diagnosis of operating SOFCs.

Method of electrode fabrication for solid oxide electrochemical cells

DOEpatents

Jensen, R.R.

1990-11-20

A process for fabricating cermet electrodes for solid oxide electrochemical cells by sintering is disclosed. First, a porous metal electrode is fabricated on a solid oxide cell, such as a fuel cell by, for example, sintering, and is then infiltrated with a high volume fraction stabilized zirconia suspension. A second sintering step is used to sinter the infiltrated zirconia to a high density in order to more securely attach the electrode to the solid oxide electrolyte of the cell. High performance fuel electrodes can be obtained with this process. Further electrode performance enhancement may be achieved if stabilized zirconia doped with cerium oxide, chromium oxide, titanium oxide, and/or praseodymium oxide for electronic conduction is used. 5 figs.

Method of electrode fabrication for solid oxide electrochemical cells

DOEpatents

Jensen, Russell R.

1990-01-01

A process for fabricating cermet electrodes for solid oxide electrochemical cells by sintering is disclosed. First, a porous metal electrode is fabricated on a solid oxide cell, such as a fuel cell by, for example, sintering, and is then infiltrated with a high volume fraction stabilized zirconia suspension. A second sintering step is used to sinter the infiltrated zirconia to a high density in order to more securely attach the electrode to the solid oxide electrolyte of the cell. High performance fuel electrodes can be obtained with this process. Further electrode performance enhancement may be achieved if stabilized zirconia doped with cerium oxide, chromium oxide, titanium oxide, and/or praseodymium oxide for electronic conduction is used.

46 CFR 194.05-11 - Flammable solids and oxidizing materials-Detail requirements.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 46 Shipping 7 2012-10-01 2012-10-01 false Flammable solids and oxidizing materials-Detail... and Marking § 194.05-11 Flammable solids and oxidizing materials—Detail requirements. (a) Flammable... 194.20. (b) Oxidizing materials used as blasting agents are regulated by the appropriate portions of...

46 CFR 194.05-11 - Flammable solids and oxidizing materials-Detail requirements.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 46 Shipping 7 2013-10-01 2013-10-01 false Flammable solids and oxidizing materials-Detail... and Marking § 194.05-11 Flammable solids and oxidizing materials—Detail requirements. (a) Flammable... 194.20. (b) Oxidizing materials used as blasting agents are regulated by the appropriate portions of...

46 CFR 194.05-11 - Flammable solids and oxidizing materials-Detail requirements.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 46 Shipping 7 2014-10-01 2014-10-01 false Flammable solids and oxidizing materials-Detail... and Marking § 194.05-11 Flammable solids and oxidizing materials—Detail requirements. (a) Flammable... 194.20. (b) Oxidizing materials used as blasting agents are regulated by the appropriate portions of...

Preliminary Electrochemical Characterization of Anode Supported Solid Oxide Cell (AS-SOC) Produced in the Institute of Power Engineering Operated in Electrolysis Mode (SOEC)

NASA Astrophysics Data System (ADS)

Kupecki, Jakub; Motyliński, Konrad; Skrzypkiewicz, Marek; Wierzbicki, Michał; Naumovich, Yevgeniy

2017-12-01

The article discusses the operation of solid oxide electrochemical cells (SOC) developed in the Institute of Power Engineering as prospective key components of power-to-gas systems. The fundamentals of the solid oxide cells operated as fuel cells (SOFC - solid oxide fuel cells) and electrolysers (SOEC - solid oxide fuel cells) are given. The experimental technique used for electrochemical characterization of cells is presented. The results obtained for planar cell with anodic support are given and discussed. Based on the results, the applicability of the cells in power-to-gas systems (P2G) is evaluated.

Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dang-Long, T., E-mail: 3TE14098G@kyushu-u.ac.jp; Quang-Tuyen, T., E-mail: tran.tuyen.quang.314@m.kyushu-u.ac.jp; Shiratori, Y., E-mail: shiratori.yusuke.500@m.kyushu-u.ac.jp

2016-06-03

Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH{sub 4} and CO{sub 2} and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidatemore » for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO{sub 2} reforming of CH{sub 4} and electrochemical oxidation of the produced syngas (H{sub 2}–CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH{sub 4}–CO{sub 2} mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO{sub 2} had strong influences on both reaction processes. The increase in CO{sub 2} partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH{sub 4}−CO{sub 2} mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.« less

Selenium Speciation and Management in Wet FGD Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Searcy, K; Richardson, M; Blythe, G

2012-02-29

This report discusses results from bench- and pilot-scale simulation tests conducted to determine the factors that impact selenium speciation and phase partitioning in wet FGD systems. The selenium chemistry in wet FGD systems is highly complex and not completely understood, thus extrapolation and scale-up of these results may be uncertain. Control of operating parameters and application of scrubber additives have successfully demonstrated the avoidance or decrease of selenite oxidation at the bench and pilot scale. Ongoing efforts to improve sample handling methods for selenium speciation measurements are also discussed. Bench-scale scrubber tests explored the impacts of oxidation air rate, tracemore » metals, scrubber additives, and natural limestone on selenium speciation in synthetic and field-generated full-scale FGD liquors. The presence and concentration of redox-active chemical species as well as the oxidation air rate contribute to the oxidation-reduction potential (ORP) conditions in FGD scrubbers. Selenite oxidation to the undesirable selenate form increases with increasing ORP conditions, and decreases with decreasing ORP conditions. Solid-phase manganese [Mn(IV)] appeared to be the significant metal impacting the oxidation of selenite to selenate. Scrubber additives were tested for their ability to inhibit selenite oxidation. Although dibasic acid and other scrubber additives showed promise in early clear liquor (sodium based and without calcium solids) bench-scale tests, these additives did not show strong inhibition of selenite oxidation in tests with higher manganese concentrations and with slurries from full-scale wet FGD systems. In bench-tests with field liquors, addition of ferric chloride at a 250:1 iron-to-selenium mass ratio sorbed all incoming selenite to the solid phase, although addition of ferric salts had no impact on native selenate that already existed in the field slurry liquor sample. As ORP increases, selenite may oxidize to selenate more rapidly than it sorbs to ferric solids. Though it was not possible to demonstrate a decrease in selenium concentrations to levels below the project'ale testing were evident at the pilot scale. Specifically, reducing oxidation air rate and ORP tends to either retain selenium as selenite in the liquor or shift selenium phase partitioning to the solid phase. Oxidation air flow rate control may be one option for managing selenium behavior in FGD scrubbers. Units that cycle load widely may find it more difficult to impact ORP conditions with oxidation air flow rate control alone. Because decreasing oxidation air rates to the reaction tank showed that all new selenium reported to the solids, the addition of ferric chloride to the pilot scrubber could not show further improvements in selenium behavior. Ferric chloride addition did shift mercury to the slurry solids, specifically to the fine particles. Several competing pathways may govern the reporting of selenium to the slurry solids: co-precipitation with gypsum into the bulk solids and sorption or co-precipitation with iron into the fine particles. Simultaneous measurement of selenium and mercury behavior suggests a holistic management strategy is best to optimize the fate of both of these elements in FGD waters. Work conducted under this project evaluated sample handling and analytical methods for selenium speciation in FGD waters. Three analytical techniques and several preservation methods were employed. Measurements of selenium speciation over time indicated that for accurate selenium speciation, it is best to conduct measurements on unpreserved, filtered samples as soon after sampling as possible. The capital and operating costs for two selenium management strategies were considered: ferric chloride addition and oxidation air flow rate control. For ferric chloride addition, as might be expected the reagent makeup costs dominate the overall costs, and range from 0.22 to 0.29 mills/kWh. For oxidation air flow rate control, a cursory comparison of capital costs and turndown capabilities for multi-stage and single-stage centrifugal blowers and several flow control methods was completed. For greenfield systems, changing the selection of blower type and flow control method may have payback periods of 4 to 5 years or more if based on energy savings alone. However, the benefits to managing redox chemistry in the scrubber could far outweigh the savings in electricity costs under some circumstances.« less

Electrochemical reduction behavior of simplified simulants of vitrified radioactive waste in molten CaCl2

NASA Astrophysics Data System (ADS)

Katasho, Yumi; Yasuda, Kouji; Nohira, Toshiyuki

2018-05-01

The electrochemical reduction of two types of simplified simulants of vitrified radioactive waste, simulant 1 (glass component only: SiO2, B2O3, Na2O, Al2O3, CaO, Li2O, and ZnO) and simulant 2 (also containing long-lived fission product oxides, ZrO2, Cs2O, PdO, and SeO2), was investigated in molten CaCl2 at 1103 K. The behavior of each element was predicted from the potential-pO2- diagram constructed from thermodynamic data. After the immersion of simulant 1 into molten CaCl2 without electrolysis, the dissolution of Na, Li, and Cs was confirmed by inductively coupled plasma atomic emission spectrometry and mass spectrometry analysis of the samples. The scanning electron microscopy/energy dispersive X-ray and X-ray diffraction analyses of simulants 1 and 2 electrolyzed at 0.9 V vs. Ca2+/Ca confirmed that most of SiO2 had been reduced to Si. After the electrolysis of simulants 1 and 2, Al, Zr, and Pd remained in the solid phase. In addition, SeO2 was found to remain partially in the solid phase and partially evaporate, although a small quantity dissolved into the molten salt.

Regenerative process and system for the simultaneous removal of particulates and the oxides of sulfur and nitrogen from a gas stream

DOEpatents

Cohen, Mitchell R.; Gal, Eli

1993-01-01

A process and system for simultaneously removing from a gaseous mixture, sulfur oxides by means of a solid sulfur oxide acceptor on a porous carrier, nitrogen oxides by means of ammonia gas and particulate matter by means of filtration and for the regeneration of loaded solid sulfur oxide acceptor. Finely-divided solid sulfur oxide acceptor is entrained in a gaseous mixture to deplete sulfur oxides from the gaseous mixture, the finely-divided solid sulfur oxide acceptor being dispersed on a porous carrier material having a particle size up to about 200 microns. In the process, the gaseous mixture is optionally pre-filtered to remove particulate matter and thereafter finely-divided solid sulfur oxide acceptor is injected into the gaseous The government of the United States of America has rights in this invention pursuant to Contract No. DE-AC21-88MC 23174 awarded by the U.S. Department of Energy.

Phosphine polymerization by nitric oxide: experimental characterization and theoretical predictions of mechanism.

PubMed

Zhao, Yi-Lei; Flora, Jason W; Thweatt, William David; Garrison, Stephen L; Gonzalez, Carlos; Houk, K N; Marquez, Manuel

2009-02-02

A yellow solid material [P(x)H(y)] has been obtained in the reaction of phosphine (PH(3)) and nitric oxide (NO) at room temperature and characterized by thermogravimetric analysis mass spectrometry (TGA-MS) and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. In this work using complete basis set (CBS-QB3) methods a plausible mechanism has been investigated for phosphine polymerization in the presence of nitric oxide (NO). Theoretical explorations with the ab initio method suggest (a) instead of the monomer the nitric oxide dimer acts as an initial oxidant, (b) the resulting phosphine oxides (H(3)P=O <--> H(3)P(+)O(-)) in the gas phase draw each other via strong dipolar interactions between the P-O groups, and (c) consequently an autocatalyzed polymerization occurs among the phosphine oxides, forming P-P chemical bonds and losing water. The possible structures of polyhydride phosphorus polymer were discussed. In the calculations a series of cluster models was computed to simulate polymerization.

TEM/STEM study of Zircaloy-2 with protective FeAl(Cr) layers under simulated BWR environment and high-temperature steam exposure

NASA Astrophysics Data System (ADS)

Park, Donghee; Mouche, Peter A.; Zhong, Weicheng; Mandapaka, Kiran K.; Was, Gary S.; Heuser, Brent J.

2018-04-01

FeAl(Cr) thin-film depositions on Zircaloy-2 were studied using transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) with respect to oxidation behavior under simulated boiling water reactor (BWR) conditions and high-temperature steam. Columnar grains of FeAl with Cr in solid solution were formed on Zircaloy-2 coupons using magnetron sputtering. NiFe2O4 precipitates on the surface of the FeAl(Cr) coatings were observed after the sample was exposed to the simulated BWR environment. High-temperature steam exposure resulted in grain growth and consumption of the FeAl(Cr) layer, but no delamination at the interface. Outward Al diffusion from the FeAl(Cr) layer occurred during high-temperature steam exposure (700 °C for 3.6 h) to form a 100-nm-thick alumina oxide layer, which was effective in mitigating oxidation of the Zircaloy-2 coupons. Zr intermetallic precipitates formed near the FeAl(Cr) layer due to the inward diffusion of Fe and Al. The counterflow of vacancies in response to the Al and Fe diffusion led to porosity within the FeAl(Cr) layer.

Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

DOEpatents

Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

2010-03-02

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

DOEpatents

Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

2010-11-23

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

Experimental and numerical investigation on the ignition and combustion stability in solid fuel ramjet with swirling flow

NASA Astrophysics Data System (ADS)

Musa, Omer; Xiong, Chen; Changsheng, Zhou

2017-08-01

The present article investigates experimentally and numerically the ignition and flame stability of high-density polyethylene solid fuel with incoming swirling air through a solid fuel ramjet (SFRJ). A new design of swirler is proposed and used in this work. Experiments on connected pipes test facility were performed for SFRJ with and without swirl. An in-house code has been developed to simulate unsteady, turbulent, reacting, swirling flow in the SFRJ. Four different swirl intensities are utilized to study experimentally and numerically the effect of swirl number on the transient regression, ignition of the solid fuel in a hot-oxidizing flow and combustion phenomenon in the SFRJ. The results showed that using swirl flow decreases the ignition time delay, recirculation zone length, and the distance between the flame and the wall, meanwhile, increases the residence time, heat transfer, regression rate and mixing degree, thus, improving the combustion efficiency and stability.

Numerical and experimental analysis of heat transfer in injector plate of hydrogen peroxide hybrid rocket motor

NASA Astrophysics Data System (ADS)

Cai, Guobiao; Li, Chengen; Tian, Hui

2016-11-01

This paper is aimed to analyze heat transfer in injector plate of hydrogen peroxide hybrid rocket motor by two-dimensional axisymmetric numerical simulations and full-scale firing tests. Long-time working, which is an advantage of hybrid rocket motor over conventional solid rocket motor, puts forward new challenges for thermal protection. Thermal environments of full-scale hybrid rocket motors designed for long-time firing tests are studied through steady-state coupled numerical simulations of flow field and heat transfer in chamber head. The motor adopts 98% hydrogen peroxide (98HP) oxidizer and hydroxyl-terminated poly-butadiene (HTPB) based fuel as the propellants. Simulation results reveal that flowing liquid 98HP in head oxidizer chamber could cool the injector plate of the motor. The cooling of 98HP is similar to the regenerative cooling in liquid rocket engines. However, the temperature of the 98HP in periphery portion of the head oxidizer chamber is higher than its boiling point. In order to prevent the liquid 98HP from unexpected decomposition, a thermal protection method for chamber head utilizing silica-phenolics annular insulating board is proposed. The simulation results show that the annular insulating board could effectively decrease the temperature of the 98HP in head oxidizer chamber. Besides, the thermal protection method for long-time working hydrogen peroxide hybrid rocket motor is verified through full-scale firing tests. The ablation of the insulating board in oxygen-rich environment is also analyzed.

Solid oxide fuel cell with single material for electrodes and interconnect

DOEpatents

McPheeters, Charles C.; Nelson, Paul A.; Dees, Dennis W.

1994-01-01

A solid oxide fuel cell having a plurality of individual cells. A solid oxide fuel cell has an anode and a cathode with electrolyte disposed therebetween, and the anode, cathode and interconnect elements are comprised of substantially one material.

Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

DOEpatents

Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

2010-07-20

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

49 CFR 176.400 - Stowage of Division 1.5, Class 4 (flammable solids) and Class 5 (oxidizers and organic peroxides...

Code of Federal Regulations, 2011 CFR

2011-10-01

... 49 Transportation 2 2011-10-01 2011-10-01 false Stowage of Division 1.5, Class 4 (flammable solids... Solids), Class 5 (Oxidizers and Organic Peroxides), and Division 1.5 Materials § 176.400 Stowage of Division 1.5, Class 4 (flammable solids) and Class 5 (oxidizers and organic peroxides) materials. (a) Class...

Solid oxide fuel cell with single material for electrodes and interconnect

DOEpatents

McPheeters, C.C.; Nelson, P.A.; Dees, D.W.

1994-07-19

A solid oxide fuel cell is described having a plurality of individual cells. A solid oxide fuel cell has an anode and a cathode with electrolyte disposed there between, and the anode, cathode and interconnect elements are comprised of substantially one material. 9 figs.

Isothermal Oxidation of Magnetite to Hematite in Air and Cyclic Reduction/Oxidation Under Carbon Looping Combustion Conditions

NASA Astrophysics Data System (ADS)

Simmonds, Tegan; Hayes, Peter C.

2017-12-01

In the carbon looping combustion process the oxygen carrier is regenerated through oxidation in air; this process has been simulated by the oxidation of dense synthetic magnetite for selected temperatures and times. The oxidation of magnetite in air is shown to occur through the formation of dense hematite layers on the particle surface. This dense hematite forms through lath type shear transformations or solid-state diffusion through the product layer. Cyclic reduction in CO-CO2/oxidation in air of hematite single crystals has been carried out under controlled laboratory conditions at 1173 K (900 °C). It has been shown that the initial reduction step is critical to determining the product microstructure, which consists of gas pore dendrites in the magnetite matrix with blocky hematite formed on the pore surfaces. The progressive growth of the magnetite layer with the application of subsequent cycles appears to continue until no original hematite remains, after which physical disintegration of the particles takes place.

Feasibility study of solid oxide fuel cell engines integrated with sprinter gas turbines: Modeling, design and control

NASA Astrophysics Data System (ADS)

Jia, Zhenzhong; Sun, Jing; Dobbs, Herb; King, Joel

2015-02-01

Conventional recuperating solid oxide fuel cell (SOFC)/gas turbine (GT) system suffers from its poor dynamic capability and load following performance. To meet the fast, safe and efficient load following requirements for mobile applications, a sprinter SOFC/GT system concept is proposed in this paper. In the proposed system, an SOFC stack operating at fairly constant temperature provides the baseline power with high efficiency while the fast dynamic capability of the GT-generator is fully explored for fast dynamic load following. System design and control studies have been conducted by using an SOFC/GT system model consisting of experimentally-verified component models. In particular, through analysis of the steady-state simulation results, an SOFC operation strategy is proposed to maintain fairly constant SOFC power (less than 2% power variation) and temperature (less than 2 K temperature variation) over the entire load range. A system design procedure well-suited to the proposed system has also been developed to help determining component sizes and the reference steady-state operation line. In addition, control analysis has been studied for both steady-state and transient operations. Simulation results suggest that the proposed system holds the promise to achieve fast and safe transient operations by taking full advantage of the fast dynamics of the GT-generator.

Solid oxide fuel cell simulation and design optimization with numerical adjoint techniques

NASA Astrophysics Data System (ADS)

Elliott, Louie C.

This dissertation reports on the application of numerical optimization techniques as applied to fuel cell simulation and design. Due to the "multi-physics" inherent in a fuel cell, which results in a highly coupled and non-linear behavior, an experimental program to analyze and improve the performance of fuel cells is extremely difficult. This program applies new optimization techniques with computational methods from the field of aerospace engineering to the fuel cell design problem. After an overview of fuel cell history, importance, and classification, a mathematical model of solid oxide fuel cells (SOFC) is presented. The governing equations are discretized and solved with computational fluid dynamics (CFD) techniques including unstructured meshes, non-linear solution methods, numerical derivatives with complex variables, and sensitivity analysis with adjoint methods. Following the validation of the fuel cell model in 2-D and 3-D, the results of the sensitivity analysis are presented. The sensitivity derivative for a cost function with respect to a design variable is found with three increasingly sophisticated techniques: finite difference, direct differentiation, and adjoint. A design cycle is performed using a simple optimization method to improve the value of the implemented cost function. The results from this program could improve fuel cell performance and lessen the world's dependence on fossil fuels.

Solid Oxide Fuel Cell short stack performance testing - part B: Operation in carbon capture applications and degradation issues

NASA Astrophysics Data System (ADS)

Mastropasqua, L.; Campanari, S.; Brouwer, J.

2017-12-01

The need to experimentally understand the performance of Solid Oxide Fuel Cells (SOFC) stacks under Carbon Capture and Storage (CCS) mode operating conditions, hence with anode recirculation, has prompted this two-part study. The steady state performance of a 6-cell short stack of Y2O3 stabilised Zirconia (YSZ) with Ni/YSZ anodes and composite Sr-doped LaMnO3 (LSM)/YSZ cathodes is experimentally evaluated. In Part A, the electrical and environmental performance are assessed and the results are compared with the commercial full-scale micro-Combined Heat and Power system, which comprises the same cells. In Part B of this work, a specific set of stack operating conditions important to CCS applications is explored. The experimental inlet composition is changed in order to reproduce a simulated syngas in CCS mode operation for different fuel utilisation factors. Operation with the simulated anode recycle syngas leads to lower voltage when the anode recycle is lower, mainly due to higher internal reforming and polarisation losses. A clear voltage trend is observed when the amount of CO content in the inlet fuel is increased, signalling an improvement of the polarisation performance at constant current density and fixed inlet equivalent hydrogen content. Stack degradation is measured and results in line with manufacturer's data.

Kinetics of sorption and abiotic oxidation of arsenic(III) by aquifer materials

USGS Publications Warehouse

Amirbahman, A.; Kent, D.B.; Curtis, G.P.; Davis, J.A.

2006-01-01

The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6-0.9 m2 g-1) and reductively extractable iron contents (18-26 ??mol m-2), but with varying total manganese contents (0.5-3.5 ??mol m-2) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation of As(III). Under all conditions, dissolved As(V) concentrations were very low. A quantitative model was developed to simulate the extent and kinetics of arsenic transformation by aquifer materials. The model included: (1) reversible rate-limited adsorption of As(III) onto both oxidative and non-oxidative (adsorptive) sites, (2) irreversible rate-limited oxidation of As(III), and (3) equilibrium adsorption of As(V) onto adsorptive sites. Rate constants for these processes, as well as the total oxidative site densities were used as the fitting parameters. The total adsorptive site densities were estimated based on the measured specific surface area of each material. The best fit was provided by considering one fast and one slow site for each adsorptive and oxidative site. The fitting parameters were obtained using the kinetic data for the most reactive aquifer material at different initial As(III) concentrations. Using the same parameters to simulate As(III) and As(V) surface reactions, the model predictions were compared to observations for aquifer materials with different manganese contents. The model simulated the experimental data very well for all materials at all initial As(III) concentrations. The As(V) production rate was related to the concentrations of the free oxidative surface sites and dissolved As(III), as r As(V) = k???ox [Mn(IV) OH3][AsO3] with apparent second-order rate constants of koxf??? = 6.28 ?? 10-1 and koxs??? = 1.25 ?? 10-2 M-1 s-1 for the fast and the slow oxidative sites, respectively. The As(III) removal rate decreased approximately by half for a pH increase from 4 to 7. The pH dependence was explained using the acid-base behavior of the surface oxidative sites by considering a surface pKa = 6.2 (I = 0). In the presence of excess surface adsorptive and oxidative sites, phosphate diminished the rate of As(III) removal and As(V) production only slightly due to its interaction with the oxidative sites. The observed As(III) oxidation rate here is consistent with previous observations of As(III) oxidation over short transport distances during field-scale transport experiments. The model developed here may be incorporated into groundwater transport models to predict arsenic speciation and transport in chemically heterogeneous systems. ?? 2005 Elsevier Inc. All rights reserved.

Accelerated evaporation of water on graphene oxide.

PubMed

Wan, Rongzheng; Shi, Guosheng

2017-03-29

Using molecular dynamics simulations, we show that the evaporation of nanoscale volumes of water on patterned graphene oxide is faster than that on homogeneous graphene oxide. The evaporation rate of water is insensitive to variation in the oxidation degree of the oxidized regions, so long as the water film is only distributed on the oxidized regions. The evaporation rate drops when the water film spreads onto the unoxidized regions. Further analysis showed that varying the oxidation degree observably changed the interaction between the outmost water molecules and the solid surface, but the total interaction for the outmost water molecules only changed a very limited amount due to the correspondingly regulated water-water interaction when the water film is only distributed on the oxidized regions. When the oxidation degree is too low and some unoxidized regions are also covered by the water film, the thickness of the water film decreases, which extends the lifetime of the hydrogen bonds for the outmost water molecules and lowers the evaporation rate of the water. The insensitivity of water evaporation to the oxidation degree indicates that we only need to control the scale of the unoxidized and oxidized regions for graphene oxide to regulate the evaporation of nanoscale volumes of water.

Comparison of iron and copper doped manganese cobalt spinel oxides as protective coatings for solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Talic, Belma; Molin, Sebastian; Wiik, Kjell; Hendriksen, Peter Vang; Lein, Hilde Lea

2017-12-01

MnCo2O4, MnCo1.7Cu0.3O4 and MnCo1.7Fe0.3O4 are investigated as coatings for corrosion protection of metallic interconnects in solid oxide fuel cell stacks. Electrophoretic deposition is used to deposit the coatings on Crofer 22 APU alloy. All three coating materials reduce the parabolic oxidation rate in air at 900 °C and 800 °C. At 700 °C there is no significant difference in oxidation rate between coated samples and uncoated pre-oxidized Crofer 22 APU. The cross-scale area specific resistance (ASR) is measured in air at 800 °C using La0.85Sr0.1Mn1.1O3 (LSM) contact plates to simulate the interaction with the cathode in a SOFC stack. All coated samples have three times lower ASR than uncoated Crofer 22 APU after 4370 h aging. The ASR increase with time is lowest with the MnCo2O4 coating, followed by the MnCo1.7Fe0.3O4 and MnCo1.7Cu0.3O4 coatings. LSM plates contacted to uncoated Crofer 22 APU contain significant amounts of Cr after aging, while all three coatings effectively prevent Cr diffusion into the LSM. A complex Cr-rich reaction layer develops at the coating-alloy interface during oxidation. Cu and Fe doping reduce the extent of this reaction layer at 900 °C, while at 800 °C the effect of doping is insignificant.

Aluminum/water reactions under extreme conditions

NASA Astrophysics Data System (ADS)

Hooper, Joseph

2013-03-01

We discuss mechanisms that may control the reaction of aluminum and water under extreme conditions. We are particularly interested in the high-temperature, high-strain regime where the native oxide layer is destroyed and fresh aluminum is initially in direct contact with liquid or supercritical water. Disparate experimental data over the years have suggested rapid oxidation of aluminum is possible in such situations, but no coherent picture has emerged as to the basic oxidation mechanism or the physical processes that govern the extent of reaction. We present theoretical and computational analysis of traditional metal/water reaction mechanisms that treat diffusion through a dynamic oxide layer or reaction limited by surface kinetics. Diffusion through a fresh solid oxide layer is shown to be far too slow to have any effect on the millisecond timescale (even at high temperatures). Quantum molecular dynamics simulations of liquid Al and water surface reactions show rapid water decomposition at the interface, catalyzed by adjacent water molecules in a Grotthus-like relay mechanism. The surface reaction barriers are far too low for this to be rate-limiting in any way. With these straightforward mechanisms ruled out, we investigate two more complex possibilities for the rate-limiting factor; first, we explore the possibility that newly formed oxide remains a metastable liquid well below its freezing point, allowing for diffusion-limited reactions through the oxide shell but on a much faster timescale. The extent of reaction would then be controlled by the solidification kinetics of alumina. Second, we discuss preliminary analysis on surface erosion and turbulent mixing, which may play a prominent role during hypervelocity penetration of solid aluminum projectiles into water.

Optical fingerprints of solid-liquid interfaces: a joint ATR-IR and first principles investigation

NASA Astrophysics Data System (ADS)

Yang, L.; Niu, F.; Tecklenburg, S.; Pander, M.; Nayak, S.; Erbe, A.; Wippermann, S.; Gygi, F.; Galli, G.

Despite the importance of understanding the structural and bonding properties of solid-liquid interfaces for a wide range of (photo-)electrochemical applications, there are presently no experimental techniques available to directly probe the microscopic structure of solid-liquid interfaces. To develop robust strategies to interpret experiments and validate theory, we carried out attenuated total internal reflection (ATR-IR) spectroscopy measurements and ab initio molecular dynamics (AIMD) simulations of the vibrational properties of interfaces between liquid water and well-controlled prototypical semiconductor substrates. We show the Ge(100)/H2O interface to feature a reversible potential-dependent surface phase transition between Ge-H and Ge-OH termination. The Si(100)/H2O interface is proposed as a model system for corrosion and oxidation processes. We performed AIMD calculations under finite electric fields, revealing different pathways for initial oxidation. These pathways are predicted to exhibit unique spectral signatures. A significant increase in surface specificity can be achieved utilizing an angle-dependent ATR-IR experiment, which allows to detect such signatures at the interfacial layer and consequently changes in the hydrogen bond network. Funding from DOE-BES Grant No. DE-SS0008939 and the Deutsche Forschungsgemeinschaft (RESOLV, EXC 1069) are gratefully acknowledged.

Optimal design and operation of solid oxide fuel cell systems for small-scale stationary applications

NASA Astrophysics Data System (ADS)

Braun, Robert Joseph

The advent of maturing fuel cell technologies presents an opportunity to achieve significant improvements in energy conversion efficiencies at many scales; thereby, simultaneously extending our finite resources and reducing "harmful" energy-related emissions to levels well below that of near-future regulatory standards. However, before realization of the advantages of fuel cells can take place, systems-level design issues regarding their application must be addressed. Using modeling and simulation, the present work offers optimal system design and operation strategies for stationary solid oxide fuel cell systems applied to single-family detached dwellings. A one-dimensional, steady-state finite-difference model of a solid oxide fuel cell (SOFC) is generated and verified against other mathematical SOFC models in the literature. Fuel cell system balance-of-plant components and costs are also modeled and used to provide an estimate of system capital and life cycle costs. The models are used to evaluate optimal cell-stack power output, the impact of cell operating and design parameters, fuel type, thermal energy recovery, system process design, and operating strategy on overall system energetic and economic performance. Optimal cell design voltage, fuel utilization, and operating temperature parameters are found using minimization of the life cycle costs. System design evaluations reveal that hydrogen-fueled SOFC systems demonstrate lower system efficiencies than methane-fueled systems. The use of recycled cell exhaust gases in process design in the stack periphery are found to produce the highest system electric and cogeneration efficiencies while achieving the lowest capital costs. Annual simulations reveal that efficiencies of 45% electric (LHV basis), 85% cogenerative, and simple economic paybacks of 5--8 years are feasible for 1--2 kW SOFC systems in residential-scale applications. Design guidelines that offer additional suggestions related to fuel cell-stack sizing and operating strategy (base-load or load-following and cogeneration or electric-only) are also presented.

UTC Power/Delphi SECA CBS Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gorman, Michael; Kerr, Rich

2013-04-04

The subject report summarizes the results of solid oxide fuel cell development conducted by UTC Power in conjunction with Delphi Automotive Systems under a cost-share program with from October 2008 through March of 2013. Over that period Delphi Automotive Systems developed a nearly four times larger area solid oxide fuel cell stack capable of operating on pre-reformed natural gas and simulated coal gas with durability demonstrated to 5,000 hours and projected to exceed 10,000 hours. The new stack design was scaled to 40-cell stacks with power output in excess of 6.25kW. Delphi also made significant strides in improving the manufacturability,more » yield and production cost of these solid oxide fuel cells over the course of the program. Concurrently, UTC Power developed a conceptual design for a 120 MW Integrated Gasification Fuel Cell (IGFC) operating on coal syngas with as high as 57% Higher Heating Value (HHV) efficiency as a measure of the feasibility of the technology. Subsequently a 400 kW on-site system preliminary design with 55% Lower Heating Value (LHV) efficiency operating on natural gas was down-selected from eighteen candidate designs. That design was used as the basis for a 25kW breadboard power plant incorporating four Delphi cell stacks that was tested on natural gas before the program was discontinued due to the sale of UTC Power in early 2013. Though the program was cut short of the endurance target of 3,000 hours, many aspects of the technology were proven including: large-area, repeatable cell manufacture, cell stack operation on simulated coal gas and natural gas and integrated power plant operation on natural gas. The potential of the technology for high efficiency stationary electric power generation is clear. Acceptable production costs, durability, and reliability in real world environments are the remaining challenges to commercialization.« less

A simulation model for methane emissions from landfills with interaction of vegetation and cover soil.

PubMed

Bian, Rongxing; Xin, Danhui; Chai, Xiaoli

2018-01-01

Global climate change and ecological problems brought about by greenhouse gas effect have become a severe threat to humanity in the 21st century. Vegetation plays an important role in methane (CH 4 ) transport, oxidation and emissions from municipal solid waste (MSW) landfills as it modifies the physical and chemical properties of the cover soil, and transports CH 4 to the atmosphere directly via their conduits, which are mainly aerenchymatous structures. In this study, a novel 2-D simulation CH 4 emission model was established, based on an interactive mechanism of cover soil and vegetation, to model CH 4 transport, oxidation and emissions in landfill cover soil. Results of the simulation model showed that the distribution of CH 4 concentration and emission fluxes displayed a significant difference between vegetated and non-vegetated areas. CH 4 emission flux was 1-2 orders of magnitude higher than bare areas in simulation conditions. Vegetation play a negative role in CH 4 emissions from landfill cover soil due to the strong CH 4 transport capacity even though vegetation also promotes CH 4 oxidation via changing properties of cover soil and emitting O 2 via root system. The model will be proposed to allow decision makers to reconsider the actual CH 4 emission from vegetated and non-vegetated covered landfills. Copyright © 2017 Elsevier Ltd. All rights reserved.

Creep analysis of solid oxide fuel cell with bonded compliant seal design

NASA Astrophysics Data System (ADS)

Jiang, Wenchun; Zhang, Yucai; Luo, Yun; Gong, J. M.; Tu, S. T.

2013-12-01

Solid oxide fuel cell (SOFC) requires good sealant because it works in harsh conditions (high temperature, thermal cycle, oxidative and reducing gas environments). Bonded compliant seal (BCS) is a new sealing method for planar SOFC. It uses a thin foil metal to bond the window frame and cell, achieving the seal between window frame and cell. At high temperature, a comprehensive evaluation of its creep strength is essential for the adoption of BCS design. In order to characterize the creep behavior, the creep induced by thermal stresses in SOFC with BCS design is simulated by finite element method. The results show that the foil is compressed and large thermal stresses are generated. The initial peak thermal stress is located in the thin foil because the foil acts as a spring stores the thermal stresses by elastic and plastic deformation in itself. Serving at high temperature, initial thermal displacement is partially recovered because of the creep relaxation, which becomes a new discovered advantage for BCS design. It predicts that the failures are likely to happen in the middle of the cell edge and BNi-2 filler metal, because the maximum residual displacement and creep strain are located.

A facile synthesis of high quality nanostructured CeO2 and Gd2O3-doped CeO2 solid electrolytes for improved electrochemical performance.

PubMed

Kuo, Yu-Lin; Su, Yu-Ming; Chou, Hung-Lung

2015-06-07

This study describes the use of a composite nitrate salt solution as a precursor to synthesize CeO2 and Gd2O3-doped CeO2 (GDC) nanoparticles (NPs) using an atmospheric pressure plasma jet (APPJ). The microstructures of CeO2 and GDC NPs were found to be cubical and spherical shaped nanocrystallites with average particle sizes of 10.5 and 6.7 nm, respectively. Reactive oxygen species, detected by optical emission spectroscopy (OES), are believed to be the major oxidative agents for the formation of oxide materials in the APPJ process. Based on the material characterization and OES observations, the study effectively demonstrated the feasibility of preparing well-crystallized GDC NPs by the APPJ system as well as the gas-to-particle mechanism. Notably, the Bader charge of CeO2 and Ce0.9Gd0.1O2 characterized by density function theory (DFT) simulation and AC impedance measurements shows that Gd helps in increasing the charge on Ce0.9Gd0.1O2 NPs, thus improving their conductivity and making them candidate materials for electrolytes in solid oxide fuel cells.

Rational design of novel cathode materials in solid oxide fuel cells using first-principles simulations

NASA Astrophysics Data System (ADS)

Choi, YongMan; Lin, M. C.; Liu, Meilin

The search for clean and renewable sources of energy represents one of the most vital challenges facing us today. Solid oxide fuel cells (SOFCs) are among the most promising technologies for a clean and secure energy future due to their high energy efficiency and excellent fuel flexibility (e.g., direct utilization of hydrocarbons or renewable fuels). To make SOFCs economically competitive, however, development of new materials for low-temperature operation is essential. Here we report our results on a computational study to achieve rational design of SOFC cathodes with fast oxygen reduction kinetics and rapid ionic transport. Results suggest that surface catalytic properties are strongly correlated with the bulk transport properties in several material systems with the formula of La 0.5Sr 0.5BO 2.75 (where B = Cr, Mn, Fe, or Co). The predictions seem to agree qualitatively with available experimental results on these materials. This computational screening technique may guide us to search for high-efficiency cathode materials for a new generation of SOFCs.

The role of biomineralization in microbiologically influenced corrosion

NASA Technical Reports Server (NTRS)

Little, B.; Wagner, P.; Hart, K.; Ray, R.; Lavoie, D.; Nealson, K.; Aguilar, C.

1998-01-01

Synthetic iron oxides (goethite, alpha-FeO.OH; hematite, Fe2O3; and ferrihydrite, Fe(OH)3) were used as model compounds to simulate the mineralogy of surface films on carbon steel. Dissolution of these oxides exposed to pure cultures of the metal-reducing bacterium, Shewanella putrefaciens, was followed by direct atomic absorption spectroscopy measurement of ferrous iron coupled with microscopic analyses using confocal laser scanning and environmental scanning electron microscopies. During an 8-day exposure the organism colonized mineral surfaces and reduced solid ferric oxides to soluble ferrous ions. Elemental composition, as monitored by energy dispersive x-ray spectroscopy, indicated mineral replacement reactions with both ferrihydrite and goethite as iron reduction occurred. When carbon steel electrodes were exposed to S. putrefaciens, microbiologically influenced corrosion was demonstrated electrochemically and microscopically.

Three-dimensional numerical and experimental studies on transient ignition of hybrid rocket motor

NASA Astrophysics Data System (ADS)

Tian, Hui; Yu, Ruipeng; Zhu, Hao; Wu, Junfeng; Cai, Guobiao

2017-11-01

This paper presents transient simulations and experimental studies of the ignition process of the hybrid rocket motors (HRMs) using 90% hydrogen peroxide (HP) as the oxidizer and polymethyl methacrylate (PMMA) and Polyethylene (PE) as fuels. A fluid-solid coupling numerically method is established based on the conserved form of the three-dimensional unsteady Navier-Stokes (N-S) equations, considering gas fluid with chemical reactions and heat transfer between the fluid and solid region. Experiments are subsequently conducted using high-speed camera to record the ignition process. The flame propagation, chamber pressurizing process and average fuel regression rate of the numerical simulation results show good agreement with the experimental ones, which demonstrates the validity of the simulations in this study. The results also indicate that the flame propagation time is mainly affected by fluid dynamics and it increases with an increasing grain port area. The chamber pressurizing process begins when the flame propagation completes in the grain port. Furthermore, the chamber pressurizing time is about 4 times longer than the time of flame propagation.

Solid oxide fuel cell operable over wide temperature range

DOEpatents

Baozhen, Li; Ruka, Roswell J.; Singhal, Subhash C.

2001-01-01

Solid oxide fuel cells having improved low-temperature operation are disclosed. In one embodiment, an interfacial layer of terbia-stabilized zirconia is located between the air electrode and electrolyte of the solid oxide fuel cell. The interfacial layer provides a barrier which controls interaction between the air electrode and electrolyte. The interfacial layer also reduces polarization loss through the reduction of the air electrode/electrolyte interfacial electrical resistance. In another embodiment, the solid oxide fuel cell comprises a scandia-stabilized zirconia electrolyte having high electrical conductivity. The scandia-stabilized zirconia electrolyte may be provided as a very thin layer in order to reduce resistance. The scandia-stabilized electrolyte is preferably used in combination with the terbia-stabilized interfacial layer. The solid oxide fuel cells are operable over wider temperature ranges and wider temperature gradients in comparison with conventional fuel cells.

Interfacial material for solid oxide fuel cell

DOEpatents

Baozhen, Li; Ruka, Roswell J.; Singhal, Subhash C.

1999-01-01

Solid oxide fuel cells having improved low-temperature operation are disclosed. In one embodiment, an interfacial layer of terbia-stabilized zirconia is located between the air electrode and electrolyte of the solid oxide fuel cell. The interfacial layer provides a barrier which controls interaction between the air electrode and electrolyte. The interfacial layer also reduces polarization loss through the reduction of the air electrode/electrolyte interfacial electrical resistance. In another embodiment, the solid oxide fuel cell comprises a scandia-stabilized zirconia electrolyte having high electrical conductivity. The scandia-stabilized zirconia electrolyte may be provided as a very thin layer in order to reduce resistance. The scandia-stabilized electrolyte is preferably used in combination with the terbia-stabilized interfacial layer. The solid oxide fuel cells are operable over wider temperature ranges and wider temperature gradients in comparison with conventional fuel cells.

Fluidized-bed catalytic coal-gasification process. [US patent; pretreatment to minimize agglomeration

DOEpatents

Euker, C.A. Jr.; Wesselhoft, R.D.; Dunkleman, J.J.; Aquino, D.C.; Gouker, T.R.

1981-09-14

Coal or similar carbonaceous solids impregnated with gasification catalyst constituents are oxidized by contact with a gas containing between 2 vol % and 21 vol % oxygen at a temperature between 50 and 250/sup 0/C in an oxidation zone and the resultant oxidized, catalyst impregnated solids are then gasified in a fluidized bed gasification zone at an elevated pressure. The oxidation of the catalyst impregnated solids under these conditions insures that the bed density in the fluidized bed gasification zone will be relatively high even though the solids are gasified at elevated pressure and temperature.

Structural characterization combined with the first principles simulations of barium/strontium cobaltite/ferrite as promising material for solid oxide fuel cells cathodes and high-temperature oxygen permeation membranes.

PubMed

Gangopadhayay, Shruba; Inerbaev, Talgat; Masunov, Artëm E; Altilio, Deanna; Orlovskaya, Nina

2009-07-01

Mixed ionic-electronic conducting perovskite type oxides with a general formula ABO(3) (where A = Ba, Sr, Ca and B = Co, Fe, Mn) often have high mobility of the oxygen vacancies and exhibit strong ionic conductivity. They are key materials that find use in several energy related applications, including solid oxide fuel cell (SOFC), sensors, oxygen separation membranes, and catalysts. Barium/strontium cobaltite/ferrite (BSCF) Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-delta) was recently identified as a promising candidate for cathode material in intermediate temperature SOFCs. In this work, we perform experimental and theoretical study of the local atomic structure of BSFC. Micro-Raman spectroscopy was performed to characterize the vibrational properties of BSCF. The Jahn-Teller distortion of octahedral coordination around Co(4+) cations was observed experimentally and explained theoretically. Different cations and oxygen vacancies ordering are examined using plane wave pseudopotential density functional theory. We find that cations are completely disordered, whereas oxygen vacancies exhibit a strong trend for aggregation in L-shaped trimer and square tetramer structure. On the basis of our results, we suggest a new explanation for BSCF phase stability. Instead of linear vacancy ordering, which must take place before the phase transition into brownmillerite structure, the oxygen vacancies in BSCF prefer to form the finite clusters and preserve the disordered cubic structure. This structural feature could be found only in the first-principles simulations and can not be explained by the effect of the ionic radii alone.

Interaction between municipal solid waste leachate and Bauru aquifer system: a study case in Brazil.

PubMed

de Faria, Gabriel Messias Moura; Mondelli, Giulliana

2017-12-01

Leachate contamination is a chronic and urgent problem present in municipal solid waste (MSW) landfill. Geochemical mathematical models in this work was suitable to study the dynamics of the leachate from an MSW landfill located in the Midwest of Sao Paulo, Brazil, a region with high precipitation and temperature and rich in chalcophile compounds and lithophile compounds, despite contamination with nitrogenous compounds. After 13 years of local aquifer monitoring, some groundwater samplings in Feb. 2004, Aug. 2007, Nov. 2009, and Feb. 2014 were chosen to be simulated. The hydrolysis is the main process at the landfill, together with absorption, adsorption, complexation, dilution, cation exchange, and oxidation, besides nitrification, reoxidation, and reduction.

Spark Plasma Sintering As a Solid-State Recycling Technique: The Case of Aluminum Alloy Scrap Consolidation

PubMed Central

Paraskevas, Dimos; Vanmeensel, Kim; Vleugels, Jef; Dewulf, Wim; Deng, Yelin; Duflou, Joost R.

2014-01-01

Recently, “meltless” recycling techniques have been presented for the light metals category, targeting both energy and material savings by bypassing the final recycling step of remelting. In this context, the use of spark plasma sintering (SPS) is proposed in this paper as a novel solid-state recycling technique. The objective is two-fold: (I) to prove the technical feasibility of this approach; and (II) to characterize the recycled samples. Aluminum (Al) alloy scrap was selected to demonstrate the SPS effectiveness in producing fully-dense samples. For this purpose, Al alloy scrap in the form of machining chips was cold pre-compacted and sintered bellow the solidus temperature at 490 °C, under elevated pressure of 200 MPa. The dynamic scrap compaction, combined with electric current-based joule heating, achieved partial fracture of the stable surface oxides, desorption of the entrapped gases and activated the metallic surfaces, resulting in efficient solid-state chip welding eliminating residual porosity. The microhardness, the texture, the mechanical properties, the microstructure and the density of the recycled specimens have been investigated. An X-ray computed tomography (CT) analysis confirmed the density measurements, revealing a void-less bulk material with homogeneously distributed intermetallic compounds and oxides. The oxide content of the chips incorporated within the recycled material slightly increases its elastic properties. Finally, a thermal distribution simulation of the process in different segments illustrates the improved energy efficiency of this approach. PMID:28788153

A review of high temperature co-electrolysis of H2O and CO2 to produce sustainable fuels using solid oxide electrolysis cells (SOECs): advanced materials and technology.

PubMed

Zheng, Yun; Wang, Jianchen; Yu, Bo; Zhang, Wenqiang; Chen, Jing; Qiao, Jinli; Zhang, Jiujun

2017-03-06

High-temperature solid oxide electrolysis cells (SOECs) are advanced electrochemical energy storage and conversion devices with high conversion/energy efficiencies. They offer attractive high-temperature co-electrolysis routes that reduce extra CO 2 emissions, enable large-scale energy storage/conversion and facilitate the integration of renewable energies into the electric grid. Exciting new research has focused on CO 2 electrochemical activation/conversion through a co-electrolysis process based on the assumption that difficult C[double bond, length as m-dash]O double bonds can be activated effectively through this electrochemical method. Based on existing investigations, this paper puts forth a comprehensive overview of recent and past developments in co-electrolysis with SOECs for CO 2 conversion and utilization. Here, we discuss in detail the approaches of CO 2 conversion, the developmental history, the basic principles, the economic feasibility of CO 2 /H 2 O co-electrolysis, and the diverse range of fuel electrodes as well as oxygen electrode materials. SOEC performance measurements, characterization and simulations are classified and presented in this paper. SOEC cell and stack designs, fabrications and scale-ups are also summarized and described. In particular, insights into CO 2 electrochemical conversions, solid oxide cell material behaviors and degradation mechanisms are highlighted to obtain a better understanding of the high temperature electrolysis process in SOECs. Proposed research directions are also outlined to provide guidelines for future research.

Spark Plasma Sintering As a Solid-State Recycling Technique: The Case of Aluminum Alloy Scrap Consolidation.

PubMed

Paraskevas, Dimos; Vanmeensel, Kim; Vleugels, Jef; Dewulf, Wim; Deng, Yelin; Duflou, Joost R

2014-08-06

Recently, "meltless" recycling techniques have been presented for the light metals category, targeting both energy and material savings by bypassing the final recycling step of remelting. In this context, the use of spark plasma sintering (SPS) is proposed in this paper as a novel solid-state recycling technique. The objective is two-fold: (I) to prove the technical feasibility of this approach; and (II) to characterize the recycled samples. Aluminum (Al) alloy scrap was selected to demonstrate the SPS effectiveness in producing fully-dense samples. For this purpose, Al alloy scrap in the form of machining chips was cold pre-compacted and sintered bellow the solidus temperature at 490 °C, under elevated pressure of 200 MPa. The dynamic scrap compaction, combined with electric current-based joule heating, achieved partial fracture of the stable surface oxides, desorption of the entrapped gases and activated the metallic surfaces, resulting in efficient solid-state chip welding eliminating residual porosity. The microhardness, the texture, the mechanical properties, the microstructure and the density of the recycled specimens have been investigated. An X-ray computed tomography (CT) analysis confirmed the density measurements, revealing a void-less bulk material with homogeneously distributed intermetallic compounds and oxides. The oxide content of the chips incorporated within the recycled material slightly increases its elastic properties. Finally, a thermal distribution simulation of the process in different segments illustrates the improved energy efficiency of this approach.

Enhanced reversibility and durability of a solid oxide Fe-air redox battery by carbothermic reaction derived energy storage materials.

PubMed

Zhao, Xuan; Li, Xue; Gong, Yunhui; Huang, Kevin

2014-01-18

The recently developed solid oxide metal-air redox battery is a new technology capable of high-rate chemistry. Here we report that the performance, reversibility and stability of a solid oxide iron-air redox battery can be significantly improved by nanostructuring energy storage materials from a carbothermic reaction.

Roles of Cationic and Elemental Calcium in the Electro-Reduction of Solid Metal Oxides in Molten Calcium Chloride

NASA Astrophysics Data System (ADS)

Qiu, Guohong; Jiang, Kai; Ma, Meng; Wang, Dihua; Jin, Xianbo; Chen, George Z.

2007-06-01

Previous work, mainly from this research group, is re-visited on electrochemical reduction of solid metal oxides, in the form of compacted powder, in molten CaCl2, aiming at further understanding of the roles of cationic and elemental calcium. The discussion focuses on six aspects: 1.) debate on two mechanisms proposed in the literature, i. e. electro-metallothermic reduction and electro-reduction (or electro-deoxidation), for the electrolytic removal of oxygen from solid metals or metal oxides in molten CaCl2; 2.) novel metallic cavity working electrodes for electrochemical investigations of compacted metal oxide powders in high temperature molten salts assisted by a quartz sealed Ag/AgCl reference electrode (650 ºC- 950 ºC); 3.) influence of elemental calcium on the background current observed during electrolysis of solid metal oxides in molten CaCl2; 4.) electrochemical insertion/ inclusion of cationic calcium into solid metal oxides; 5.) typical features of cyclic voltammetry and chronoamperometry (potentiostatic electrolysis) of metal oxide powders in molten CaCl2; and 6.) some kinetic considerations on the electrolytic removal of oxygen.

Liquid-phase and solid-phase microwave irradiations for reduction of graphite oxide

NASA Astrophysics Data System (ADS)

Zhao, Na; Wen, Chen-Yu; Zhang, David Wei; Wu, Dong-Ping; Zhang, Zhi-Bin; Zhang, Shi-Li

2014-12-01

In this paper, two microwave irradiation methods: (i) liquid-phase microwave irradiation (MWI) reduction of graphite oxide suspension dissolved in de-ionized water and N, N-dimethylformamide, respectively, and (ii) solid-phase MWI reduction of graphite oxide powder have been successfully carried out to reduce graphite oxide. The reduced graphene oxide products are thoroughly characterized by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectral analysis, Raman spectroscopy, UV-Vis absorption spectral analysis, and four-point probe conductivity measurements. The results show that both methods can efficiently remove the oxygen-containing functional groups attached to the graphite layers, though the solid-phase MWI reduction method can obtain far more efficiently a higher quality-reduced graphene oxide with fewer defects. The I(D)/I(G) ratio of the solid-phase MWI sample is as low as 0.46, which is only half of that of the liquid-phase MWI samples. The electrical conductivity of the reduced graphene oxide by the solid method reaches 747.9 S/m, which is about 25 times higher than that made by the liquid-phase method.

Small Systems Use of a Solid Arsenic Oxidizing Media in Place of Chemical Oxidation to Enhance Arsenic Removal

EPA Science Inventory

Presentation provides information on the need to oxidize As III to As V to increase arsenic removal followed by information on the results of an arsenic demonstration project (Plainview CDS) using a solid oxidizing media (Filox) to oxidize As III. The presentation includes a sho...

Aluminum Complexes of N2O23- Formazanate Ligands Supported by Phosphine Oxide Donors.

PubMed

Maar, Ryan R; Rabiee Kenaree, Amir; Zhang, Ruizhong; Tao, Yichen; Katzman, Benjamin D; Staroverov, Viktor N; Ding, Zhifeng; Gilroy, Joe B

2017-10-16

The synthesis and characterization of a new family of phosphine oxide supported aluminum formazanate complexes (7a,b, 8a, 9a) are reported. X-ray diffraction studies showed that the aluminum atoms in the complexes adopt an octahedral geometry in the solid state. The equatorial positions are occupied by an N 2 O 2 3- formazanate ligand, and the axial positions are occupied by L-type phosphine oxide donors. UV-vis absorption spectroscopy revealed that the complexes were strongly absorbing (ε ≈ 30000 M -1 cm -1 ) between 500 and 700 nm. The absorption maxima in this region were simulated using time-dependent density functional theory. With the exception of 3-cyano-substituted complex 7b, which showed maximum luminescence intensity in the presence of excess phosphine oxide, the title complexes are nonemissive in solution and the solid state. The electrochemical properties of the complexes were probed using cyclic voltammetry. Each complex underwent sequential one-electron oxidations in potential ranges of -0.12 to 0.29 V and 0.62 to 0.97 V, relative to the ferrocene/ferrocenium redox couple. Electrochemical reduction events were observed at potentials between -1.34 and -1.75 V. In combination with tri-n-propylamine as a coreactant, complex 7b acted as an electrochemiluminescence emitter with a maximum electrochemiluminescence intensity at a wavelength of 735 nm, red-shifted relative to the photoluminescence maximum of the same compound.

Sustainable synthesis of aldehydes, ketones or acids from neat alcohols using nitrogen dioxide gas, and related reactions.

PubMed

Naimi-Jamal, M Reza; Hamzeali, Hamideh; Mokhtari, Javad; Boy, Jürgen; Kaupp, Gerd

2009-01-01

Benzylic alcohols are quantitatively oxidized by gaseous nitrogen dioxide to give pure aromatic aldehydes. The reaction gas mixtures are transformed to nitric acid, which renders the processes free of waste. The exothermic gas-liquid or gas-solid reactions profit from the solubility of nitrogen dioxide in the neat benzylic alcohols. The acid formed impedes further oxidation of the benzaldehydes. The neat isolated benzaldehydes and nitrogen dioxide quantitatively give the benzoic acids. Solid long-chain primary alcohols are directly and quantitatively oxidized with nitrogen dioxide gas to give the fatty acids in the solid state. The oxidations with ubiquitous nitrogen dioxide are extended to solid heterocyclic thioamides, which gives disulfides, and to diphenylamine, which gives tetraphenylhydrazine. These sustainable (green) specific oxidation procedures produce no dangerous residues from the oxidizing agent or from auxiliaries.

Tailoring gadolinium-doped ceria-based solid oxide fuel cells to achieve 2 W cm(-2) at 550 °C.

PubMed

Lee, Jin Goo; Park, Jeong Ho; Shul, Yong Gun

2014-06-04

Low-temperature operation is necessary for next-generation solid oxide fuel cells due to the wide variety of their applications. However, significant increases in the fuel cell losses appear in the low-temperature solid oxide fuel cells, which reduce the cell performance. To overcome this problem, here we report Gd0.1Ce0.9O1.95-based low-temperature solid oxide fuel cells with nanocomposite anode functional layers, thin electrolytes and core/shell fibre-structured Ba0.5Sr0.5Co0.8Fe0.2O3-δ-Gd0.1Ce0.9O1.95 cathodes. In particular, the report describes the use of the advanced electrospinning and Pechini process in the preparation of the core/shell-fibre-structured cathodes. The fuel cells show a very high performance of 2 W cm(-2) at 550 °C in hydrogen, and are stable for 300 h even under the high current density of 1 A cm(-2). Hence, the results suggest that stable and high-performance solid oxide fuel cells at low temperatures can be achieved by modifying the microstructures of solid oxide fuel cell components.

Simultaneous NOx and hydrocarbon emissions control for lean-burn engines using low-temperature solid oxide fuel cell at open circuit.

PubMed

Huang, Ta-Jen; Hsu, Sheng-Hsiang; Wu, Chung-Ying

2012-02-21

The high fuel efficiency of lean-burn engines is associated with high temperature and excess oxygen during combustion and thus is associated with high-concentration NO(x) emission. This work reveals that very high concentration of NO(x) in the exhaust can be reduced and hydrocarbons (HCs) can be simultaneously oxidized using a low-temperature solid oxide fuel cell (SOFC). An SOFC unit is constructed with Ni-YSZ as the anode, YSZ as the electrolyte, and La(0.6)Sr(0.4)CoO(3) (LSC)-Ce(0.9)Gd(0.1)O(1.95) as the cathode, with or without adding vanadium to LSC. SOFC operation at 450 °C and open circuit can effectively treat NO(x) over the cathode at a very high concentration in the simulated exhaust. Higher NO(x) concentration up to 5000 ppm can result in a larger NO(x) to N(2) rate. Moreover, a higher oxygen concentration promotes NO conversion. Complete oxidation of HCs can be achieved by adding silver to the LSC current collecting layer. The SOFC-based emissions control system can treat NO(x) and HCs simultaneously, and can be operated without consuming the anode fuel (a reductant) at near the engine exhaust temperature to eliminate the need for reductant refilling and extra heating.

Reactive solute transport in streams: A surface complexation approach for trace metal sorption

USGS Publications Warehouse

Runkel, Robert L.; Kimball, Briant A.; McKnight, Diane M.; Bencala, Kenneth E.

1999-01-01

A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

Electrolytes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Fergus, Jeffrey W.

The high operating temperature of solid oxide fuel cells (SOFCs), as compared to polymer electrolyte membrane fuel cells (PEMFCs), improves tolerance to impurities in the fuel, but also creates challenges in the development of suitable materials for the various fuel cell components. In response to these challenges, intermediate temperature solid oxide fuel cells (IT-SOFCs) are being developed to reduce high-temperature material requirements, which will extend useful lifetime, improve durability and reduce cost, while maintaining good fuel flexibility. A major challenge in reducing the operating temperature of SOFCs is the development of solid electrolyte materials with sufficient conductivity to maintain acceptably low ohmic losses during operation. In this paper, solid electrolytes being developed for solid oxide fuel cells, including zirconia-, ceria- and lanthanum gallate-based materials, are reviewed and compared. The focus is on the conductivity, but other issues, such as compatibility with electrode materials, are also discussed.

Dissolution of uranium oxides from simulated environmental swipes using ammonium bifluoride

DOE PAGES

Meyers, Lisa A.; Yoshida, Thomas M.; Chamberlin, Rebecca M.; ...

2016-11-01

We developed an analytical chemistry method to quantitatively recover microgram quanties of solid uranium oxides from swipe media using ammonium bifluoride (ABF, NH 4HF 2) solution. Recovery of uranium from surrogate swipe media (filter paper) was demonstrated at initial uranium loading levels between 3 and 20 µg filter -1. Moreover, the optimal conditions for extracting U 3O 8 and UO 2 are using 1 % ABF solution and incubating at 80 °C for one hour. The average uranium recoveries are 100 % for U 3O 8, and 90 % for UO 2. Finally, with this method, uranium concentration as lowmore » as 3 µg filter -1 can be recovered for analysis.« less

Quadrupolar magic angle spinning NMR spectra fitted using the Pearson IV function.

PubMed

Mironenko, Roman M; Belskaya, Olga B; Talsi, Valentin P; Likholobov, Vladimir A

2014-01-01

The Pearson IV function was used to fit the asymmetric solid-state (27)Al NMR spectra of alumina based catalysts. A high convergence (correlation coefficient is no less than 0.997) between experimental and simulated spectra was achieved. The decomposition of the (27)Al NMR spectra of zinc/aluminum mixed oxides with different Zn/Al molar ratio revealed an increased fraction (6-9%) of pentacoordinated aluminum atoms in these oxides as compared to γ-Al2O3. As the Zn/Al ratio is raised, the fraction of [AlO6] octahedral units decreases, while the fraction of [AlO4] tetrahedra increases. Copyright © 2014 Elsevier Inc. All rights reserved.

Quantitative 3D evolution of colloidal nanoparticle oxidation in solution

DOE PAGES

Sun, Yugang; Zuo, Xiaobing; Sankaranarayanan, Subramanian K. R. S.; ...

2017-04-21

Real-time tracking three-dimensional (3D) evolution of colloidal nanoparticles in solution is essential for understanding complex mechanisms involved in nanoparticle growth and transformation. We simultaneously use time-resolved small-angle and wide-angle x-ray scattering to monitor oxidation of highly uniform colloidal iron nanoparticles, enabling the reconstruction of intermediate 3D morphologies of the nanoparticles with a spatial resolution of ~5 Å. The in-situ probing combined with large-scale reactive molecular dynamics simulations reveals the transformational details from the solid metal nanoparticles to hollow metal oxide nanoshells via nanoscale Kirkendall process, for example, coalescence of voids upon their growth, reversing of mass diffusion direction depending onmore » crystallinity, and so forth. In conclusion, our results highlight the complex interplay between defect chemistry and defect dynamics in determining nanoparticle transformation and formation.« less

Quantitative 3D evolution of colloidal nanoparticle oxidation in solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Yugang; Zuo, Xiaobing; Sankaranarayanan, Subramanian K. R. S.

Real-time tracking three-dimensional (3D) evolution of colloidal nanoparticles in solution is essential for understanding complex mechanisms involved in nanoparticle growth and transformation. We simultaneously use time-resolved small-angle and wide-angle x-ray scattering to monitor oxidation of highly uniform colloidal iron nanoparticles, enabling the reconstruction of intermediate 3D morphologies of the nanoparticles with a spatial resolution of ~5 Å. The in-situ probing combined with large-scale reactive molecular dynamics simulations reveals the transformational details from the solid metal nanoparticles to hollow metal oxide nanoshells via nanoscale Kirkendall process, for example, coalescence of voids upon their growth, reversing of mass diffusion direction depending onmore » crystallinity, and so forth. In conclusion, our results highlight the complex interplay between defect chemistry and defect dynamics in determining nanoparticle transformation and formation.« less

Hardware simulation of fuel cell/gas turbine hybrids

NASA Astrophysics Data System (ADS)

Smith, Thomas Paul

Hybrid solid oxide fuel cell/gas turbine (SOFC/GT) systems offer high efficiency power generation, but face numerous integration and operability challenges. This dissertation addresses the application of hardware-in-the-loop simulation (HILS) to explore the performance of a solid oxide fuel cell stack and gas turbine when combined into a hybrid system. Specifically, this project entailed developing and demonstrating a methodology for coupling a numerical SOFC subsystem model with a gas turbine that has been modified with supplemental process flow and control paths to mimic a hybrid system. This HILS approach was implemented with the U.S. Department of Energy Hybrid Performance Project (HyPer) located at the National Energy Technology Laboratory. By utilizing HILS the facility provides a cost effective and capable platform for characterizing the response of hybrid systems to dynamic variations in operating conditions. HILS of a hybrid system was accomplished by first interfacing a numerical model with operating gas turbine hardware. The real-time SOFC stack model responds to operating turbine flow conditions in order to predict the level of thermal effluent from the SOFC stack. This simulated level of heating then dynamically sets the turbine's "firing" rate to reflect the stack output heat rate. Second, a high-speed computer system with data acquisition capabilities was integrated with the existing controls and sensors of the turbine facility. In the future, this will allow for the utilization of high-fidelity fuel cell models that infer cell performance parameters while still computing the simulation in real-time. Once the integration of the numeric and the hardware simulation components was completed, HILS experiments were conducted to evaluate hybrid system performance. The testing identified non-intuitive transient responses arising from the large thermal capacitance of the stack that are inherent to hybrid systems. Furthermore, the tests demonstrated the capabilities of HILS as a research tool for investigating the dynamic behavior of SOFC/GT hybrid power generation systems.

Geochemical modeling of leaching of Ca, Mg, Al, and Pb from cementitious waste forms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martens, E., E-mail: evelien.martens@csiro.a; Jacques, D.; Van Gerven, T.

2010-08-15

Results from extraction tests on cement-waste samples were simulated with a thermodynamic equilibrium model using a consistent database, to which lead data were added. Subsequent diffusion tests were modeled by means of a 3D diffusive transport model combined with the geochemical model derived from the extraction tests. Modeling results of the leached major element concentrations for both uncarbonated and (partially) carbonated samples agreed well with the extraction test using the set of pure minerals and solid solutions present in the database. The observed decrease in Ca leaching with increasing carbonation level was qualitatively predicted. Simulations also revealed that Pb leachingmore » is not controlled by dissolution/precipitation only. The addition of the calcite-cerrusite solid solution and adsorption reactions on amorphous Fe- and Al-oxides improved the predictions and are considered to control the Pb leaching during the extractions tests. The dynamic diffusive leaching tests were appropriately modeled for Na, K, Ca and Pb.« less

Characterization of ash melting behaviour at high temperatures under conditions simulating combustible solid waste gasification.

PubMed

Niu, Miaomiao; Dong, Qing; Huang, Yaji; Jin, Baosheng; Wang, Hongyan; Gu, Haiming

2018-05-01

To achieve high-temperature gasification-melting of combustible solid waste, ash melting behaviour under conditions simulating high-temperature gasification were studied. Raw ash (RA) and gasified ash (GA) were prepared respectively by waste ashing and fluidized bed gasification. Results of microstructure and composition of the two-ash indicated that GA showed a more porous structure and higher content of alkali and alkali earth metals among metallic elements. Higher temperature promoted GA melting and could reach a complete flowing state at about 1250°C. The order of melting rate of GA under different atmospheres was reducing condition > inert condition > oxidizing condition, which might be related to different existing forms of iron during melting and different flux content with atmosphere. Compared to RA, GA showed lower melting activity at the same condition due to the existence of an unconverted carbon and hollow structure. The melting temperature for sufficient melting and separation of GA should be at least 1250°C in this work.

Dynamic Modeling, Model-Based Control, and Optimization of Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Spivey, Benjamin James

2011-07-01

Solid oxide fuel cells are a promising option for distributed stationary power generation that offers efficiencies ranging from 50% in stand-alone applications to greater than 80% in cogeneration. To advance SOFC technology for widespread market penetration, the SOFC should demonstrate improved cell lifetime and load-following capability. This work seeks to improve lifetime through dynamic analysis of critical lifetime variables and advanced control algorithms that permit load-following while remaining in a safe operating zone based on stress analysis. Control algorithms typically have addressed SOFC lifetime operability objectives using unconstrained, single-input-single-output control algorithms that minimize thermal transients. Existing SOFC controls research has not considered maximum radial thermal gradients or limits on absolute temperatures in the SOFC. In particular, as stress analysis demonstrates, the minimum cell temperature is the primary thermal stress driver in tubular SOFCs. This dissertation presents a dynamic, quasi-two-dimensional model for a high-temperature tubular SOFC combined with ejector and prereformer models. The model captures dynamics of critical thermal stress drivers and is used as the physical plant for closed-loop control simulations. A constrained, MIMO model predictive control algorithm is developed and applied to control the SOFC. Closed-loop control simulation results demonstrate effective load-following, constraint satisfaction for critical lifetime variables, and disturbance rejection. Nonlinear programming is applied to find the optimal SOFC size and steady-state operating conditions to minimize total system costs.

Impact of Microstructure on MoS 2 Oxidation and Friction

DOE PAGES

Curry, John F.; Wilson, Mark A.; Luftman, Henry S.; ...

2017-07-31

In this work, we demonstrate the role of microstructure in the friction and oxidation behavior of the lamellar solid lubricant molybdenum disulfide (MoS 2). We report on systematic investigations of oxidation and friction for two MoS 2 films with distinctively different microstructures—amorphous and planar/highly-ordered—before and after exposure to atomic oxygen (AO) and high-temperature (250 °C) molecular oxygen. A combination of experimental tribology, molecular dynamics simulations, X-ray photoelectron spectroscopy (XPS), and high-sensitivity low-energy ion scattering (HS-LEIS) was used to reveal new insights about the links between structure and properties of these widely utilized low-friction materials. Initially, ordered MoS 2 films showedmore » a surprising resistance to both atomic and molecular oxygens (even at elevated temperature), retaining characteristic low friction after exposure to extreme oxidative environments. Finally, XPS shows comparable oxidation of both coatings via AO; however, monolayer resolved compositional depth profiles from HS-LEIS reveal that the microstructure of the ordered coatings limits oxidation to the first atomic layer.« less

Impact of Microstructure on MoS 2 Oxidation and Friction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Curry, John F.; Wilson, Mark A.; Luftman, Henry S.

In this work, we demonstrate the role of microstructure in the friction and oxidation behavior of the lamellar solid lubricant molybdenum disulfide (MoS 2). We report on systematic investigations of oxidation and friction for two MoS 2 films with distinctively different microstructures—amorphous and planar/highly-ordered—before and after exposure to atomic oxygen (AO) and high-temperature (250 °C) molecular oxygen. A combination of experimental tribology, molecular dynamics simulations, X-ray photoelectron spectroscopy (XPS), and high-sensitivity low-energy ion scattering (HS-LEIS) was used to reveal new insights about the links between structure and properties of these widely utilized low-friction materials. Initially, ordered MoS 2 films showedmore » a surprising resistance to both atomic and molecular oxygens (even at elevated temperature), retaining characteristic low friction after exposure to extreme oxidative environments. Finally, XPS shows comparable oxidation of both coatings via AO; however, monolayer resolved compositional depth profiles from HS-LEIS reveal that the microstructure of the ordered coatings limits oxidation to the first atomic layer.« less

Experimental and modeling study of high performance direct carbon solid oxide fuel cell with in situ catalytic steam-carbon gasification reaction

NASA Astrophysics Data System (ADS)

Xu, Haoran; Chen, Bin; Zhang, Houcheng; Tan, Peng; Yang, Guangming; Irvine, John T. S.; Ni, Meng

2018-04-01

In this paper, 2D models for direct carbon solid oxide fuel cells (DC-SOFCs) with in situ catalytic steam-carbon gasification reaction are developed. The simulation results are found to be in good agreement with experimental data. The performance of DC-SOFCs with and without catalyst are compared at different operating potential, anode inlet gas flow rate and operating temperature. It is found that adding suitable catalyst can significantly speed up the in situ steam-carbon gasification reaction and improve the performance of DC-SOFC with H2O as gasification agent. The potential of syngas and electricity co-generation from the fuel cell is also evaluated, where the composition of H2 and CO in syngas can be adjusted by controlling the anode inlet gas flow rate. In addition, the performance DC-SOFCs and the percentage of fuel in the outlet gas are both increased with increasing operating temperature. At a reduced temperature (below 800 °C), good performance of DC-SOFC can still be obtained with in-situ catalytic carbon gasification by steam. The results of this study form a solid foundation to understand the important effect of catalyst and related operating conditions on H2O-assisted DC-SOFCs.

Characterization of ammonia borane for chemical propulsion applications

NASA Astrophysics Data System (ADS)

Weismiller, Michael

Ammonia borane (NH3BH3; AB), which has a hydrogen content of 19.6% by weight, has been studied recently as a potential means of hydrogen storage for use in fuel cell applications. Its gaseous decomposition products have a very low molecular weight, which makes AB attractive in a propulsion application, since specific impulse is inversely related to the molecular weight of the products. AB also contains boron, which is a fuel of interest for solid propellants because of its high energy density per unit volume. Although boron particles are difficult to ignite due to their passivation layer, the boron molecularly bound in AB may react more readily. The concept of fuel depots in low-earth orbit has been proposed for use in deep space exploration. These would require propellants that are easily storable for long periods of time. AB is a solid at standard temperature and pressure and would not suffer from mass loss due to boil-off like cryogenic hydrogen. The goal of this work is to evaluate AB as a viable fuel in chemical propulsion. Many studies have examined AB decomposition at slow heating rates, but in a propellant, AB will experience rapid heating. Since heating rate has been shown to affect the thermolysis pathways in energetic materials, AB thermolysis was studied at high heating rates using molecular dynamics simulations with a ReaxFF reactive force field and experimental studies with a confined rapid thermolysis set-up using time-of-flight mass spectrometry and FTIR absorption spectroscopy diagnostics. Experimental results showed the formation of NH3, H2NBH2, H2, and at later times, c-(N3B3H6) in the gas phase, while polymer formation was observed in the condensed phase. Molecular dynamics simulations provided an atomistic description of the reactions which likely form these compounds. Another subject which required investigation was the reaction of AB in oxidizing environments, as there were no previous studies in the literature. Oxygen bond descriptions were added to the ReaxFF force field and molecular dynamics simulations were performed to identify important species and reactions in the AB oxidation. Since the thermodynamic properties of many of these species were unknown, density functional theory (DFT) calculations were performed in the Jaguear 7.8 program using the B3LYP functional and 6-311G**++ basis set to calculate enthalpy and entropy of formation, as well as specific heat as a function of temperature. These results were used to create a gas-phase chemical kinetic mechanism for AB combustion. New elementary reactions (57) were combined with those found in the literature for ammonia and boron oxidation, to form a mechanism of 201 reversible reactions. Results from a simple homogenous, constant pressure and energy calculation are presented in this work. The results show that H2NBH2 can be dehydrogenated via radical attack when temperatures are too low to overcome the hydrogen elimination barrier and pressures are low enough to allow sufficient radicals to form. Molecular dynamics calculations require very high pressures to facilitate reactions over a short simulation time, and show the formation of heavy B/N/H/O molecules, such as HNBOH and H2NB(OH)2. On the other hand, the chemical kinetics calculations at 1 atm show that if the HNBO molecule is further oxidized, the products will likely fission with B-N bond cleavage. The final objective towards the research goal was to study how AB can be effectively integrated into a propulsion application. AB was added to a paraffin wax binder to form a heterogeneous solid fuel matrix. Opposed-flow burner experiments were performed where a flow of gaseous oxygen was impinged on the solid fuel surface and regression rates were measured. Regression rates were shown to increase with small additions of AB, but the condensed phase product build-up at higher AB concentrations limited the solid fuel regression. Solid fuel grains with various amounts of AB were manufactured and tested in a lab scale hybrid rocket engine, where performance parameters such as thrust, chamber pressure, specific impulse (Isp) and characteristic exhaust velocity (C*), were measured. AB addition was shown to increase I sp and C*, but large additions were shown to reduce the overall thrust due to the hindrance of the solid fuel regression.

Simulation of local ion transport in lamellar block copolymer electrolytes based on electron micrographs

DOE PAGES

Chintapalli, Mahati; Higa, Kenneth; Chen, X. Chelsea; ...

2016-12-19

A method is presented in this paper to relate local morphology and ionic conductivity in a solid, lamellar block copolymer electrolyte for lithium batteries, by simulating conductivity through transmission electron micrographs. The electrolyte consists of polystyrene-block-poly(ethylene oxide) mixed with lithium bis(trifluoromethanesulfonyl) imide salt (SEO/LiTFSI), where the polystyrene phase is structural phase and the poly(ethylene oxide)/LiTFSI phase is ionically conductive. The electric potential distribution is simulated in binarized micrographs by solving the Laplace equation with constant potential boundary conditions. A morphology factor, f, is reported for each image by calculating the effective conductivity relative to a homogenous conductor. Images from twomore » samples are examined, one annealed with large lamellar grains and one unannealed with small grains. The average value off is 0.45 ± 0.04 for the annealed sample, and 0.37 ± 0.03 for the unannealed sample, both close to the value predicted by effective medium theory, 1/2. Simulated conductivities are compared to published experimental conductivities. The value of f Unannealed/f Annealed is 0.82 for simulations and 6.2 for experiments. Simulation results correspond well to predictions by effective medium theory but do not explain the experimental measurements. Finally, observation of nanoscale morphology over length scales greater than the size of the micrographs (~1 μm) may be required to explain the experimental results.« less

Simulation of local ion transport in lamellar block copolymer electrolytes based on electron micrographs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chintapalli, Mahati; Higa, Kenneth; Chen, X. Chelsea

A method is presented in this paper to relate local morphology and ionic conductivity in a solid, lamellar block copolymer electrolyte for lithium batteries, by simulating conductivity through transmission electron micrographs. The electrolyte consists of polystyrene-block-poly(ethylene oxide) mixed with lithium bis(trifluoromethanesulfonyl) imide salt (SEO/LiTFSI), where the polystyrene phase is structural phase and the poly(ethylene oxide)/LiTFSI phase is ionically conductive. The electric potential distribution is simulated in binarized micrographs by solving the Laplace equation with constant potential boundary conditions. A morphology factor, f, is reported for each image by calculating the effective conductivity relative to a homogenous conductor. Images from twomore » samples are examined, one annealed with large lamellar grains and one unannealed with small grains. The average value off is 0.45 ± 0.04 for the annealed sample, and 0.37 ± 0.03 for the unannealed sample, both close to the value predicted by effective medium theory, 1/2. Simulated conductivities are compared to published experimental conductivities. The value of f Unannealed/f Annealed is 0.82 for simulations and 6.2 for experiments. Simulation results correspond well to predictions by effective medium theory but do not explain the experimental measurements. Finally, observation of nanoscale morphology over length scales greater than the size of the micrographs (~1 μm) may be required to explain the experimental results.« less

Nanocrystal-polymer nanocomposite electrochromic device

DOEpatents

Milliron, Delia; Runnerstrom, Evan; Helms, Brett; Llordes, Anna; Buonsanti, Raffaella; Garcia, Guillermo

2015-12-08

Described is an electrochromic nanocomposite film comprising a solid matrix of an oxide based material, the solid matrix comprising a plurality of transparent conducting oxide (TCO) nanostructures dispersed in the solid matrix and a lithium salt dispersed in the solid matrix. Also described is a near infrared nanostructured electrochromic device having a functional layer comprising the electrochromic nanocomposite film.

Effect of calcium oxide on the efficiency of ferrous ion oxidation and total iron precipitation during ferrous ion oxidation in simulated acid mine drainage treatment with inoculation of Acidithiobacillus ferrooxidans.

PubMed

Liu, Fenwu; Zhou, Jun; Jin, Tongjun; Zhang, Shasha; Liu, Lanlan

2016-01-01

Calcium oxide was added into ferrous ion oxidation system in the presence of Acidithiobacillus ferrooxidans at concentrations of 0-4.00 g/L. The pH, ferrous ion oxidation efficiency, total iron precipitation efficiency, and phase of the solid minerals harvested from different treatments were investigated during the ferrous ion oxidation process. In control check (CK) system, pH of the solution decreased from 2.81 to 2.25 when ferrous ions achieved complete oxidation after 72 h of Acidithiobacillus ferrooxidans incubation without the addition of calcium oxide, and total iron precipitation efficiency reached 20.2%. Efficiency of ferrous ion oxidation and total iron precipitation was significantly improved when the amount of calcium oxide added was ≤1.33 g/L, and the minerals harvested from systems were mainly a mixture of jarosite and schwertmannite. For example, the ferrous ion oxidation efficiency reached 100% at 60 h and total iron precipitation efficiency was increased to 32.1% at 72 h when 1.33 g/L of calcium oxide was added. However, ferrous ion oxidation and total iron precipitation for jarosite and schwertmannite formation were inhibited if the amount of calcium oxide added was above 2.67 g/L, and large amounts of calcium sulfate dihydrate were generated in systems.

Delivery system for molten salt oxidation of solid waste

DOEpatents

Brummond, William A.; Squire, Dwight V.; Robinson, Jeffrey A.; House, Palmer A.

2002-01-01

The present invention is a delivery system for safety injecting solid waste particles, including mixed wastes, into a molten salt bath for destruction by the process of molten salt oxidation. The delivery system includes a feeder system and an injector that allow the solid waste stream to be accurately metered, evenly dispersed in the oxidant gas, and maintained at a temperature below incineration temperature while entering the molten salt reactor.

Oxygen potential of uranium--plutonium oxide as determined by controlled- atmosphere thermogravimetry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swanson, Gerald C.

1975-10-01

The oxygen-to-metal atom ratio, or O/M, of solid solution uranium- plutonium oxide reactor fuel is a measure of the concentration of crystal defects in the oxide which affect many fuel properties, particularly, fuel oxygen potential. Fabrication of a high-temperature oxygen electrode, employing an electro-active tip of oxygen-deficient solid-state electrolyte, intended to confirm gaseous oxygen potentials is described. Uranium oxide and plutonium oxide O/M reference materials were prepared by in situ oxidation of high purity metals in the thermobalance. A solid solution uranium-plutonium oxide O/M reference material was prepared by alloying the uranium and plutonium metals in a yttrium oxide cruciblemore » at 1200°C and oxidizing with moist He at 250°C. The individual and solid solution oxides were isothermally equilibrated with controlled oxygen potentials between 800 and 1300°C and the equilibrated O/ M ratios calculated with corrections for impurities and buoyancy effects. Use of a reference oxygen potential of -100 kcal/mol to produce an O/M of 2.000 is confirmed by these results. However, because of the lengthy equilibration times required for all oxides, use of the O/M reference materials rather than a reference oxygen potential is recommended for O/M analysis methods calibrations.« less

Colossal super saturation of oxygen at the iron-aluminum interfaces fabricated using solid state welding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sridharan, Niyanth; Isheim, D.; Seidman, David N.

Solid state joining is achieved in three steps, (i) interface asperity deformation, (ii) oxide dispersion, followed by (iii) atomic contact and bonding. Atomically clean metallic surfaces without an oxide layer bond spontaneously. Despite its importance the oxide dispersion mechanism is not well studied. In this work the first ever atom probe study of iron-aluminum solid state welds show that the oxygen concentration at the interface is 20 at.%. This is significantly lower than any equilibrium oxide concentration. Here, we therefore propose that the high-strain rate deformation at the interfaces renders the oxide unstable resulting in the observed concentration of oxygen.

Colossal super saturation of oxygen at the iron-aluminum interfaces fabricated using solid state welding

DOE PAGES

Sridharan, Niyanth; Isheim, D.; Seidman, David N.; ...

2016-12-14

Solid state joining is achieved in three steps, (i) interface asperity deformation, (ii) oxide dispersion, followed by (iii) atomic contact and bonding. Atomically clean metallic surfaces without an oxide layer bond spontaneously. Despite its importance the oxide dispersion mechanism is not well studied. In this work the first ever atom probe study of iron-aluminum solid state welds show that the oxygen concentration at the interface is 20 at.%. This is significantly lower than any equilibrium oxide concentration. Here, we therefore propose that the high-strain rate deformation at the interfaces renders the oxide unstable resulting in the observed concentration of oxygen.

Effects of temperature and pressure on the performance of a solid oxide fuel cell running on steam reformate of kerosene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chick, Lawrence A.; Marina, Olga A.; Coyle, Christopher A.

2013-08-15

A button solid oxide fuel cell with a La0.6Sr0.4Co0.2Fe0.8O3 cathode and a nickel-YSZ anode was tested over a range of temperatures from 650 to 800°C and a range of pressures from 101 to 724 kPa. The fuel was simulated steam-reformed kerosene and the oxidant was air. The observed increases in open circuit voltages (OCV) were accurately predicted by the Nernst equation. Kinetics also increased, although the power boost due to kinetics was about two thirds as large as the boost due to OCV. The total power boost in going from 101 to 724 kPa at 750°C and 0.8 volts wasmore » 66%. Impedance spectroscopy demonstrated a significant decrease in electrodic losses at elevated pressures. Complex impedance spectra were dominated by a combination of low frequency processes that decreased markedly with increasing pressure. A composite of high-frequency processes also decreased with pressure, but to a lesser extent. An empirical algorithm that accurately predicts the increased fuel cell performance at elevated pressures was developed for our results and was also suitable for some, but not all, data reported in the literature.« less

Immobilization of 99-Technetium (VII) by Fe(II)-Goethite and Limited Reoxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Um, Wooyong; Chang, Hyun-Shik; Icenhower, Jonathan P.

2011-05-04

Synthesized goethite was successfully used with addition of Fe(II) to sequester Tc present in both deionized water and simulated off-gas scrubber waste solutions. Pertechnetate concentration in solution decreased immediately when the pH was raised above 7 by addition of sodium hydroxide. Removal of Tc(VII) from solution occurred most likely as a result of heterogeneous surface-catalyzed reduction to Tc(IV) and subsequent co-precipitation onto the goethite. The final Tc-bearing solid was identified as goethite-dominated Fe(III)-(oxy)hydroxide based on XRD analysis, confirming the widespread observation of its characteristic acicular habit by TEM/SEM images. Analysis of the solid precipitate by XAFS showed that the dominantmore » oxidation state of Tc was Tc(IV) and was in octahedral coordination with Tc-O, Fe-O, and Tc-Fe bond distances that are consistent with direct substitution of Tc for Fe in the goethite structure. In some experiments the final Tc-goethite product was subsequently armored with additional layers of freshly precipitated goethite. Successful incorporation of Tc(IV) within the goethite mineral lattice and subsequent goethite armoring can limit re-oxidation of Tc(IV) and its subsequent release from Tc-goethite waste forms, even when the final product is placed in oxidizing environments that typify shallow waste burial facilities.« less

Application of PAC and flocculants for improving settling of solid particles in oilfield wastewater with high salinity and Ca2.

PubMed

Liu, Guoliang; Zhang, Fusheng; Qu, Yuanzhi; Liu, He; Zhao, Lun; Cui, Mingyue; Ou, Yangjian; Geng, Dongshi

2017-09-01

The suspended solids in wastewater from Rekabak oilfield, Kazakhstan, were characterized and treated with flocculants to enhance settling. The wastewater contained a high concentration of total dissolved solids and calcium ion. Scanning electron microscopy and energy dispersive X-ray analyses showed that suspended solids were mainly composed of corrosion products (iron oxides) and silicon dioxide particles. Also, much salt deposition from wastewater caused a large increase in the suspended solids value. The settling of solid particles in wastewater was investigated by turbidity decrease within 60 min. The particle settling was enhanced by adding polyaluminum chloride (PAC) as coagulant and hydrolyzed polyacryamide (HPAM) or cationic polyacrylamide (CPAM) as flocculant. At optimal dose, the particle settling ability with PAC and CPAM was better than that with PAC and HPAM. Particle size analysis showed that HPAM or CPAM with high molecular weight played an important role for enlarging the particle size. The experiments with simulated wastewater showed that particle settling by using HPAM deteriorated significantly compared to that by CPAM at high calcium ion. This study provides further understanding about the effect of high salinity and Ca 2+ on solids formation, flocculant performance and particle settling. Meanwhile, the results are also helpful to develop novel flocculants used for high salinity wastewater.

49 CFR 177.838 - Class 4 (flammable solid) materials, Class 5 (oxidizing) materials, and Division 4.2 (pyroforic...

Code of Federal Regulations, 2014 CFR

2014-10-01

... (flammable solid) or Class 5 (oxidizing) materials shall be contained entirely within the body of the motor.... Special care shall also be taken in the loading of any motor vehicle with Class 4 (flammable solid) or... 49 Transportation 2 2014-10-01 2014-10-01 false Class 4 (flammable solid) materials, Class 5...

49 CFR 177.838 - Class 4 (flammable solid) materials, Class 5 (oxidizing) materials, and Division 4.2 (pyroforic...

Code of Federal Regulations, 2013 CFR

2013-10-01

... (flammable solid) or Class 5 (oxidizing) materials shall be contained entirely within the body of the motor.... Special care shall also be taken in the loading of any motor vehicle with Class 4 (flammable solid) or... 49 Transportation 2 2013-10-01 2013-10-01 false Class 4 (flammable solid) materials, Class 5...

49 CFR 177.838 - Class 4 (flammable solid) materials, Class 5 (oxidizing) materials, and Division 4.2 (pyroforic...

Code of Federal Regulations, 2012 CFR

2012-10-01

... (flammable solid) or Class 5 (oxidizing) materials shall be contained entirely within the body of the motor.... Special care shall also be taken in the loading of any motor vehicle with Class 4 (flammable solid) or... 49 Transportation 2 2012-10-01 2012-10-01 false Class 4 (flammable solid) materials, Class 5...

High-Temperature Desulfurization of Heavy Fuel-Derived Reformate Gas Streams for SOFC Applications

NASA Technical Reports Server (NTRS)

Flytzani-Stephanopoulos, Maria; Surgenor, Angela D.

2007-01-01

Desulfurization of the hot reformate gas produced by catalytic partial oxidation or autothermal reforming of heavy fuels, such as JP-8 and jet fuels, is required prior to using the gas in a solid oxide fuel cell (SOFC). Development of suitable sorbent materials involves the identification of sorbents with favorable sulfidation equilibria, good kinetics, and high structural stability and regenerability at the SOFC operating temperatures (650 to 800 C). Over the last two decades, a major barrier to the development of regenerable desulfurization sorbents has been the gradual loss of sorbent performance in cyclic sulfidation and regeneration at such high temperatures. Mixed oxide compositions based on ceria were examined in this work as regenerable sorbents in simulated reformate gas mixtures and temperatures greater than 650 C. Regeneration was carried out with dilute oxygen streams. We have shown that under oxidative regeneration conditions, high regeneration space velocities (greater than 80,000 h(sup -1)) can be used to suppress sulfate formation and shorten the total time required for sorbent regeneration. A major finding of this work is that the surface of ceria and lanthanan sorbents can be sulfided and regenerated completely, independent of the underlying bulk sorbent. This is due to reversible adsorption of H2S on the surface of these sorbents even at temperatures as high as 800 C. La-rich cerium oxide formulations are excellent for application to regenerative H2S removal from reformate gas streams at 650 to 800 C. These results create new opportunities for compact sorber/regenerator reactor designs to meet the requirements of solid oxide fuel cell systems at any scale.

Solid waste treatment processes for space station

NASA Technical Reports Server (NTRS)

Marrero, T. R.

1983-01-01

The purpose of this study was to evaluate the state-of-the-art of solid waste(s) treatment processes applicable to a Space Station. From the review of available information a source term model for solid wastes was determined. An overall system is proposed to treat solid wastes under constraints of zero-gravity and zero-leakage. This study contains discussion of more promising potential treatment processes, including supercritical water oxidation, wet air (oxygen) oxidation, and chemical oxidation. A low pressure, batch-type treament process is recommended. Processes needed for pretreatment and post-treatment are hardware already developed for space operations. The overall solid waste management system should minimize transfer of wastes from their collection point to treatment vessel.

Symmetrical, bi-electrode supported solid oxide fuel cell

NASA Technical Reports Server (NTRS)

Sofie, Stephen W. (Inventor); Cable, Thomas L. (Inventor)

2009-01-01

The present invention is a symmetrical bi-electrode supported solid oxide fuel cell comprising a sintered monolithic framework having graded pore electrode scaffolds that, upon treatment with metal solutions and heat subsequent to sintering, acquire respective anodic and cathodic catalytic activity. The invention is also a method for making such a solid oxide fuel cell. The graded pore structure of the graded pore electrode scaffolds in achieved by a novel freeze casting for YSZ tape.

Process for treating effluent from a supercritical water oxidation reactor

DOEpatents

Barnes, Charles M.; Shapiro, Carolyn

1997-01-01

A method for treating a gaseous effluent from a supercritical water oxidation reactor containing entrained solids is provided comprising the steps of expanding the gas/solids effluent from a first to a second lower pressure at a temperature at which no liquid condenses; separating the solids from the gas effluent; neutralizing the effluent to remove any acid gases; condensing the effluent; and retaining the purified effluent to the supercritical water oxidation reactor.

Oxygen partial pressure sensor

DOEpatents

Dees, D.W.

1994-09-06

A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured. 1 fig.

Oxygen partial pressure sensor

DOEpatents

Dees, Dennis W.

1994-01-01

A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured.

Alternate nozzle ablative materials program

NASA Technical Reports Server (NTRS)

Kimmel, N. A.

1984-01-01

Four subscale solid rocket motor tests were conducted successfully to evaluate alternate nozzle liner, insulation, and exit cone structural overwrap components for possible application to the Space Shuttle Solid Rocket Motor (SRM) nozzle asasembly. The 10,000 lb propellant motor tests were simulated, as close as practical, the configuration and operational environment of the full scale SRM. Fifteen PAN based and three pitch based materials had no filler in the phenolic resin, four PAN based materials had carbon microballoons in the resin, and the rest of the materials had carbon powder in the resin. Three nozzle insulation materials were evaluated; an aluminum oxide silicon oxide ceramic fiber mat phenolic material with no resin filler and two E-glass fiber mat phenolic materials with no resin filler. It was concluded by MTI/WD (the fabricator and evaluator of the test nozzles) and NASA-MSFC that it was possible to design an alternate material full scale SRM nozzle assembly, which could provide an estimated 360 lb increased payload capability for Space Shuttle launches over that obtainable with the current qualified SRM design.

A Mechanistic-Based Healing Model for Self-Healing Glass Seals Used in Solid Oxide Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Wei; Sun, Xin; Stephens, Elizabeth V.

The usage of self-healing glass as hermetic seals is a recent advancement in sealing technology development for the planar solid oxide fuel cells (SOFCs). Because of its capability of restoring the mechanical properties at elevated temperatures, the self-healing glass seal is expected to provide high reliability in maintaining the long-term structural integrity and functionality of SOFCs. In order to accommodate the design and to evaluate the effectiveness of such engineering seals under various thermo-mechanical operating conditions, computational modeling framework needs to be developed to accurately capture and predict the healing behavior of the glass material. In the present work, amore » mechanistic-based two-stage model was developed to study the stress and temperature-dependent crack healing of the self-healing glass materials. The model was first calibrated by experimental measurements combined with the kinetic Monte Carlo (kMC) simulation results and then implemented into the finite element analysis (FEA). The effects of various factors, i.e. stress, temperature, crack morphology, on the healing behavior of the glass were investigated and discussed.« less

Thermal Modeling and Management of Solid Oxide Fuel Cells Operating with Internally Reformed Methane

NASA Astrophysics Data System (ADS)

Wu, Yiyang; Shi, Yixiang; Cai, Ningsheng; Ni, Meng

2018-06-01

A detailed three-dimensional mechanistic model of a large-scale solid oxide fuel cell (SOFC) unit running on partially pre-reformed methane is developed. The model considers the coupling effects of chemical and electrochemical reactions, mass transport, momentum and heat transfer in the SOFC unit. After model validation, parametric simulations are conducted to investigate how the methane pre-reforming ratio affects the transport and electrochemistry of the SOFC unit. It is found that the methane steam reforming reaction has a "smoothing effect", which can achieve more uniform distributions of gas compositions, current density and temperature among the cell plane. In the case of 1500 W/m2 power density output, adding 20% methane absorbs 50% of internal heat production inside the cell, reduces the maximum temperature difference inside the cell from 70 K to 22 K and reduces the cathode air supply by 75%, compared to the condition of completely pre-reforming of methane. Under specific operating conditions, the pre-reforming ratio of methane has an optimal range for obtaining a good temperature distribution and good cell performance.

Distributed Optical Fiber Sensors with Ultrafast Laser Enhanced Rayleigh Backscattering Profiles for Real-Time Monitoring of Solid Oxide Fuel Cell Operations.

PubMed

Yan, Aidong; Huang, Sheng; Li, Shuo; Chen, Rongzhang; Ohodnicki, Paul; Buric, Michael; Lee, Shiwoo; Li, Ming-Jun; Chen, Kevin P

2017-08-24

This paper reports a technique to enhance the magnitude and high-temperature stability of Rayleigh back-scattering signals in silica fibers for distributed sensing applications. With femtosecond laser radiation, more than 40-dB enhancement of Rayleigh backscattering signal was generated in silica fibers using 300-nJ laser pulses at 250 kHz repetition rate. The laser-induced Rayleigh scattering defects were found to be stable from the room temperature to 800 °C in hydrogen gas. The Rayleigh scatter at high temperatures was correlated to the formation and modification of nanogratings in the fiber core. Using optical fibers with enhanced Rayleigh backscattering profiles as distributed temperature sensors, we demonstrated real-time monitoring of solid oxide fuel cell (SOFC) operations with 5-mm spatial resolution at 800 °C. Information gathered by these fiber sensor tools can be used to verify simulation results or operated in a process-control system to improve the operational efficiency and longevity of SOFC-based energy generation systems.

Model predictive control of the solid oxide fuel cell stack temperature with models based on experimental data

NASA Astrophysics Data System (ADS)

Pohjoranta, Antti; Halinen, Matias; Pennanen, Jari; Kiviaho, Jari

2015-03-01

Generalized predictive control (GPC) is applied to control the maximum temperature in a solid oxide fuel cell (SOFC) stack and the temperature difference over the stack. GPC is a model predictive control method and the models utilized in this work are ARX-type (autoregressive with extra input), multiple input-multiple output, polynomial models that were identified from experimental data obtained from experiments with a complete SOFC system. The proposed control is evaluated by simulation with various input-output combinations, with and without constraints. A comparison with conventional proportional-integral-derivative (PID) control is also made. It is shown that if only the stack maximum temperature is controlled, a standard PID controller can be used to obtain output performance comparable to that obtained with the significantly more complex model predictive controller. However, in order to control the temperature difference over the stack, both the stack minimum and the maximum temperature need to be controlled and this cannot be done with a single PID controller. In such a case the model predictive controller provides a feasible and effective solution.

Non-Metallic Ti Oxides and MnS/FeS2 Complex Precipitation in Ti-Killed Steel

NASA Astrophysics Data System (ADS)

Chen, Jieyun; Zhao, Dan; Li, Huigai; Zheng, Shaobo

Titanium deoxidized experiments can be carried in vacuum induction furnace by adding Ti-Fe alloy in molten steel to simulate strip casting. Sub-rapid solidification samples were obtained in the method of suing copper mold. The morphology, the chemical composition and the structures of nanometer precipitations were carried out to investigate by transmission electron microscope (TEM) with Energy Dispersive X ray Spectrum (EDX) and by collecting diffraction patterns with carbon extraction specimens. It has been found that titanium oxides were TiO monoclinic, Ti4O7 anorthic and TiO2 orthogonal structure in one nanometer inclusion, as the composite oxide was precipitated MnS/FeS2 cubic structure during sub-rapid solidification. Thermodynamic calculation analysis showed that it was possible to precipitate different kinds of nonstoichiometric TiOx. The solid solution between MnS/FeS2 will precipitate on the surface of titanium oxides because of good coherency relationship.

Cover and startup gas supply system for solid oxide fuel cell generator

DOEpatents

Singh, P.; George, R.A.

1999-07-27

A cover and startup gas supply system for a solid oxide fuel cell power generator is disclosed. Hydrocarbon fuel, such as natural gas or diesel fuel, and oxygen-containing gas are supplied to a burner. Combustion gas exiting the burner is cooled prior to delivery to the solid oxide fuel cell. The system mixes the combusted hydrocarbon fuel constituents with hydrogen which is preferably stored in solid form to obtain a non-explosive gas mixture. The system may be used to provide both non-explosive cover gas and hydrogen-rich startup gas to the fuel cell. 4 figs.

Cover and startup gas supply system for solid oxide fuel cell generator

DOEpatents

Singh, Prabhakar; George, Raymond A.

1999-01-01

A cover and startup gas supply system for a solid oxide fuel cell power generator is disclosed. Hydrocarbon fuel, such as natural gas or diesel fuel, and oxygen-containing gas are supplied to a burner. Combustion gas exiting the burner is cooled prior to delivery to the solid oxide fuel cell. The system mixes the combusted hydrocarbon fuel constituents with hydrogen which is preferably stored in solid form to obtain a non-explosive gas mixture. The system may be used to provide both non-explosive cover gas and hydrogen-rich startup gas to the fuel cell.

Evaluation of Cathode Air Flow Transients in a SOFC/GT Hybrid System Using Hardware in the Loop Simulation.

PubMed

Zhou, Nana; Yang, Chen; Tucker, David

2015-02-01

Thermal management in the fuel cell component of a direct fired solid oxide fuel cell gas turbine (SOFC/GT) hybrid power system can be improved by effective management and control of the cathode airflow. The disturbances of the cathode airflow were accomplished by diverting air around the fuel cell system through the manipulation of a hot-air bypass valve in open loop experiments, using a hardware-based simulation facility designed and built by the U.S. Department of Energy, National Energy Technology Laboratory (NETL). The dynamic responses of the fuel cell component and hardware component of the hybrid system were studied in this paper.

Structure and transport properties of nanostructured materials.

PubMed

Sonwane, C G; Li, Q

2005-03-31

In the present manuscript, we have presented the simulation of nanoporous aluminum oxide using a molecular-dynamics approach with recently developed dynamic charge transfer potential using serial/parallel programming techniques (Streitz and Mintmire Phys. Rev. B 1994, 50, 11996). The structures resembling recently invented ordered nanoporous crystalline material, MCM-41/SBA-15 (Kresge et al. Nature 1992, 359, 710), and inverted porous solids (hollow nanospheres) with up to 10 000 atoms were fabricated and studied in the present work. These materials have been used for separation of gases and catalysis. On several occasions including the design of the reactor, the knowledge of surface diffusion is necessary. In the present work, a new method for estimating surface transport of gases based on a hybrid Monte Carlo method with unbiased random walk of tracer atom on the pore surface has been introduced. The nonoverlapping packings used in the present work were fabricated using an algorithm of very slowly settling rigid spheres from a dilute suspension into a randomly packed bed. The algorithm was modified to obtain unimodal, homogeneous Gaussian and segregated bimodal porous solids. The porosity of these solids was varied by densification using an arbitrary function or by coarsening from a highly densified pellet. The surface tortuosity for the densified solids indicated an inverted bell shape curve consistent with the fact that at very high porosities there is a reduction in the connectivity while at low porosities the pores become inaccessible or dead-end. The first passage time distribution approach was found to be more efficient in terms of computation time (fewer tracer atoms needed for the linearity of Einstein's plot). Results by hybrid discrete-continuum simulations were close to the discrete simulations for a boundary layer thickness of 5lambda.

Solid lubricant materials for high temperatures: A review

NASA Technical Reports Server (NTRS)

Sliney, Harold E.

1985-01-01

Solid lubricants that can be used above 300 C in air are discussed, including coatings and self-lubricating composite bearing materials. The lubricants considered are representative dichalcogenides, graphite, graphite fluoride, polyimides, soft oxides, oxidatively stable fluorides, and hard coating materials. A few general design considerations revelant to solid lubrication are interspersed.

Catalysts compositions for use in fuel cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chuang, Steven S.C.

2015-12-01

The present invention generally relates to the generation of electrical energy from a solid-state fuel. In one embodiment, the present invention relates to a solid-oxide fuel cell for generating electrical energy from a carbon-based fuel, and to catalysts for use in a solid-oxide fuel cell.

Solid oxide fuel cell steam reforming power system

DOEpatents

Chick, Lawrence A.; Sprenkle, Vincent L.; Powell, Michael R.; Meinhardt, Kerry D.; Whyatt, Greg A.

2013-03-12

The present invention is a Solid Oxide Fuel Cell Reforming Power System that utilizes adiabatic reforming of reformate within this system. By utilizing adiabatic reforming of reformate within the system the system operates at a significantly higher efficiency than other Solid Oxide Reforming Power Systems that exist in the prior art. This is because energy is not lost while materials are cooled and reheated, instead the device operates at a higher temperature. This allows efficiencies higher than 65%.

Process for treating effluent from a supercritical water oxidation reactor

DOEpatents

Barnes, C.M.; Shapiro, C.

1997-11-25

A method for treating a gaseous effluent from a supercritical water oxidation reactor containing entrained solids is provided comprising the steps of expanding the gas/solids effluent from a first to a second lower pressure at a temperature at which no liquid condenses; separating the solids from the gas effluent; neutralizing the effluent to remove any acid gases; condensing the effluent; and retaining the purified effluent to the supercritical water oxidation reactor. 6 figs.

EFRT M12 Issue Resolution: Comparison of PEP and Bench-Scale Oxidative Leaching Results

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rapko, Brian M.; Brown, Christopher F.; Eslinger, Paul W.

2009-08-14

Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed and constructed and is to be operated as part of a plan to respond to issue M12, “Undemonstrated Leaching Processes.” The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. The PEP replicates the WTP leaching processesmore » using prototypic equipment and control strategies. The PEP also includes non-prototypic ancillary equipment to support the core processing. Two operating scenarios are currently being evaluated for the ultrafiltration process (UFP) and leaching operations. The first scenario has caustic leaching performed in the UFP-2 ultrafiltration feed vessels (i.e., vessel UFP-VSL-T02A in the PEP; and vessels UFP-VSL-00002A and B in the WTP PTF). The second scenario has caustic leaching conducted in the UFP-1 ultrafiltration feed preparation vessels (i.e., vessels UFP-VSL-T01A and B in the PEP; vessels UFP-VSL-00001A and B in the WTP PTF). In both scenarios, 19-M sodium hydroxide solution (NaOH, caustic) is added to the waste slurry in the vessels to dissolve solid aluminum compounds (e.g., gibbsite, boehmite). Caustic addition is followed by a heating step that uses direct steam injection to accelerate the leaching process. Following the caustic leach, the vessel contents are cooled using vessel cooling jackets and/or external heat exchangers. The main difference between the two scenarios is that for leaching in UFP1, the 19-M NaOH is added to un-concentrated waste slurry (3 to 8 wt% solids), while for leaching in UFP2, the slurry is concentrated to nominally 20 wt% solids using cross-flow ultrafiltration before the addition of caustic. For wastes that have significantly high chromium content, the caustic leaching and slurry dewatering is followed by adding sodium permanganate to UFP-VSL-T02A, and the slurry is subjected to oxidative leaching at nominally ambient temperature. The purpose of the oxidative leaching is to selectively oxidize the poorly alkaline-soluble Cr(III) believed to be the insoluble form in Hanford tank sludge to the much more alkaline-soluble Cr(VI), e.g., chromate. The work described in this report provides the test results that are related to the efficiency of the oxidative leaching process to support process modeling based on tests performed with a Hanford waste simulant. The tests were completed both at the lab-bench scale and in the PEP. The purpose of this report is to summarize the results from both scales that are related to oxidative leaching chemistry to support a scale factor for the submodels to be used in the G2 model, which predicts WTP operating performance. Owing to schedule constraints, the PEP test data to be included in this report are limited to those from Integrated Tests A (T01 A/B caustic leaching) and B (T02A caustic leaching).« less

Computational designing and screening of solid materials for CO2capture

NASA Astrophysics Data System (ADS)

Duan, Yuhua

In this presentation, we will update our progress on computational designing and screening of solid materials for CO2 capture. By combining thermodynamic database mining with first principles density functional theory and phonon lattice dynamics calculations, a theoretical screening methodology to identify the most promising CO2 sorbent candidates from the vast array of possible solid materials have been proposed and validated at NETL. The advantage of this method is that it identifies the thermodynamic properties of the CO2 capture reaction as a function of temperature and pressure without any experimental input beyond crystallographic structural information of the solid phases involved. The calculated thermodynamic properties of different classes of solid materials versus temperature and pressure changes were further used to evaluate the equilibrium properties for the CO2 adsorption/desorption cycles. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO2 capture reactions by the solids of interest, we were able to identify only those solid materials for which lower capture energy costs are expected at the desired working conditions. In addition, we present a simulation scheme to increase and decrease the turnover temperature (Tt) of solid capturing CO2 reaction by mixing other solids. Our results also show that some solid sorbents can serve as bi-functional materials: CO2 sorbent and CO oxidation catalyst. Such dual functionality could be used for removing both CO and CO2 after water-gas-shift to obtain pure H2.

Regression rate behaviors of HTPB-based propellant combinations for hybrid rocket motor

NASA Astrophysics Data System (ADS)

Sun, Xingliang; Tian, Hui; Li, Yuelong; Yu, Nanjia; Cai, Guobiao

2016-02-01

The purpose of this paper is to characterize the regression rate behavior of hybrid rocket motor propellant combinations, using hydrogen peroxide (HP), gaseous oxygen (GOX), nitrous oxide (N2O) as the oxidizer and hydroxyl-terminated poly-butadiene (HTPB) as the based fuel. In order to complete this research by experiment and simulation, a hybrid rocket motor test system and a numerical simulation model are established. Series of hybrid rocket motor firing tests are conducted burning different propellant combinations, and several of those are used as references for numerical simulations. The numerical simulation model is developed by combining the Navies-Stokes equations with the turbulence model, one-step global reaction model, and solid-gas coupling model. The distribution of regression rate along the axis is determined by applying simulation mode to predict the combustion process and heat transfer inside the hybrid rocket motor. The time-space averaged regression rate has a good agreement between the numerical value and experimental data. The results indicate that the N2O/HTPB and GOX/HTPB propellant combinations have a higher regression rate, since the enhancement effect of latter is significant due to its higher flame temperature. Furthermore, the containing of aluminum (Al) and/or ammonium perchlorate(AP) in the grain does enhance the regression rate, mainly due to the more energy released inside the chamber and heat feedback to the grain surface by the aluminum combustion.

Why solid oxide cells can be reversibly operated in solid oxide electrolysis cell and fuel cell modes?

PubMed

Chen, Kongfa; Liu, Shu-Sheng; Ai, Na; Koyama, Michihisa; Jiang, San Ping

2015-12-14

High temperature solid oxide cells (SOCs) are attractive for storage and regeneration of renewable energy by operating reversibly in solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes. However, the stability of SOCs, particularly the deterioration of the performance of oxygen electrodes in the SOEC operation mode, is the most critical issue in the development of high performance and durable SOCs. In this study, we investigate in detail the electrochemical activity and stability of La0.8Sr0.2MnO3 (LSM) oxygen electrodes in cyclic SOEC and SOFC modes. The results show that the deterioration of LSM oxygen electrodes caused by anodic polarization can be partially or completely recovered by subsequent cathodic polarization. Using in situ assembled LSM electrodes without pre-sintering, we demonstrate that the deteriorated LSM/YSZ interface can be repaired and regenerated by operating the cells under cathodic polarization conditions. This study for the first time establishes the foundation for the development of truly reversible and stable SOCs for hydrogen fuel production and electricity generation in cyclic SOEC and SOFC operation modes.

Hybrid propulsion technology program: Phase 1, volume 4

NASA Technical Reports Server (NTRS)

Claflin, S. E.; Beckman, A. W.

1989-01-01

The use of a liquid oxidizer-solid fuel hybrid propellant combination in booster rocket motors appears extremely attractive due to the integration of the best features of liquid and solid propulsion systems. The hybrid rocket combines the high performance, clean exhaust, and safety of liquid propellant engines with the low cost and simplicity of solid propellant motors. Additionally, the hybrid rocket has unique advantages such as an inert fuel grain and a relative insensitivity to fuel grain and oxidizer injection anomalies. The advantages mark the hybrid rocket as a potential replacement or alternative for current and future solid propellant booster systems. The issues are addressed and recommendations are made concerning oxidizer feed systems, injectors, and ignition systems as related to hybrid rocket propulsion. Early in the program a baseline hybrid configuration was established in which liquid oxygen would be injected through ports in a solid fuel whose composition is based on hydroxyl terminated polybutadiene (HTPB). Liquid oxygen remained the recommended oxidizer and thus all of the injector concepts which were evaluated assumed only liquid would be used as the oxidizer.

Solid oxide fuel cells, and air electrode and electrical interconnection materials therefor

DOEpatents

Bates, J. Lambert

1992-01-01

In one aspect of the invention, an air electrode material for a solid oxide fuel cell comprises Y.sub.1-a Q.sub.a MnO.sub.3, where "Q" is selected from the group consisting of Ca and Sr or mixtures thereof and "a" is from 0.1 to 0.8. Preferably, "a" is from 0.4 to 0.7. In another aspect of the invention, an electrical interconnection material for a solid oxide fuel cell comprises Y.sub.1-b Ca.sub.b Cr.sub.1-c Al.sub.c O.sub.3, where "b" is from 0.1 to 0.6 and "c" is from 0 to 9.3. Preferably, "b" is from 0.3 to 0.5 and "c" is from 0.05 to 0.1. A composite solid oxide electrochemical fuel cell incorporating these materials comprises: a solid oxide air electrode and an adjacent solid oxide electrical interconnection which commonly include the cation Y, the air electrode comprising Y.sub.1-a Q.sub.a MnO.sub.3, where "Q" is selected from the group consisting of Ca and Sr or mixtures thereof and "a" is from 0.1 to 0.8, the electrical interconnection comprising Y.sub.1-b Ca.sub.b Cr.sub.1-c Al.sub.c O.sub.3, where "b" is from 0.1 to 0.6 and "c" is from 0.0 to 0.3; a yttrium stabilized solid electrolyte comprising (1-d)ZrO.sub.2 -(d)Y.sub.2 O.sub.3 where "d" is from 0.06 to 0.5; and a solid fuel electrode comprising X-ZrO.sub.2, where "X" is an elemental metal.

Solid oxide fuel cells, and air electrode and electrical interconnection materials therefor

DOEpatents

Bates, J.L.

1992-09-01

In one aspect of the invention, an air electrode material for a solid oxide fuel cell comprises Y[sub 1[minus]a]Q[sub a]MnO[sub 3], where Q is selected from the group consisting of Ca and Sr or mixtures thereof and a' is from 0.1 to 0.8. Preferably, a' is from 0.4 to 0.7. In another aspect of the invention, an electrical interconnection material for a solid oxide fuel cell comprises Y[sub 1[minus]b]Ca[sub b]Cr[sub 1[minus]c]Al[sub c]O[sub 3], where b' is from 0.1 to 0.6 and c' is from 0 to 9.3. Preferably, b' is from 0.3 to 0.5 and c' is from 0.05 to 0.1. A composite solid oxide electrochemical fuel cell incorporating these materials comprises: a solid oxide air electrode and an adjacent solid oxide electrical interconnection which commonly include the cation Y, the air electrode comprising Y[sub 1[minus]a]Q[sub a]MnO[sub 3], where Q is selected from the group consisting of Ca and Sr or mixtures thereof and a' is from 0.1 to 0.8, the electrical interconnection comprising Y[sub 1[minus]b]Ca[sub b]Cr[sub 1[minus]c]Al[sub c]O[sub 3], where b' is from 0.1 to 0.6 and c' is from 0.0 to 0.3; a yttrium stabilized solid electrolyte comprising (1[minus]d)ZrO[sub 2]-(d)Y[sub 2]O[sub 3] where d' is from 0.06 to 0.5; and a solid fuel electrode comprising X-ZrO[sub 2], where X' is an elemental metal. 5 figs.

High Capacity Garnet-Based All-Solid-State Lithium Batteries: Fabrication and 3D-Microstructure Resolved Modeling.

PubMed

Finsterbusch, Martin; Danner, Timo; Tsai, Chih-Long; Uhlenbruck, Sven; Latz, Arnulf; Guillon, Olivier

2018-06-21

The development of high-capacity, high-performance all-solid-state batteries requires the specific design and optimization of its components, especially on the positive electrode side. For the first time, we were able to produce a completely inorganic mixed positive electrode consisting only of LiCoO 2 and Ta-substituted Li 7 La 3 Zr 2 O 12 (LLZ:Ta) without the use of additional sintering aids or conducting additives, which has a high theoretical capacity density of 1 mAh/cm 2 . A true all-solid-state cell composed of a Li metal negative electrode, a LLZ:Ta garnet electrolyte, and a 25 μm thick LLZ:Ta + LiCoO 2 mixed positive electrode was manufactured and characterized. The cell shows 81% utilization of theoretical capacity upon discharging at elevated temperatures and rather high discharge rates of 0.1 mA (0.1 C). However, even though the room temperature performance is also among the highest reported so far for similar cells, it still falls far short of the theoretical values. Therefore, a 3D reconstruction of the manufactured mixed positive electrode was used for the first time as input for microstructure-resolved continuum simulations. The simulations are able to reproduce the electrochemical behavior at elevated temperature favorably, however fail completely to predict the performance loss at room temperature. Extensive parameter studies were performed to identify the limiting processes, and as a result, interface phenomena occurring at the cathode active material/solid-electrolyte interface were found to be the most probable cause for the low performance at room temperature. Furthermore, the simulations are used for a sound estimation of the optimization potential that can be realized with this type of cell, which provides important guidelines for future oxide based all-solid-state battery research and fabrication.

Magnetic graphene oxide modified by imidazole-based ionic liquids for the magnetic-based solid-phase extraction of polysaccharides from brown alga.

PubMed

Wang, Xiaoqin; Li, Guizhen; Row, Kyung Ho

2017-08-01

Magnetic graphene oxide was modified by four imidazole-based ionic liquids to synthesize materials for the extraction of polysaccharides by magnetic solid-phase extraction. Fucoidan and laminarin were chosen as the representative polysaccharides owing to their excellent pharmaceutical value and availability. Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, and thermogravimetric analysis were applied to characterize the synthesized materials. Single-factor experiments showed that the extraction efficiency of polysaccharides was affected by the amount of ionic liquids for modification, solid-liquid ratio of brown alga and ethanol, the stirring time of brown alga and ionic liquid-modified magnetic graphene oxide materials, and amount of 1-(3-aminopropyl)imidazole chloride modified magnetic graphene oxide materials added to the brown alga sample solution. The results indicated that 1-(3-aminopropyl)imidazole chloride modified magnetic graphene oxide possessed better extraction ability than graphene oxide, magnetic graphene oxide, and other three ionic-liquid-modified magnetic graphene oxide materials. The highest extraction recoveries of fucoidan and laminarin extracted by 1-(3-aminopropyl)imidazole chloride modified magnetic graphene oxide were 93.3 and 87.2%, respectively. In addition, solid materials could be separated and reused easily owing to their magnetic properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process for removing copper in a recoverable form from solid scrap metal

DOEpatents

Hartman, Alan D.; Oden, Laurance L.; White, Jack C.

1995-01-01

A process for removing copper in a recoverable form from a copper/solid ferrous scrap metal mix is disclosed. The process begins by placing a copper/solid ferrous scrap metal mix into a reactor vessel. The atmosphere within the reactor vessel is purged with an inert gas or oxidizing while the reactor vessel is heated in the area of the copper/solid ferrous scrap metal mix to raise the temperature within the reactor vessel to a selected elevated temperature. Air is introduced into the reactor vessel and thereafter hydrogen chloride is introduced into the reactor vessel to obtain a desired air-hydrogen chloride mix. The air-hydrogen chloride mix is operable to form an oxidizing and chloridizing atmosphere which provides a protective oxide coating on the surface of the solid ferrous scrap metal in the mix and simultaneously oxidizes/chloridizes the copper in the mix to convert the copper to a copper monochloride gas for transport away from the solid ferrous scrap metal. After the copper is completely removed from the copper/solid ferrous scrap metal mix, the flows of air and hydrogen chloride are stopped and the copper monochloride gas is collected for conversion to a recoverable copper species.

Fabrication of copper-based anodes via atmosphoric plasma spraying techniques

DOEpatents

Lu, Chun [Monroeville, PA

2012-04-24

A fuel electrode anode (18) for a solid oxide fuel cell is made by presenting a solid oxide fuel cell having an electrolyte surface (15), mixing copper powder with solid oxide electrolyte in a mixing step (24, 44) to provide a spray feedstock (30,50) which is fed into a plasma jet (32, 52) of a plasma torch to melt the spray feed stock and propel it onto an electrolyte surface (34, 54) where the spray feed stock flattens into lamellae layer upon solidification, where the layer (38, 59) is an anode coating with greater than 35 vol. % based on solids volume.

Method of burning sulfur-containing fuels in a fluidized bed boiler

DOEpatents

Jones, Brian C.

1982-01-01

A method of burning a sulfur-containing fuel in a fluidized bed of sulfur oxide sorbent wherein the overall utilization of sulfur oxide sorbent is increased by comminuting the bed drain solids to a smaller average particle size, preferably on the order of 50 microns, and reinjecting the comminuted bed drain solids into the bed. In comminuting the bed drain solids, particles of spent sulfur sorbent contained therein are fractured thereby exposing unreacted sorbent surface. Upon reinjecting the comminuted bed drain solids into the bed, the newly-exposed unreacted sorbent surface is available for sulfur oxide sorption, thereby increasing overall sorbent utilization.

Calorimetric determination of energetics of solid solutions of UO 2+ x with CaO and Y 2O 3

NASA Astrophysics Data System (ADS)

Mazeina, Lena; Navrotsky, Alexandra; Greenblatt, Martha

2008-02-01

Quantitative study of thermodynamic properties of solid solutions of UO 2+ x with divalent and trivalent oxides is important for predicting the behavior of oxide fuel. Although early literature work measured vapor pressure in some of these solid solutions, direct calorimetric measurements of enthalpies of formation have been hampered by the refractory nature of such oxides. First measurements of the enthalpies of formation in the systems UO 2+ x-CaO and UO 2+ x-YO 1.5, obtained by high-temperature oxide melt solution calorimetry, are reported. Both systems show significantly negative (exothermic) heats of formation from binary oxides (UO 2, plus O 2 and CaO or YO 1.5, as well as from UO 2 plus UO 3 and CaO or YO 1.5), consistent with reported free energy measurements in the urania-yttria system. The energetic contributions of oxygen content (oxidation of U 4+) and of charge balanced ionic substitution as well as defect clustering are discussed. Behavior of urania-yttria is compared to that of corresponding systems in which the tetravalent ion is Ce, Zr, or Hf. The substantial additional stability in the solid solutions compared to pure UO 2+ x may retard, in both thermodynamic and kinetic sense, the oxidation and leaching of spent fuel to form aqueous U 6+ and solid uranyl phases.

Coal-fuelled systems for peaking power with 100% CO2 capture through integration of solid oxide fuel cells with compressed air energy storage

NASA Astrophysics Data System (ADS)

Nease, Jake; Adams, Thomas A.

2014-04-01

In this study, a coal-fuelled integrated solid oxide fuel cell (SOFC) and compressed air energy storage (CAES) system in a load-following power production scenario is discussed. Sixteen SOFC-based plants with optional carbon capture and sequestration (CCS) and syngas shifting steps are simulated and compared to a state-of-the-art supercritical pulverised coal (SCPC) plant. Simulations are performed using a combination of MATLAB and Aspen Plus v7.3. It was found that adding CAES to a SOFC-based plant can provide load-following capabilities with relatively small effects on efficiencies (1-2% HHV depending on the system configuration) and levelized costs of electricity (∼0.35 ¢ kW-1 h-1). The load-following capabilities, as measured by least-squares metrics, show that this system may utilize coal and achieve excellent load-tracking that is not adversely affected by the inclusion of CCS. Adding CCS to the SOFC/CAES system reduces measurable direct CO2 emission to zero. A seasonal partial plant shutdown schedule is found to reduce fuel consumption by 9.5% while allowing for cleaning and maintenance windows for the SOFC stacks without significantly affecting the performance of the system (∼1% HHV reduction in efficiency). The SOFC-based systems with CCS are found to become economically attractive relative to SCPC above carbon taxes of 22 ton-1.

Thermal Transport in Graphene Oxide – From Ballistic Extreme to Amorphous Limit

PubMed Central

Mu, Xin; Wu, Xufei; Zhang, Teng; Go, David B.; Luo, Tengfei

2014-01-01

Graphene oxide is being used in energy, optical, electronic and sensor devices due to its unique properties. However, unlike its counterpart – graphene – the thermal transport properties of graphene oxide remain unknown. In this work, we use large-scale molecular dynamics simulations with reactive potentials to systematically study the role of oxygen adatoms on the thermal transport in graphene oxide. For pristine graphene, highly ballistic thermal transport is observed. As the oxygen coverage increases, the thermal conductivity is significantly reduced. An oxygen coverage of 5% can reduce the graphene thermal conductivity by ~90% and a coverage of 20% lower it to ~8.8 W/mK. This value is even lower than the calculated amorphous limit (~11.6 W/mK for graphene), which is usually regarded as the minimal possible thermal conductivity of a solid. Analyses show that the large reduction in thermal conductivity is due to the significantly enhanced phonon scattering induced by the oxygen defects which introduce dramatic structural deformations. These results provide important insight to the thermal transport physics in graphene oxide and offer valuable information for the design of graphene oxide-based materials and devices. PMID:24468660

Insight into fast ion migration kinetics of a new hybrid single Li-ion conductor based on aluminate complexes for solid-state Li-ion batteries.

PubMed

Feng, Yancong; Tan, Rui; Zhao, Yan; Gao, Rongtan; Yang, Luyi; Yang, Jinlong; Li, Hao; Zhou, Guofu; Chen, Haibiao; Pan, Feng

2018-03-29

A novel hybrid single Li-ion conductor (SLIC) for a Li-ion solid electrolyte was prepared by mixing aluminate complexes-polyethylene glycol (LiAl-PEG) and polyethylene oxide (PEO) for solid-state Li-ion batteries. The LiAl-PEG/PEO blend possesses high thermal stability and electrochemical stability with an oxidation decomposition voltage up to 4.8 V. Notably, this hybrid SLIC exhibits not only excellent Li-ion migration kinetics, but also good ionic conductivity as high as 4.0 × 10-5 and 2.6 × 10-4 S cm-1 at 30 and 100 °C, respectively, which is much higher than previously reported SLICs. Importantly, by the combination of molecular dynamics simulations and experiment measurements, the mechanisms of Li-ion migration across the SLIC (LiAl-PEG), the salt-in-polymer (LiClO4/PEO) and the optimized SLIC (LiAl-PEG/PEO) were systematically investigated for the first time. The new hopping transport mechanism was verified for the SLIC system at the nanoscale. As for the hybrid SLIC, PEO chains enhance the segmental mobility of the ether-chains bonded with Al atoms, improve the ionicity, and provide extra ionic paths for Li transfer, resulting in the optimized Li-ion migration kinetics of LiAl-PEG/PEO.

Methods and systems for producing syngas

DOEpatents

Hawkes, Grant L; O& #x27; Brien, James E; Stoots, Carl M; Herring, J. Stephen; McKellar, Michael G; Wood, Richard A; Carrington, Robert A; Boardman, Richard D

2013-02-05

Methods and systems are provided for producing syngas utilizing heat from thermochemical conversion of a carbonaceous fuel to support decomposition of at least one of water and carbon dioxide using one or more solid-oxide electrolysis cells. Simultaneous decomposition of carbon dioxide and water or steam by one or more solid-oxide electrolysis cells may be employed to produce hydrogen and carbon monoxide. A portion of oxygen produced from at least one of water and carbon dioxide using one or more solid-oxide electrolysis cells is fed at a controlled flow rate in a gasifier or combustor to oxidize the carbonaceous fuel to control the carbon dioxide to carbon monoxide ratio produced.

High temperature resistant cermet and ceramic compositions

NASA Technical Reports Server (NTRS)

Phillips, W. M. (Inventor)

1978-01-01

Cermet compositions having high temperature oxidation resistance, high hardness and high abrasion and wear resistance, and particularly adapted for production of high temperature resistant cermet insulator bodies are presented. The compositions are comprised of a sintered body of particles of a high temperature resistant metal or metal alloy, preferably molybdenum or tungsten particles, dispersed in and bonded to a solid solution formed of aluminum oxide and silicon nitride, and particularly a ternary solid solution formed of a mixture of aluminum oxide, silicon nitride and aluminum nitride. Also disclosed are novel ceramic compositions comprising a sintered solid solution of aluminum oxide, silicon nitride and aluminum nitride.

Solid film lubricants and thermal control coatings flown aboard the EOIM-3 MDA sub-experiment

NASA Technical Reports Server (NTRS)

Murphy, Taylor J.; David, Kaia E.; Babel, Hank W.

1995-01-01

Additional experimental data were desired to support the selection of candidate thermal control coatings and solid film lubricants for the McDonnell Douglas Aerospace (MDA) Space Station hardware. The third Evaluation of Oxygen Interactions With Materials Mission (EOIM-3) flight experiment presented an opportunity to study the effects of the low Earth orbit environment on thermal control coatings and solid film lubricants. MDA provided five solid film lubricants and two anodic thermal control coatings for EOIM-3. The lubricant sample set consisted of three solid film lubricants with organic binders one solid film lubricant with an inorganic binder, and one solid film lubricant with no binder. The anodize coating sample set consisted of undyed sulfuric acid anodize and cobalt sulfide dyed sulfuric acid anodize, each on two different substrate aluminum alloys. The organic and inorganic binders in the solid film lubricants experienced erosion, and the lubricating pigments experienced oxidation. MDA is continuing to assess the effect of exposure to the low Earth orbit environment on the life and friction properties of the lubricants. Results to date support the design practice of shielding solid film lubricants from the low Earth orbit environment. Post-flight optical property analysis of the anodized specimens indicated that there were limited contamination effects and some atomic oxygen and ultraviolet radiation effects. These effects appeared to be within the values predicted by simulated ground testing and analysis of these materials, and they were different for each coating and substrate.

Prediction of La0.6Sr0.4Co0.2Fe0.8O3 cathode microstructures during sintering: Kinetic Monte Carlo (KMC) simulations calibrated by artificial neural networks

NASA Astrophysics Data System (ADS)

Yan, Zilin; Kim, Yongtae; Hara, Shotaro; Shikazono, Naoki

2017-04-01

The Potts Kinetic Monte Carlo (KMC) model, proven to be a robust tool to study all stages of sintering process, is an ideal tool to analyze the microstructure evolution of electrodes in solid oxide fuel cells (SOFCs). Due to the nature of this model, the input parameters of KMC simulations such as simulation temperatures and attempt frequencies are difficult to identify. We propose a rigorous and efficient approach to facilitate the input parameter calibration process using artificial neural networks (ANNs). The trained ANN reduces drastically the number of trial-and-error of KMC simulations. The KMC simulation using the calibrated input parameters predicts the microstructures of a La0.6Sr0.4Co0.2Fe0.8O3 cathode material during sintering, showing both qualitative and quantitative congruence with real 3D microstructures obtained by focused ion beam scanning electron microscopy (FIB-SEM) reconstruction.

Solid-to-solid oxidation of a vanadium(IV) to a vanadium(V) compound: chemisty of a sulfur-containing siderophore.

PubMed

Chatterjee, Pabitra B; Crans, Debbie C

2012-09-03

Visible light facilitates a solid-to-solid photochemical aerobic oxidation of a hunter-green microcrystalline oxidovanadium(IV) compound (1) to form a black powder of cis-dioxidovanadium(V) (2) at ambient temperature. The siderophore ligand pyridine-2,6-bis(thiocarboxylic acid), H(2)L, is secreted by a microorganism from the Pseudomonas genus. This irreversible transformation of a metal monooxo to a metal dioxo complex in the solid state in the absence of solvent is unprecedented. It serves as a proof-of-concept reaction for green chemistry occurring in solid matrixes.

Combinatorial synthesis of phosphors using arc-imaging furnace

PubMed Central

Ishigaki, Tadashi; Toda, Kenji; Yoshimura, Masahiro; Uematsu, Kazuyoshi; Sato, Mineo

2011-01-01

We have applied a novel ‘melt synthesis technique’ rather than a conventional solid-state reaction to rapidly synthesize phosphor materials. During a synthesis, the mixture of oxides or their precursors is melted by light pulses (10–60 s) in an arc-imaging furnace on a water-cooled copper hearth to form a globule of 1–5 mm diameter, which is then rapidly cooled by turning off the light. Using this method, we synthesized several phosphor compounds including Y3Al5O12:Ce(YAG) and SrAl2O4:Eu,Dy. Complex phosphor oxides are difficult to produce by conventional solid-state reaction techniques because of the slow reaction rates among solid oxides; as a result, the oxides form homogeneous compounds or solid solutions. On the other hand, melt reactions are very fast (10–60 s) and result in homogeneous compounds owing to rapid diffusion and mixing in the liquid phase. Therefore, melt synthesis techniques are suitable for preparing multi component homogeneous compounds and solid solutions. PMID:27877432

Combinatorial synthesis of phosphors using arc-imaging furnace

NASA Astrophysics Data System (ADS)

Ishigaki, Tadashi; Toda, Kenji; Yoshimura, Masahiro; Uematsu, Kazuyoshi; Sato, Mineo

2011-10-01

We have applied a novel 'melt synthesis technique' rather than a conventional solid-state reaction to rapidly synthesize phosphor materials. During a synthesis, the mixture of oxides or their precursors is melted by light pulses (10-60 s) in an arc-imaging furnace on a water-cooled copper hearth to form a globule of 1-5 mm diameter, which is then rapidly cooled by turning off the light. Using this method, we synthesized several phosphor compounds including Y3Al5O12:Ce(YAG) and SrAl2O4:Eu,Dy. Complex phosphor oxides are difficult to produce by conventional solid-state reaction techniques because of the slow reaction rates among solid oxides; as a result, the oxides form homogeneous compounds or solid solutions. On the other hand, melt reactions are very fast (10-60 s) and result in homogeneous compounds owing to rapid diffusion and mixing in the liquid phase. Therefore, melt synthesis techniques are suitable for preparing multi component homogeneous compounds and solid solutions.

Low temperature ozone oxidation of solid waste surrogates

NASA Astrophysics Data System (ADS)

Nabity, James A.; Lee, Jeffrey M.

2015-09-01

Solid waste management presents a significant challenge to human spaceflight and especially, long-term missions beyond Earth orbit. A six-month mission will generate over 300 kg of solid wastes per crewmember that must be dealt with to eliminate the need for storage and prevent it from becoming a biological hazard to the crew. There are several methods for the treatment of wastes that include oxidation via ozone, incineration, microbial oxidation or pyrolysis and physical methods such as microwave drying and compaction. In recent years, a low temperature oxidation process using ozonated water has been developed for the chemical conversion of organic wastes to CO2 and H2O. Experiments were conducted to evaluate the rate and effectiveness with which ozone oxidized several different waste materials. Increasing the surface area by chopping or shredding the solids into small pieces more than doubled the rate of oxidation. A greater flow of ozone and agitation of the ozonated water system also increased processing rates. Of the materials investigated, plastics have proven the most difficult to oxidize. The processing of plastics above the glass transition temperatures caused the plastics to clump together which reduced the exposed surface area, while processing at lower temperatures reduced surface reaction kinetics.

Supercritical water oxidation - Microgravity solids separation

NASA Technical Reports Server (NTRS)

Killilea, William R.; Hong, Glenn T.; Swallow, Kathleen C.; Thomason, Terry B.

1988-01-01

This paper discusses the application of supercritical water oxidation (SCWO) waste treatment and water recycling technology to the problem of waste disposal in-long term manned space missions. As inorganic constituents present in the waste are not soluble in supercritical water, they must be removed from the organic-free supercritical fluid reactor effluent. Supercritical water reactor/solids separator designs capable of removing precipitated solids from the process' supercritical fluid in zero- and low- gravity environments are developed and evaluated. Preliminary experiments are then conducted to test the concepts. Feed materials for the experiments are urine, feces, and wipes with the addition of reverse osmosis brine, the rejected portion of processed hygiene water. The solid properties and their influence on the design of several oxidation-reactor/solids-separator configurations under study are presented.

Using 238U/235U ratios to understand the formation and oxidation of reduced uranium solids in naturally reduced zones

NASA Astrophysics Data System (ADS)

Jemison, N.; Johnson, T. M.; Druhan, J. L.; Davis, J. A.

2016-12-01

Uranium occurs in groundwater primarily as soluble and mobile U(VI), which can be reduced to immobile U(IV), often observed in sediments as uraninite. Numerous U(VI)-contaminated sites, such as the DOE field site in Rifle, CO, contain naturally reduced zones (NRZ's) that have relatively high concentrations of organic matter. Reduction of heavy metals occurs within NRZ's, producing elevated concentrations of iron sulfides and U(IV). Slow, natural oxidation of U(IV) from NRZ's may prolong U(VI) contamination of groundwater. The reduction of U(VI) produces U(IV) with a higher 238U/235U ratio. Samples from two NRZ sediment cores recovered from the Rifle site revealed that the outer fringes of the NRZ contain U(IV) with a high 238U/235U ratio, while lower values are observed in the center . We suggest that as aqueous U(VI) was reduced in the NRZ, it was driven to lower 238U/235U values, such that U(IV) formed in the core of the NRZ reflects a lower 238U/235U. Two oxidation experiments were conducted by injecting groundwater containing between 14.9 and 21.2 mg/L dissolved O2 as an oxidant into the NRZ. The oxidation of U(IV) from this NRZ increased aqueous U(VI) concentrations and caused a shift to higher 238U/235U in groundwater as U(IV) was oxidized primarily on the outer fringes of the NRZ. In total these observations suggest that the stability of solid phase uranium is governed by coupled reaction and transport processes. To better understand various reactive transport scenarios we developed a model for the formation and oxidation of NRZ's utilizing the reactive transport software CrunchTope. These simulations suggest that the development of isotopically heterogeneous U(IV) within NRZ's is largely controlled by permeability of the NRZ and the U(VI) reduction rate. Oxidation of U(IV) from the NRZ's is constrained by the oxidation rate of U(IV) as well as iron sulfides, which can prevent oxidation of U(IV) by scavenging dissolved oxygen.

Low voltage solid-state lateral coloration electrochromic device

DOEpatents

Tracy, C.E.; Benson, D.K.; Ruth, M.R.

1984-12-21

A solid-state transition metal oxide device comprising a plurality of layers having a predisposed orientation including an electrochromic oxide layer. Conductive material including anode and cathode contacts is secured to the device. Coloration is actuated within the electrochromic oxide layer after the application of a predetermined potential between the contacts. The coloration action is adapted to sweep or dynamically extend across the length of the electrochromic oxide layer.

Low voltage solid-state lateral coloration electrochromic device

DOEpatents

Tracy, C. Edwin; Benson, David K.; Ruth, Marta R.

1987-01-01

A solid-state transition metal oxide device comprising a plurality of lay having a predisposed orientation including an electrochromic oxide layer. Conductive material including anode and cathode contacts is secured to the device. Coloration is actuated within the electrochromic oxide layer after the application of a predetermined potential between the contacts. The coloration action is adapted to sweep or dynamically extend across the length of the electrochromic oxide layer.

Numerical simulations on unsteady operation processes of N2O/HTPB hybrid rocket motor with/without diaphragm

NASA Astrophysics Data System (ADS)

Zhang, Shuai; Hu, Fan; Wang, Donghui; Okolo. N, Patrick; Zhang, Weihua

2017-07-01

Numerical simulations on processes within a hybrid rocket motor were conducted in the past, where most of these simulations carried out majorly focused on steady state analysis. Solid fuel regression rate strongly depends on complicated physicochemical processes and internal fluid dynamic behavior within the rocket motor, which changes with both space and time during its operation, and are therefore more unsteady in characteristics. Numerical simulations on the unsteady operational processes of N2O/HTPB hybrid rocket motor with and without diaphragm are conducted within this research paper. A numerical model is established based on two dimensional axisymmetric unsteady Navier-Stokes equations having turbulence, combustion and coupled gas/solid phase formulations. Discrete phase model is used to simulate injection and vaporization of the liquid oxidizer. A dynamic mesh technique is applied to the non-uniform regression of fuel grain, while results of unsteady flow field, variation of regression rate distribution with time, regression process of burning surface and internal ballistics are all obtained. Due to presence of eddy flow, the diaphragm increases regression rate further downstream. Peak regression rates are observed close to flow reattachment regions, while these peak values decrease gradually, and peak position shift further downstream with time advancement. Motor performance is analyzed accordingly, and it is noticed that the case with diaphragm included results in combustion efficiency and specific impulse efficiency increase of roughly 10%, and ground thrust increase of 17.8%.

Actinide recovery process

DOEpatents

Muscatello, Anthony C.; Navratil, James D.; Saba, Mark T.

1987-07-28

Process for the removal of plutonium polymer and ionic actinides from aqueous solutions by absorption onto a solid extractant loaded on a solid inert support such as polystyrenedivinylbenzene. The absorbed actinides can then be recovered by incineration, by stripping with organic solvents, or by acid digestion. Preferred solid extractants are trioctylphosphine oxide and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and the like.

Actinide recovery process

DOEpatents

Muscatello, A.C.; Navratil, J.D.; Saba, M.T.

1985-06-13

Process for the removal of plutonium polymer and ionic actinides from aqueous solutions by absorption onto a solid extractant loaded on a solid inert support such as polystyrene-divinylbenzene. The absorbed actinides can then be recovered by incineration, by stripping with organic solvents, or by acid digestion. Preferred solid extractants are trioctylphosphine oxide and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and the like. 2 tabs.

Effects of acid rain on grapevines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Forsline, P.L.; Musselman, R.C.; Dee, R.J.

1983-01-01

Mature vineyard-growing Concord grapevines were sprayed with simulated acid rain solutions ranging from pH 2.5 to 5.5 both as acute treatments at anthesis and chronically throughout the season in 1980 and 1981. In 1981, 8 additional varieties were also treated with simulated acid rain solutions at pH 2.75 and 3.25. With Concord in 1981, few foliar lesions on leaves were visible at pH 2.75. In contrast, many leaf lesions with decreased fruit soluble solids were observed at pH 2.5 in 1980. The relationship between acid-rain and oxidant stipple, chlorosis, and soluble solids in the absence of acid rain leaf lesionsmore » at pH>2.5 remains unclear. Acute sprays (pH2.75) at anthesis reduced pollen germination in four grape cultivars. However, fruit set was reduced in only one of these. Grape yields were not influenced by acid rain treatments. There was no evidence that acid-rain at ambient pH levels had negative effects on grape production or fruit quality.« less

Mass reduction patterning of silicon-on-oxide-based micromirrors

NASA Astrophysics Data System (ADS)

Hall, Harris J.; Green, Andrew; Dooley, Sarah; Schmidt, Jason D.; Starman, LaVern A.; Langley, Derrick; Coutu, Ronald A.

2016-10-01

It has long been recognized in the design of micromirror-based optical systems that balancing static flatness of the mirror surface through structural design with the system's mechanical dynamic response is challenging. Although a variety of mass reduction approaches have been presented in the literature to address this performance trade, there has been little quantifiable comparison reported. In this work, different mass reduction approaches, some unique to the work, are quantifiably compared with solid plate thinning in both curvature and mass using commercial finite element simulation of a specific square silicon-on-insulator-based micromirror geometry. Other important considerations for micromirror surfaces, including surface profile and smoothness, are also discussed. Fabrication of one of these geometries, a two-dimensional tessellated square pattern, was performed in the presence of a 400-μm-tall central post structure using a simple single mask process. Limited experimental curvature measurements of fabricated samples are shown to correspond well with properly characterized simulation results and indicate ˜67% improvement in radius of curvature in comparison to a solid plate design of equivalent mass.

Glass/BNNT Composite for Sealing Solid Oxide Fuel Cells

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Hurst, Janet B.; Choi, Sung R.

2007-01-01

A material consisting of a barium calcium aluminosilicate glass reinforced with 4 weight percent of boron nitride nanotubes (BNNTs) has shown promise for use as a sealant in planar solid oxide fuel cells (SOFCs).

Model anodes and anode models for understanding the mechanism of hydrogen oxidation in solid oxide fuel cells.

PubMed

Bessler, Wolfgang G; Vogler, Marcel; Störmer, Heike; Gerthsen, Dagmar; Utz, Annika; Weber, André; Ivers-Tiffée, Ellen

2010-11-14

This article presents a literature review and new results on experimental and theoretical investigations of the electrochemistry of solid oxide fuel cell (SOFC) model anodes, focusing on the nickel/yttria-stabilized zirconia (Ni/YSZ) materials system with operation under H(2)/H(2)O atmospheres. Micropatterned model anodes were used for electrochemical characterization under well-defined operating conditions. Structural and chemical integrity was confirmed by ex situ pre-test and post-test microstructural and chemical analysis. Elementary kinetic models of reaction and transport processes were used to assess reaction pathways and rate-determining steps. The comparison of experimental and simulated electrochemical behaviors of pattern anodes shows quantitative agreement over a wide range of operating conditions (p(H(2)) = 8×10(2) - 9×10(4) Pa, p(H(2)O) = 2×10(1) - 6×10(4) Pa, T = 400-800 °C). Previously published experimental data on model anodes show a strong scatter in electrochemical performance. Furthermore, model anodes exhibit a pronounced dynamics on multiple time scales which is not reproduced in state-of-the-art models and which is also not observed in technical cermet anodes. Potential origin of these effects as well as consequences for further steps in model anode and anode model studies are discussed.

Carbon deposition behaviour in metal-infiltrated gadolinia doped ceria electrodes for simulated biogas upgrading in solid oxide electrolysis cells

NASA Astrophysics Data System (ADS)

Duboviks, V.; Lomberg, M.; Maher, R. C.; Cohen, L. F.; Brandon, N. P.; Offer, G. J.

2015-10-01

One of the attractive applications for reversible Solid Oxide Cells (SOCs) is to convert CO2 into CO via high temperature electrolysis, which is particularly important for biogas upgrading. To improve biogas utility, the CO2 component can be converted into fuel via electrolysis. A significant issue for SOC operation on biogas is carbon-induced catalyst deactivation. Nickel is widely used in SOC electrodes for reasons of cost and performance, but it has a low tolerance to carbon deposition. Two different modes of carbon formation on Ni-based electrodes are proposed in the present work based on ex-situ Raman measurements which are in agreement with previous studies. While copper is known to be resistant towards carbon formation, two significant issues have prevented its application in SOC electrodes - namely its relatively low melting temperature, inhibiting high temperature sintering, and low catalytic activity for hydrogen oxidation. In this study, the electrodes were prepared through a low temperature metal infiltration technique. Since the metal infiltration technique avoids high sintering temperatures, Cu-Ce0.9Gd0.1O2-δ (Cu-CGO) electrodes were fabricated and tested as an alternative to Ni-CGO electrodes. We demonstrate that the performance of Cu-CGO electrodes is equivalent to Ni-CGO electrodes, whilst carbon formation is fully suppressed when operated on biogas mixture.

Solid State Energy Conversion Alliance Delphi SOFC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steven Shaffer; Gary Blake; Sean Kelly

2006-12-31

The following report details the results under the DOE SECA program for the period July 2006 through December 2006. Developments pertain to the development of a 3 to 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. This report details technical results of the work performed under the following tasks for the SOFC Power System: Task 1 SOFC System Development; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant Components; Task 5 Project Management; and Task 6 System Modeling & Cell Evaluation for Highmore » Efficiency Coal-Based Solid Oxide Fuel Cell Gas Turbine Hybrid System.« less

Solid oxide fuel cell with transitioned cross-section for improved anode gas management at the open end

DOEpatents

Zafred, Paolo R [Murrysville, PA; Draper, Robert [Pittsburgh, PA

2012-01-17

A solid oxide fuel cell (400) is made having a tubular, elongated, hollow, active section (445) which has a cross-section containing an air electrode (452) a fuel electrode (454) and solid oxide electrolyte (456) between them, where the fuel cell transitions into at least one inactive section (460) with a flattened parallel sided cross-section (462, 468) each cross-section having channels (472, 474, 476) in them which smoothly communicate with each other at an interface section (458).

Simple Electrolyzer Model Development for High-Temperature Electrolysis System Analysis Using Solid Oxide Electrolysis Cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

JaeHwa Koh; DuckJoo Yoon; Chang H. Oh

2010-07-01

An electrolyzer model for the analysis of a hydrogen-production system using a solid oxide electrolysis cell (SOEC) has been developed, and the effects for principal parameters have been estimated by sensitivity studies based on the developed model. The main parameters considered are current density, area specific resistance, temperature, pressure, and molar fraction and flow rates in the inlet and outlet. Finally, a simple model for a high-temperature hydrogen-production system using the solid oxide electrolysis cell integrated with very high temperature reactors is estimated.

Protective interlayer for high temperature solid electrolyte electrochemical cells

DOEpatents

Singh, P.; Vasilow, T.R.; Richards, V.L.

1996-05-14

The invention is comprised of an electrically conducting doped or admixed cerium oxide composition with niobium oxide and/or tantalum oxide for electrochemical devices, characterized by the general formula: Nb{sub x}Ta{sub y}Ce{sub 1{minus}x{minus}y}O{sub 2} where x is about 0.0 to 0.05, y is about 0.0 to 0.05, and x+y is about 0.02 to 0.05, and where x is preferably about 0.02 to 0.05 and y is 0, and a method of making the same is also described. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell, characterized by a first electrode; an electrically conductive interlayer of niobium and/or tantalum doped cerium oxide deposited over at least a first portion of the first electrode; an interconnect deposited over the interlayer; a solid electrolyte deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode deposited over the solid electrolyte. The interlayer is characterized as being porous and selected from the group consisting of niobium doped cerium oxide, tantalum doped cerium oxide, and niobium and tantalum doped cerium oxide or admixtures of the same. The first electrode, an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer is a dense yttria stabilized zirconium oxide, the interconnect layer is a dense, doped lanthanum chromite, and the second electrode, a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell can take on a plurality of shapes such as annular, planar, etc. and can be connected to a plurality of electrochemical cells in series and/or in parallel to generate electrical energy. 5 figs.

Methods for using novel cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

DOEpatents

Jacobson, Allan J.; Wang, Shuangyan; Kim, Gun Tae

2016-01-12

Methods using novel cathode, electrolyte and oxygen separation materials operating at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes include oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

Cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

DOEpatents

Jacobson, Allan J; Wang, Shuangyan; Kim, Gun Tae

2014-01-28

Novel cathode, electrolyte and oxygen separation materials are disclosed that operate at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes based on oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

Bench-Scale Filtration Testing in Support of the Pretreatment Engineering Platform (PEP)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Billing, Justin M.; Daniel, Richard C.; Kurath, Dean E.

Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed, constructed and operated as part of a plan to respond to issue M12, “Undemonstrated Leaching Processes.” The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. The PEP testing program specifies that bench-scale testing is to bemore » performed in support of specific operations, including filtration, caustic leaching, and oxidative leaching.« less

The electrochemical reduction processes of solid compounds in high temperature molten salts.

PubMed

Xiao, Wei; Wang, Dihua

2014-05-21

Solid electrode processes fall in the central focus of electrochemistry due to their broad-based applications in electrochemical energy storage/conversion devices, sensors and electrochemical preparation. The electrolytic production of metals, alloys, semiconductors and oxides via the electrochemical reduction of solid compounds (especially solid oxides) in high temperature molten salts has been well demonstrated to be an effective and environmentally friendly process for refractory metal extraction, functional materials preparation as well as spent fuel reprocessing. The (electro)chemical reduction of solid compounds under cathodic polarizations generally accompanies a variety of changes at the cathode/melt electrochemical interface which result in diverse electrolytic products with different compositions, morphologies and microstructures. This report summarizes various (electro)chemical reactions taking place at the compound cathode/melt interface during the electrochemical reduction of solid compounds in molten salts, which mainly include: (1) the direct electro-deoxidation of solid oxides; (2) the deposition of the active metal together with the electrochemical reduction of solid oxides; (3) the electro-inclusion of cations from molten salts; (4) the dissolution-electrodeposition process, and (5) the electron hopping process and carbon deposition with the utilization of carbon-based anodes. The implications of the forenamed cathodic reactions on the energy efficiency, chemical compositions and microstructures of the electrolytic products are also discussed. We hope that a comprehensive understanding of the cathodic processes during the electrochemical reduction of solid compounds in molten salts could form a basis for developing a clean, energy efficient and affordable production process for advanced/engineering materials.

Molecular dynamics study of solid-liquid heat transfer and passive liquid flow

NASA Astrophysics Data System (ADS)

Yesudasan Daisy, Sumith

High heat flux removal is a challenging problem in boilers, electronics cooling, concentrated photovoltaic and other power conversion devices. Heat transfer by phase change is one of the most efficient mechanisms for removing heat from a solid surface. Futuristic electronic devices are expected to generate more than 1000 W/cm2 of heat. Despite the advancements in microscale and nanoscale manufacturing, the maximum passive heat flux removal has been 300 W/cm2 in pool boiling. Such limitations can be overcome by developing nanoscale thin-film evaporation based devices, which however require a better understanding of surface interactions and liquid vapor phase change process. Evaporation based passive flow is an inspiration from the transpiration process that happens in trees. If we can mimic this process and develop heat removal devices, then we can develop efficient cooling devices. The existing passive flow based cooling devices still needs improvement to meet the future demands. To improve the efficiency and capacity of these devices, we need to explore and quantify the passive flow happening at nanoscales. Experimental techniques have not advanced enough to study these fundamental phenomena at the nanoscale, an alternative method is to perform theoretical study at nanoscales. Molecular dynamics (MD) simulation is a widely accepted powerful tool for studying a range of fundamental and engineering problems. MD simulations can be utilized to study the passive flow mechanism and heat transfer due to it. To study passive flow using MD, apart from the conventional methods available in MD, we need to have methods to simulate the heat transfer between solid and liquid, local pressure, surface tension, density, temperature calculation methods, realistic boundary conditions, etc. Heat transfer between solid and fluids has been a challenging area in MD simulations, and has only been minimally explored (especially for a practical fluid like water). Conventionally, an equilibrium canonical ensemble (NVT) is simulated using thermostat algorithms. For research in heat transfer involving solid liquid interaction, we need to perform non equilibrium MD (NEMD) simulations. In such NEMD simulations, the methods used for simulating heating from a surface is very important and must capture proper physics and thermodynamic properties. Development of MD simulation techniques to simulate solid-liquid heating and the study of fundamental mechanism of passive flow is the main focus of this thesis. An accurate surface-heating algorithm was developed for water which can now allow the study of a whole new set of fundamental heat transfer problems at the nanoscale like surface heating/cooling of droplets, thin-films, etc. The developed algorithm is implemented in the in-house developed C++ MD code. A direct two dimensional local pressure estimation algorithm is also formulated and implemented in the code. With this algorithm, local pressure of argon and platinum interaction is studied. Also, the surface tension of platinum-argon (solid-liquid) was estimated directly from the MD simulations for the first time. Contact angle estimation studies of water on platinum, and argon on platinum were also performed. A thin film of argon is kept above platinum plate and heated in the middle region, leading to the evaporation and pressure reduction thus creating a strong passive flow in the near surface region. This observed passive liquid flow is characterized by estimating the pressure, density, velocity and surface tension using Eulerian mapping method. Using these simulation, we have demonstrated the fundamental nature and origin of surface-driven passive flow. Heat flux removed from the surface is also estimated from the results, which shows a significant improvement can be achieved in thermal management of electronic devices by taking advantage of surface-driven strong passive liquid flow. Further, the local pressure of water on silicon di-oxide surface is estimated using the LAMMPS atomic to continuum (ATC) package towards the goal of simulating the passive flow in water.

High temperature resistant cermet and ceramic compositions. [for thermal resistant insulators and refractory coatings

NASA Technical Reports Server (NTRS)

Phillips, W. M. (Inventor)

1978-01-01

High temperature oxidation resistance, high hardness and high abrasion and wear resistance are properties of cermet compositions particularly to provide high temperature resistant refractory coatings on metal substrates, for use as electrical insulation seals for thermionic converters. The compositions comprise a sintered body of particles of a high temperature resistant metal or metal alloy, preferably molybdenum or tungsten particles, dispersed in and bonded to a solid solution formed of aluminum oxide and silicon nitride, and particularly a ternary solid solution formed of a mixture of aluminum oxide, silicon nitride and aluminum nitride. Ceramic compositions comprising a sintered solid solution of aluminum oxide, silicon nitride and aluminum nitride are also described.

Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors

Treesearch

Qifeng Zheng; Zhiyong Cai; Zhenqiang Ma; Shaoqin Gong

2015-01-01

A novel type of highly flexible and all-solid-state supercapacitor that uses cellulose nanofibril (CNF)/reduced graphene oxide (RGO)/carbon nanotube (CNT) hybrid aerogels as electrodes and H2SO4 poly (vinyl alcohol) PVA gel as the electrolyte was developed and is reported here. These flexible solid-state supercapacitors...

Chemical and thermal stability of core-shelled magnetite nanoparticles and solid silica

NASA Astrophysics Data System (ADS)

Cendrowski, Krzysztof; Sikora, Pawel; Zielinska, Beata; Horszczaruk, Elzbieta; Mijowska, Ewa

2017-06-01

Pristine nanoparticles of magnetite were coated by solid silica shell forming core/shell structure. 20 nm thick silica coating significantly enhanced the chemical and thermal stability of the iron oxide. Chemical and thermal stability of this structure has been compared to the magnetite coated by mesoporous shell and pristine magnetite nanoparticles. It is assumed that six-membered silica rings in a solid silica shell limit the rate of oxygen diffusion during thermal treatment in air and prevent the access of HCl molecules to the core during chemical etching. Therefore, the core/shell structure with a solid shell requires a longer time to induce the oxidation of iron oxide to a higher oxidation state and, basically, even strong concentrated acid such as HCl is not able to dissolve it totally in one month. This leads to the desired performance of the material in potential applications such as catalysis and environmental protection.

Chemical Weathering on Venus

NASA Astrophysics Data System (ADS)

Zolotov, Mikhail

2018-01-01

Chemical and phase compositions of Venus's surface could reflect history of gas- and fluid-rock interactions, recent and past climate changes, and a loss of water from the Earth's sister planet. The concept of chemical weathering on Venus through gas-solid type reactions has been established in 1960s after the discovery of hot and dense CO2-rich atmosphere inferred from Earth-based and Mariner 2 radio emission data. Initial works suggested carbonation, hydration, and oxidation of exposed igneous rocks and a control (buffering) of atmospheric gases by solid-gas type chemical equilibria in the near-surface lithosphere. Calcite, quartz, wollastonite, amphiboles, and Fe oxides were considered likely secondary minerals. Since the late 1970s, measurements of trace gases in the sub-cloud atmosphere by Pioneer Venus and Venera entry probes and Earth-based infrared spectroscopy doubted the likelihood of hydration and carbonation. The H2O gas content appeared to be low to allow a stable existence of hydrated and a majority of OH-bearing minerals. The concentration of SO2 was too high to allow the stability of calcite and Ca-rich silicates with respect to sulfatization to CaSO4. In 1980s, the supposed ongoing consumption of atmospheric SO2 to sulfates gained support by the detection of an elevated bulk S content at Venera and Vega landing sites. The induced composition of the near-surface atmosphere implied oxidation of ferrous minerals to magnetite and hematite, consistent with the infrared reflectance of surface materials. The likelihood of sulfatization and oxidation has been illustrated in modeling experiments at simulated Venus conditions. Venus's surface morphology suggests that hot surface rocks and fines of mainly mafic composition contacted atmospheric gases during several hundreds of millions years since a global volcanic resurfacing. Some exposed materials could have reacted at higher and lower temperatures in a presence of diverse gases at different altitudinal, volcanic, impact, and atmospheric settings. On highly deformed tessera terrains, more ancient rocks of unknown composition could reflect interactions with putative water-rich atmospheres and even aqueous solutions. Salt-, Fe oxide, or silica-rich formations would indicate past aqueous processes. The apparent diversity of affected solids, surface temperatures, pressures, and gas/fluid compositions throughout Venus's history implies multiple signs of chemical alteration, which remain to be investigated. The current understanding of chemical weathering is limited by the uncertain composition of the deep atmosphere, by the lack of direct data on the phase composition of surface materials, and by the uncertain data on thermodynamics of minerals and their solid solutions. In the preparation for further entry probe and lander missions, rock alteration needs to be investigated through chemical kinetic experiments and calculations of solid-gas(fluid) equilibria to constrain past and present processes.

Modeling of thermal expansion coefficient of perovskite oxide for solid oxide fuel cell cathode

NASA Astrophysics Data System (ADS)

Heydari, F.; Maghsoudipour, A.; Alizadeh, M.; Khakpour, Z.; Javaheri, M.

2015-09-01

Artificial intelligence models have the capacity to eliminate the need for expensive experimental investigation in various areas of manufacturing processes, including the material science. This study investigates the applicability of adaptive neuro-fuzzy inference system (ANFIS) approach for modeling the performance parameters of thermal expansion coefficient (TEC) of perovskite oxide for solid oxide fuel cell cathode. Oxides (Ln = La, Nd, Sm and M = Fe, Ni, Mn) have been prepared and characterized to study the influence of the different cations on TEC. Experimental results have shown TEC decreases favorably with substitution of Nd3+ and Mn3+ ions in the lattice. Structural parameters of compounds have been determined by X-ray diffraction, and field emission scanning electron microscopy has been used for the morphological study. Comparison results indicated that the ANFIS technique could be employed successfully in modeling thermal expansion coefficient of perovskite oxide for solid oxide fuel cell cathode, and considerable savings in terms of cost and time could be obtained by using ANFIS technique.

Simulation of thermal stresses in anode-supported solid oxide fuel cell stacks. Part II: Loss of gas-tightness, electrical contact and thermal buckling

NASA Astrophysics Data System (ADS)

Nakajo, Arata; Wuillemin, Zacharie; Van herle, Jan; Favrat, Daniel

Structural stability issues in planar solid oxide fuel cells arise from the mismatch between the coefficients of thermal expansion of the components. The stress state at operating temperature is the superposition of several contributions, which differ depending on the component. First, the cells accumulate residual stresses due to the sintering phase during the manufacturing process. Further, the load applied during assembly of the stack to ensure electric contact and flatten the cells prevents a completely stress-free expansion of each component during the heat-up. Finally, thermal gradients cause additional stresses in operation. The temperature profile generated by a thermo-electrochemical model implemented in an equation-oriented process modelling tool (gPROMS) was imported into finite-element software (ABAQUS) to calculate the distribution of stress and contact pressure on all components of a standard solid oxide fuel cell repeat unit. The different layers of the cell in exception of the cathode, i.e. anode, electrolyte and compensating layer were considered in the analysis to account for the cell curvature. Both steady-state and dynamic simulations were performed, with an emphasis on the cycling of the electrical load. The study includes two different types of cell, operation under both thermal partial oxidation and internal steam-methane reforming and two different initial thicknesses of the air and fuel compressive sealing gaskets. The results generated by the models are presented in two papers: Part I focuses on cell cracking. In the present paper, Part II, the occurrences of loss of gas-tightness in the compressive gaskets and/or electrical contact in the gas diffusion layer were identified. In addition, the dependence on temperature of both coefficients of thermal expansion and Young's modulus of the metallic interconnect (MIC) were implemented in the finite-element model to compute the plastic deformation, while the possibilities of thermal buckling were analysed in a dedicated and separate model. The value of the minimum stable thickness of the MIC is large, even though significantly affected by the operating conditions. This phenomenon prevents any unconsidered decrease of the thickness to reduce the thermal inertia of the stack. Thermal gradients and the shape of the temperature profile during operation induce significant decreases of the contact pressure on the gaskets near the fuel manifold, at the inlet or outlet, depending on the flow configuration. On the contrary, the electrical contact was ensured independently of the operating point and history, even though plastic strain developed in the gas diffusion layer.

Degradation analysis of anode-supported intermediate temperature-solid oxide fuel cells under various failure modes

NASA Astrophysics Data System (ADS)

Lee, Tae-Hee; Park, Ka-Young; Kim, Ji-Tae; Seo, Yongho; Kim, Ki Buem; Song, Sun-Ju; Park, Byoungnam; Park, Jun-Young

2015-02-01

This study focuses on mechanisms and symptoms of several simulated failure modes, which may have significant influences on the long-term durability and operational stability of intermediate temperature-solid oxide fuel cells (IT-SOFCs), including fuel/oxidation starvation by breakdown of fuel/air supply components and wet and dry cycling atmospheres. Anode-supported IT-SOFCs consisting of a Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)-Nd0.1Ce0.9O2-δ (NDC) composite cathode with an NDC electrolyte on a Ni-NDC anode substrate are fabricated via dry-pressings followed by the co-firing method. Comprehensive and systematic research based on the failure mode and effect analysis (FMEA) of anode-supported IT-SOFCs is conducted using various electrochemical and physiochemical analysis techniques to extend our understanding of the major mechanisms of performance deterioration under SOFC operating conditions. The fuel-starvation condition in the fuel-pump failure mode causes irreversible mechanical degradation of the electrolyte and cathode interface by the dimensional expansion of the anode support due to the oxidation of Ni metal to NiO. In contrast, the BSCF cathode shows poor stability under wet and dry cycling modes of cathode air due to the strong electroactivity of SrO with H2O. On the other hand, the air-depletion phenomena under air-pump failure mode results in the recovery of cell performance during the long-term operation without the visible microstructural transformation through the reduction of anode overvoltage.

A distributed real-time model of degradation in a solid oxide fuel cell, part I: Model characterization

NASA Astrophysics Data System (ADS)

Zaccaria, V.; Tucker, D.; Traverso, A.

2016-04-01

Despite the high efficiency and flexibility of fuel cells, which make them an attractive technology for the future energy generation, their economic competitiveness is still penalized by their short lifetime, due to multiple degradation phenomena. As a matter of fact, electrochemical performance of solid oxide fuel cells (SOFCs) is reduced because of different degradation mechanisms, which depend on operating conditions, fuel and air contaminants, impurities in materials, and others. In this work, a real-time, one dimensional (1D) model of a SOFC is used to simulate the effects of voltage degradation in the cell. Different mechanisms are summarized in a simple empirical expression that relates degradation rate to cell operating parameters (current density, fuel utilization and temperature), on a localized basis. Profile distributions of different variables during cell degradation are analyzed. In particular, the effect of degradation on current density, temperature, and total resistance of the cell are investigated. An analysis of localized degradation effects shows how different parts of the cell degrade at a different time rate, and how the various profiles are redistributed along the cell as consequence of different degradation rates.

Optimal fault-tolerant control strategy of a solid oxide fuel cell system

NASA Astrophysics Data System (ADS)

Wu, Xiaojuan; Gao, Danhui

2017-10-01

For solid oxide fuel cell (SOFC) development, load tracking, heat management, air excess ratio constraint, high efficiency, low cost and fault diagnosis are six key issues. However, no literature studies the control techniques combining optimization and fault diagnosis for the SOFC system. An optimal fault-tolerant control strategy is presented in this paper, which involves four parts: a fault diagnosis module, a switching module, two backup optimizers and a controller loop. The fault diagnosis part is presented to identify the SOFC current fault type, and the switching module is used to select the appropriate backup optimizer based on the diagnosis result. NSGA-II and TOPSIS are employed to design the two backup optimizers under normal and air compressor fault states. PID algorithm is proposed to design the control loop, which includes a power tracking controller, an anode inlet temperature controller, a cathode inlet temperature controller and an air excess ratio controller. The simulation results show the proposed optimal fault-tolerant control method can track the power, temperature and air excess ratio at the desired values, simultaneously achieving the maximum efficiency and the minimum unit cost in the case of SOFC normal and even in the air compressor fault.

Modeling of a thermally integrated 10 kWe planar solid oxide fuel cell system with anode offgas recycling and internal reforming by discretization in flow direction

NASA Astrophysics Data System (ADS)

Wahl, Stefanie; Segarra, Ana Gallet; Horstmann, Peter; Carré, Maxime; Bessler, Wolfgang G.; Lapicque, François; Friedrich, K. Andreas

2015-04-01

Combined heat and power production (CHP) based on solid oxide fuel cells (SOFC) is a very promising technology to achieve high electrical efficiency to cover power demand by decentralized production. This paper presents a dynamic quasi 2D model of an SOFC system which consists of stack and balance of plant and includes thermal coupling between the single components. The model is implemented in Modelica® and validated with experimental data for the stack UI-characteristic and the thermal behavior. The good agreement between experimental and simulation results demonstrates the validity of the model. Different operating conditions and system configurations are tested, increasing the net electrical efficiency to 57% by implementing an anode offgas recycle rate of 65%. A sensitivity analysis of characteristic values of the system like fuel utilization, oxygen-to-carbon ratio and electrical efficiency for different natural gas compositions is carried out. The result shows that a control strategy adapted to variable natural gas composition and its energy content should be developed in order to optimize the operation of the system.

Thin-Film Solid Oxide Fuel Cells

NASA Technical Reports Server (NTRS)

Chen, Xin; Wu, Nai-Juan; Ignatiev, Alex

2009-01-01

The development of thin-film solid oxide fuel cells (TFSOFCs) and a method of fabricating them have progressed to the prototype stage. This can result in the reduction of mass, volume, and the cost of materials for a given power level.

Removal of sulfur and nitrogen containing pollutants from discharge gases

DOEpatents

Joubert, James I.

1986-01-01

Oxides of sulfur and of nitrogen are removed from waste gases by reaction with an unsupported copper oxide powder to form copper sulfate. The resulting copper sulfate is dissolved in water to effect separation from insoluble mineral ash and dried to form solid copper sulfate pentahydrate. This solid sulfate is thermally decomposed to finely divided copper oxide powder with high specific surface area. The copper oxide powder is recycled into contact with the waste gases requiring cleanup. A reducing gas can be introduced to convert the oxide of nitrogen pollutants to nitrogen.

Stability of solid oxide fuel cell materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Armstrong, T.R.; Bates, J.L.; Chick, L.A.

1996-04-01

Interconnection materials in a solid oxide fuel cell are exposed to both highly oxidizing conditions at the cathode and to highly reducing conditions at the anode. The thermal expansion characteristics of substituted lanthanum and yttrium chromite interconnect materials were evaluated by dilatometry as a function of oxygen partial pressures from 1 atm to 10{sup -18} atm, controlled using a carbon dioxide/hydrogen buffer.

Monoclinic Sr(1-x)Na(x)SiO(3-0.5x): new superior oxide ion electrolytes.

PubMed

Singh, Preetam; Goodenough, John B

2013-07-10

Oxide ion electrolytes determine the temperature of operation of solid oxide fuel cells, oxygen separation membranes, and oxygen sensors. There is a strong incentive to lower their operating temperatures, in a solid oxide fuel cell, for example, from Top > 800 °C to Top ≈ 500 °C. The use of low-cost Na(+) rather than K(+) as the dopant in monoclinic SrSiO3 (C12/C1) is shown to provide a larger solid solution range (0 < x ≤ 0.45) in Sr1-xNaxSiO3-0.5x and to achieve an oxide ion conductivity σo ≥ 10(-2) S·cm(-1) by 525 °C as a result of lowering the temperature of a smooth transition to full disorder of the mobile oxide ions. The Sr1-xNaxSiO3-0.5x electrolytes are much less hygroscopic than Sr1-xKxSiO3-0.5x and are stable with a nickel composite anode in 5% H2/Ar as well as with cathodes such as La1-xSrxMnO3-δ and Sr0.7Y0.3CoO3-δ in air, which makes them candidate electrolytes for intermediate-temperature solid oxide fuel cells or for other applications of oxide ion electrolytes.

Solid rocket combustion simulator technology using the hybrid rocket for simulation

NASA Technical Reports Server (NTRS)

Ramohalli, Kumar

1994-01-01

The hybrid rocket is reexamined in light of several important unanswered questions regarding its performance. The well-known heat transfer limited burning rate equation is quoted, and its limitations are pointed out. Several inconsistencies in the burning rate determination through fuel depolymerization are explicitly discussed. The resolution appears to be through the postulate of (surface) oxidative degradation of the fuel. Experiments are initiated to study the fuel degradation in mixtures of nitrogen/oxygen in the 99.9 percent/0.1 percent to 98 percent/2 percent range. The overall hybrid combustion behavior is studied in a 2 in-diameter rocket motor, where a PMMA tube is used as the fuel. The results include detailed, real-time infrared video images of the combustion zone. Space- and time-averaged images give a broad indication of the temperature reached in the gases. A brief outline is shown of future work, which will specifically concentrate on the exploration of the role of the oxidizer transport to the fuel surface, and the role of the unburned fuel that is reported to escape below the classical time-averaged boundary layer flame.

Long-term behaviour of solid oxide fuel cell interconnect materials in contact with Ni-mesh during exposure in simulated anode gas at 700 and 800 °C

NASA Astrophysics Data System (ADS)

Garcia-Fresnillo, L.; Shemet, V.; Chyrkin, A.; de Haart, L. G. J.; Quadakkers, W. J.

2014-12-01

In the present study the long-term behaviour of two ferritic steels, Crofer 22 APU and Crofer 22H, in contact with a Ni-mesh during exposure in simulated anode gas, Ar-4%H2-2%H2O, at 700 and 800 °C for exposure times up to 3000 h was investigated. Ni diffusion from the Ni-mesh into the steel resulted in the formation of an austenitic zone whereas diffusion of iron and chromium from the steel into the Ni-mesh resulted in the formation of chromia base oxides in the Ni-mesh. Depending on the chemical composition of the steel, the temperature and the exposure time, interdiffusion processes between ferritic steel and Ni-mesh also resulted in σ-phase formation at the austenite-ferrite interface and in Laves-phase dissolution in the austenitic zone. The extent and morphology of the σ-phase formation are discussed on the basis of thermodynamic considerations, including reaction paths in the ternary alloy system Fe-Ni-Cr.

Large-eddy simulation of pulverized coal swirl jet flame

NASA Astrophysics Data System (ADS)

Muto, Masaya; Watanabe, Hiroaki; Kurose, Ryoichi; Komori, Satoru; Balusamy, Saravanan; Hochgreb, Simone

2013-11-01

Coal is an important energy resource for future demand for electricity, as coal reserves are much more abundant than those of other fossil fuels. In pulverized coal fired power plants, it is very important to improve the technology for the control of environmental pollutants such as nitrogen oxide, sulfur oxide and ash particles including unburned carbon. In order to achieve these requirements, understanding the pulverized coal combustion mechanism is necessary. However, the combustion process of the pulverized coal is not well clarified so far since pulverized coal combustion is a complicated phenomenon in which the maximum flame temperature exceeds 1500 degrees Celsius and some substances which can hardly be measured, for example, radical species and highly reactive solid particles are included. Accordingly, development of new combustion furnaces and burners requires high cost and takes a long period. In this study, a large-eddy simulation (LES) is applied to a pulverized coal combustion field and the results will be compared with the experiment. The results show that present LES can capture the general feature of the pulverized coal swirl jet flame.

Parametric study and performance analysis of hybrid rocket motors with double-tube configuration

NASA Astrophysics Data System (ADS)

Yu, Nanjia; Zhao, Bo; Lorente, Arnau Pons; Wang, Jue

2017-03-01

The practical implementation of hybrid rocket motors has historically been hampered by the slow regression rate of the solid fuel. In recent years, the research on advanced injector designs has achieved notable results in the enhancement of the regression rate and combustion efficiency of hybrid rockets. Following this path, this work studies a new configuration called double-tube characterized by injecting the gaseous oxidizer through a head end injector and an inner tube with injector holes distributed along the motor longitudinal axis. This design has demonstrated a significant potential for improving the performance of hybrid rockets by means of a better mixing of the species achieved through a customized injection of the oxidizer. Indeed, the CFD analysis of the double-tube configuration has revealed that this design may increase the regression rate over 50% with respect to the same motor with a conventional axial showerhead injector. However, in order to fully exploit the advantages of the double-tube concept, it is necessary to acquire a deeper understanding of the influence of the different design parameters in the overall performance. In this way, a parametric study is carried out taking into account the variation of the oxidizer mass flux rate, the ratio of oxidizer mass flow rate injected through the inner tube to the total oxidizer mass flow rate, and injection angle. The data for the analysis have been gathered from a large series of three-dimensional numerical simulations that considered the changes in the design parameters. The propellant combination adopted consists of gaseous oxygen as oxidizer and high-density polyethylene as solid fuel. Furthermore, the numerical model comprises Navier-Stokes equations, k-ε turbulence model, eddy-dissipation combustion model and solid-fuel pyrolysis, which is computed through user-defined functions. This numerical model was previously validated by analyzing the computational and experimental results obtained for conventional hybrid rocket designs. In addition, a performance analysis is conducted in order to evaluate the influence in the performance provoked by the possible growth of the diameter of the inner fuel grain holes during the motor operation. The latter phenomenon is known as burn through holes. Finally, after a statistical analysis of the data, a regression rate expression as a function of the design parameters is obtained.

Solid oxide MEMS-based fuel cells

DOEpatents

Jankowksi, Alan F.; Morse, Jeffrey D.

2007-03-13

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Laser surface treatment of porous ceramic substrate for application in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Mahmod, D. S. A.; Khan, A. A.; Munot, M. A.; Glandut, N.; Labbe, J. C.

2016-08-01

Laser has offered a large number of benefits for surface treatment of ceramics due to possibility of localized heating, very high heating/cooling rates and possibility of growth of structural configurations only produced under non-equilibrium high temperature conditions. The present work investigates oxidation of porous ZrB2-SiC sintered ceramic substrates through treatment by a 1072 ± 10 nm ytterbium fiber laser. A multi-layer structure is hence produced showing successively oxygen rich distinct layers. The porous bulk beneath these layers remained unaffected as this laser-formed oxide scale and protected the substrate from oxidation. A glassy SiO2 structure thus obtained on the surface of the substrate becomes subject of interest for further research, specifically for its utilization as solid protonic conductor in Solid Oxide Fuel Cells (SOFCs).

Three-phase boundary length in solid-oxide fuel cells: A mathematical model

NASA Astrophysics Data System (ADS)

Janardhanan, Vinod M.; Heuveline, Vincent; Deutschmann, Olaf

A mathematical model to calculate the volume specific three-phase boundary length in the porous composite electrodes of solid-oxide fuel cell is presented. The model is exclusively based on geometrical considerations accounting for porosity, particle diameter, particle size distribution, and solids phase distribution. Results are presented for uniform particle size distribution as well as for non-uniform particle size distribution.

Solid-State Reaction Between Fe-Al-Ca Alloy and Al2O3-CaO-FeO Oxide During Heat Treatment at 1473 K (1200 °C)

NASA Astrophysics Data System (ADS)

Liu, Chengsong; Yang, Shufeng; Li, Jingshe; Ni, Hongwei; Zhang, Xueliang

2017-04-01

The aim of this study was to control the physicochemical characteristics of inclusions in steel through appropriate heat treatment. Using a confocal scanning laser microscope (CSLM) and pipe furnace, the solid-state reactions between Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide during heat treatment at 1473 K (1200 °C) and the influence of these reactions on the compositions of and phases in the alloy and oxide were investigated by the diffusion couple method. Suitable pretreatment of the oxide using a CSLM and production of the diffusion couple of Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide gave good contact between the alloy and oxide. The diffusion couple was then sealed in a quartz tube with a piece of Ti foil to lower oxygen partial pressure and a block of Fe-Al-Ca alloy was introduced to conduct heat treatment experiments. Solid-state reactions between the alloy and oxide during heat treatment at 1473 K (1200 °C) were analyzed and discussed. A dynamic model to calculate the width of the particle precipitation zone based on the Wagner model of internal oxidation of metal was proposed. This model was helpful to understand the solid-state reaction mechanism between Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide.

Growth and Surface Modification of LaFeO3 Thin Films Induced By Reductive Annealing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Flynn, Brendan T.; Zhang, Hongliang; Shutthanandan, V.

2015-03-01

The electronic and ionic conductivity of perovskite oxides has enabled their use in diverse applications such as automotive exhaust catalysts, solid oxide fuel cell cathodes, and visible light photocatalysts. The redox chemistry at the surface of perovskite oxides is largely dependent on the oxidation state of the metal cations as well as the oxide surface stoichiometry. In this study, LaFeO3 (LFO) thin films grown on yttria-stabilized zirconia (YSZ) was characterized using both bulk and surface sensitive techniques. A combination of in situ reflection high energy electron diffraction (RHEED), x-ray diffraction (XRD), transmission electron microscopy (TEM) and Rutherford backscattering spectrometry (RBS)more » demonstrated that the film is highly oriented and stoichiometric. The film was annealed in an ultra-high vacuum chamber to simulate reducing conditions and studied by angle-resolved x-ray photoelectron spectroscopy (XPS). Iron was found to exist as Fe(0), Fe(II), and Fe(III) depending on the annealing conditions and the depth within the film. A decrease in the concentration of surface oxygen species was correlated with iron reduction. These results should help guide and enhance the design of perovskite materials for catalysts.« less

Propulsion and Power Rapid Response R&D Support Delivery Order 0041: Power Dense Solid Oxide Fuel Cell Systems: High Performance, High Power Density Solid Oxide Fuel Cells - Materials and Load Control

DTIC Science & Technology

2008-12-01

respectively. 2.3.1.2 Brushless DC Motor Brushless direct current ( BLDC ) motors feature high efficiency, ease of control , and astonishingly high power...modeling purposes, we ignore the modeling complexity of the BLDC controller and treat the motor and controller “as commutated”, i.e. we assume the...High Performance, High Power Density Solid Oxide Fuel Cells− Materials and Load Control Stephen W. Sofie, Steven R. Shaw, Peter A. Lindahl, and Lee H

Regeneration of sulfated metal oxides and carbonates

DOEpatents

Hubble, Bill R.; Siegel, Stanley; Cunningham, Paul T.

1978-03-28

Alkali metal or alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate found in dolomite or limestone are employed for removal of sulfur dioxide from combustion exhaust gases. The sulfated carbonates are regenerated to oxides through use of a solid-solid reaction, particularly calcium sulfide with calcium sulfate to form calcium oxide and sulfur dioxide gas. The regeneration is performed by contacting the sulfated material with a reductant gas such as hydrogen within an inert diluent to produce calcium sulfide in mixture with the sulfate under process conditions selected to permit the sulfide-sulfate, solid-state reaction to occur.

Zinc-aluminum oxide solid solution nanosheets obtained by pyrolysis of layered double hydroxide as the photoanodes for dye-sensitized solar cells.

PubMed

Xu, Zhiyuan; Shi, Jingjing; Haroone, Muhammad Sohail; Chen, Wenpeng; Zheng, Shufang; Lu, Jun

2018-04-01

Due to the superiority of metal-doped ZnO compared to TiO 2 , the Zn-M (M = Al 3+ , Ga 3+ , Cr 3+ , Ti 4+ , Ce 4+ ) mixed metal oxide solid solutions have been extensively studied for photocatalytic and photovoltaic applications. In this work, a systematic research has proceeded for the preparation of a zinc-aluminum oxide semiconductor as a photoanode for the dye-sensitized solar cells (DSSCs) by a simple pyrolysis route with the Zn-Al layered double hydroxide (LDH) as a precursor. The Zn-Al oxide solid solution has been applied for DSSCs as an electron acceptor, which is used to study the influence of different Al content and sintering temperature on the device efficiency. Finally, the Zn-Al oxide solid solution with calcination temperature 600 °C and Al 27 at.% content exhibits the best performance. The photoelectric efficiency improved 100 times when the Al 3+ content decreased from 44 to 27 at.%. The Zn x Al y O solid solution show a reasonable efficiency as photoanode materials in DSSCs, with the best preliminary performance reported so far, and shows its potential application for the photovoltaic devices. Copyright © 2018 Elsevier Inc. All rights reserved.

Infiltrated La0.4Sr0.4Fe0.03Ni0.03Ti0.94O3 based anodes for all ceramic and metal supported solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Nielsen, Jimmi; Persson, Åsa H.; Sudireddy, Bhaskar R.; Irvine, John T. S.; Thydén, Karl

2017-12-01

For improved robustness, durability and to avoid severe processing challenges alternatives to the Ni:YSZ composite electrode is highly desirable. The Ni:YSZ composite electrode is conventionally used for solid oxide fuel cell and solid oxide electrolysis cell. In the present study we report on high performing nanostructured Ni:CGO electrocatalyst coated A site deficient Lanthanum doped Strontium Titanate (La0.4Sr0.4Fe0.03Ni0.03Ti0.94O3) based anodes. The anodes were incorporated into the co-sintered DTU metal supported solid oxide fuel cell design and large sized 12 cm × 12 cm cells were fabricated. The titanate material showed good processing characteristics and surface wetting properties towards the Ni:CGO electrocatalyst coating. The cell performances were evaluated on single cell level (active area 16 cm2) and a power density at 0.7 V and 700 °C of 0.650 Wcm-2 with a fuel utilization of 31% was achieved. Taking the temperature into account the performances of the studied anodes are among the best reported for redox stable and corrosion resistant alternatives to the conventional Ni:YSZ composite solid oxide cell electrode.

Jet fuel based high pressure solid oxide fuel cell system

NASA Technical Reports Server (NTRS)

Gummalla, Mallika (Inventor); Yamanis, Jean (Inventor); Olsommer, Benoit (Inventor); Dardas, Zissis (Inventor); Bayt, Robert (Inventor); Srinivasan, Hari (Inventor); Dasgupta, Arindam (Inventor); Hardin, Larry (Inventor)

2013-01-01

A power system for an aircraft includes a solid oxide fuel cell system which generates electric power for the aircraft and an exhaust stream; and a heat exchanger for transferring heat from the exhaust stream of the solid oxide fuel cell to a heat requiring system or component of the aircraft. The heat can be transferred to fuel for the primary engine of the aircraft. Further, the same fuel can be used to power both the primary engine and the SOFC. A heat exchanger is positioned to cool reformate before feeding to the fuel cell. SOFC exhaust is treated and used as inerting gas. Finally, oxidant to the SOFC can be obtained from the aircraft cabin, or exterior, or both.

Jet Fuel Based High Pressure Solid Oxide Fuel Cell System

NASA Technical Reports Server (NTRS)

Srinivasan, Hari (Inventor); Hardin, Larry (Inventor); Gummalla, Mallika (Inventor); Yamanis, Jean (Inventor); Olsommer, Benoit (Inventor); Dardas, Zissis (Inventor); Dasgupta, Arindam (Inventor); Bayt, Robert (Inventor)

2015-01-01

A power system for an aircraft includes a solid oxide fuel cell system which generates electric power for the aircraft and an exhaust stream; and a heat exchanger for transferring heat from the exhaust stream of the solid oxide fuel cell to a heat requiring system or component of the aircraft. The heat can be transferred to fuel for the primary engine of the aircraft. Further, the same fuel can be used to power both the primary engine and the SOFC. A heat exchanger is positioned to cool reformate before feeding to the fuel cell. SOFC exhaust is treated and used as inerting gas. Finally, oxidant to the SOFC can be obtained from the aircraft cabin, or exterior, or both.

A novel accelerated oxidative stability screening method for pharmaceutical solids.

PubMed

Zhu, Donghua Alan; Zhang, Geoff G Z; George, Karen L S T; Zhou, Deliang

2011-08-01

Despite the fact that oxidation is the second most frequent degradation pathway for pharmaceuticals, means of evaluating the oxidative stability of pharmaceutical solids, especially effective stress testing, are still lacking. This paper describes a novel experimental method for peroxide-mediated oxidative stress testing on pharmaceutical solids. The method utilizes urea-hydrogen peroxide, a molecular complex that undergoes solid-state decomposition and releases hydrogen peroxide vapor at elevated temperatures (e.g., 30°C), as a source of peroxide. The experimental setting for this method is simple, convenient, and can be operated routinely in most laboratories. The fundamental parameter of the system, that is, hydrogen peroxide vapor pressure, was determined using a modified spectrophotometric method. The feasibility and utility of the proposed method in solid form selection have been demonstrated using various solid forms of ephedrine. No degradation was detected for ephedrine hydrochloride after exposure to the hydrogen peroxide vapor for 2 weeks, whereas both anhydrate and hemihydrate free base forms degraded rapidly under the test conditions. In addition, both the anhydrate and the hemihydrate free base degraded faster when exposed to hydrogen peroxide vapor at 30°C under dry condition than at 30°C/75% relative humidity (RH). A new degradation product was also observed under the drier condition. The proposed method provides more relevant screening conditions for solid dosage forms, and is useful in selecting optimal solid form(s), determining potential degradation products, and formulation screening during development. Copyright © 2011 Wiley-Liss, Inc.

A methodology for thermodynamic simulation of high temperature, internal reforming fuel cell systems

NASA Astrophysics Data System (ADS)

Matelli, José Alexandre; Bazzo, Edson

This work presents a methodology for simulation of fuel cells to be used in power production in small on-site power/cogeneration plants that use natural gas as fuel. The methodology contemplates thermodynamics and electrochemical aspects related to molten carbonate and solid oxide fuel cells (MCFC and SOFC, respectively). Internal steam reforming of the natural gas hydrocarbons is considered for hydrogen production. From inputs as cell potential, cell power, number of cell in the stack, ancillary systems power consumption, reformed natural gas composition and hydrogen utilization factor, the simulation gives the natural gas consumption, anode and cathode stream gases temperature and composition, and thermodynamic, electrochemical and practical efficiencies. Both energetic and exergetic methods are considered for performance analysis. The results obtained from natural gas reforming thermodynamics simulation show that the hydrogen production is maximum around 700 °C, for a steam/carbon ratio equal to 3. As shown in the literature, the found results indicate that the SOFC is more efficient than MCFC.

Chemical looping combustion: A new low-dioxin energy conversion technology.

PubMed

Hua, Xiuning; Wang, Wei

2015-06-01

Dioxin production is a worldwide concern because of its persistence and carcinogenic, teratogenic, and mutagenic effects. The pyrolysis-chemical looping combustion process of disposing solid waste is an alternative to traditional solid waste incineration developed to reduce the dioxin production. Based on the equilibrium composition of the Deacon reaction, pyrolysis gas oxidized by seven common oxygen carriers, namely, CuO, NiO, CaSO4, CoO, Fe2O3, Mn3O4, and FeTiO3, is studied and compared with the pyrolysis gas directly combusted by air. The result shows that the activity of the Deacon reaction for oxygen carriers is lower than that for air. For four typical oxygen carriers (CuO, NiO, Fe2O3, and FeTiO3), the influences of temperature, pressure, gas composition, and tar on the Deacon reaction are discussed in detail. According to these simulation results, the dioxin production in China, Europe, the United States, and Japan is predicted for solid waste disposal by the pyrolysis-chemical looping combustion process. Thermodynamic analysis results in this paper show that chemical looping combustion can reduce dioxin production in the disposal of solid waste. Copyright © 2015. Published by Elsevier B.V.

Paralinear Oxidation of CVD SiC in Simulated Fuel-Rich Combustion

NASA Technical Reports Server (NTRS)

Fox, Dennis S.; Opila, Elizabeth J.; Hann, Raiford E.

2000-01-01

The oxidation kinetics of CVD SiC were measured by thermogravimetric analysis (TGA) in a 4H2 (central dot) 12H2O (central dot) 10CO (central dot) 7CO2 (central dot) 67N2 gas mixture flowing at 0.44 cm/s at temperatures between 1300 and 1450 C in fused quartz furnace tubes at I atm total pressure. The SiC was oxidized to form solid SiO2. At less than or = 1350 C, the SiO2 was in turn volatilized. Volatilization kinetics were consistent with the thermodynamic predictions based on SiO formation. These two simultaneous reactions resulted in overall paralinear kinetics. A curve fitting technique was used to determine the linear and parabolic rate constants from the paralinear kinetic data. Volatilization of the protective SiO2 scale resulted in accelerated consumption of SiC. Recession rates under conditions more representative of actual combustors were estimated from the furnace data.

Method for producing metal oxide nanoparticles

DOEpatents

Phillips, Jonathan [Santa Fe, NM; Mendoza, Daniel [Santa Fe, NM; Chen, Chun-Ku [Albuquerque, NM

2008-04-15

Method for producing metal oxide nanoparticles. The method includes generating an aerosol of solid metallic microparticles, generating plasma with a plasma hot zone at a temperature sufficiently high to vaporize the microparticles into metal vapor, and directing the aerosol into the hot zone of the plasma. The microparticles vaporize in the hot zone into metal vapor. The metal vapor is directed away from the hot zone and into the cooler plasma afterglow where it oxidizes, cools and condenses to form solid metal oxide nanoparticles.

Direct hydrocarbon fuel cells

DOEpatents

Barnett, Scott A.; Lai, Tammy; Liu, Jiang

2010-05-04

The direct electrochemical oxidation of hydrocarbons in solid oxide fuel cells, to generate greater power densities at lower temperatures without carbon deposition. The performance obtained is comparable to that of fuel cells used for hydrogen, and is achieved by using novel anode composites at low operating temperatures. Such solid oxide fuel cells, regardless of fuel source or operation, can be configured advantageously using the structural geometries of this invention.

An assessment on convective and radiative heat transfer modelling in tubular solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Sánchez, D.; Muñoz, A.; Sánchez, T.

Four models of convective and radiative heat transfer inside tubular solid oxide fuel cells are presented in this paper, all of them applicable to multidimensional simulations. The work is aimed at assessing if it is necessary to use a very detailed and complicated model to simulate heat transfer inside this kind of device and, for those cases when simple models can be used, the errors are estimated and compared to those of the more complex models. For the convective heat transfer, two models are presented. One of them accounts for the variation of film coefficient as a function of local temperature and composition. This model gives a local value for the heat transfer coefficients and establishes the thermal entry length. The second model employs an average value of the transfer coefficient, which is applied to the whole length of the duct being studied. It is concluded that, unless there is a need to calculate local temperatures, a simple model can be used to evaluate the global performance of the cell with satisfactory accuracy. For the radiation heat transfer, two models are presented again. One of them considers radial radiation exclusively and, thus, radiative exchange between adjacent cells is neglected. On the other hand, the second model accounts for radiation in all directions but increases substantially the complexity of the problem. For this case, it is concluded that deviations between both models are higher than for convection. Actually, using a simple model can lead to a not negligible underestimation of the temperature of the cell.

Effects of a reactive barrier and aquifer geology on metal distribution and mobility in a mine drainage impacted aquifer.

PubMed

Doerr, Nora A; Ptacek, Carol J; Blowes, David W

2005-06-01

The Nickel Rim aquifer has been impacted for five decades by a metal-rich plume generated from the Nickel Rim mine tailings impoundment. Metals released by the oxidation of pyrrhotite in the unsaturated zone of the tailings migrate into the downgradient aquifer, affecting both the groundwater and the aquifer solids. A reactive barrier has been installed in the aquifer to remove sulfate and metals from the groundwater. The effect of the reactive barrier on metal concentrations in the aquifer solids has not previously been studied. In this study, a series of selective extraction procedures was applied to cores of aquifer sediment, to ascertain the distribution of metals among various solid phases present in the aquifer. Extraction results were combined with groundwater chemistry, geochemical modelling and solid-phase microanalyses, to assess the potential mobility of metals under changing geochemical conditions. Reactions within the reactive barrier caused an increase in the solid-phase carbonate content downgradient from the barrier. The concentrations of poorly crystalline, oxidized phases of Mn and Fe, as well as concentrations of Cr(III) associated with oxidized Fe, and poorly crystalline Zn, are lower downgradient from the barrier, whereas total solid-phase metal concentrations remain constant. Iron and Mn accumulate as oxidized, easily extractable forms in a peat layer overlying the aquifer. Although these oxides may buffer reducing plumes, they also have the potential to release metals to the groundwater, should a reduced condition be imposed on the aquifer by remedial actions.

Air feed tube support system for a solid oxide fuel cell generator

DOEpatents

Doshi, Vinod B.; Ruka, Roswell J.; Hager, Charles A.

2002-01-01

A solid oxide fuel cell generator (12), containing tubular fuel cells (36) with interior air electrodes (18), where a supporting member (82) containing a plurality of holes (26) supports oxidant feed tubes (51), which pass from an oxidant plenum (52") into the center of the fuel cells, through the holes (26) in the supporting member (82), where a compliant gasket (86) around the top of the oxidant feed tubes and on top (28) of the supporting member (82) helps support the oxidant feed tubes and center them within the fuel cells, and loosen the tolerance for centering the air feed tubes.

Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals

USGS Publications Warehouse

Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

2009-01-01

Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.

Program of scientific investigations and development of solid-oxide fuel cells (SOFC) in VIITF proposals on scientific and technical collaboration and SOFC commercialization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kleschev, Yu.N.; Chulharev, V.F.

1996-04-01

Investigations being performed at VNIITF covers the whole cycle of solid oxide fuel cell manufacturing. This report describes the main directions of investigations in materials, technologies, and commercialization.

Liquid Secondary Waste Grout Formulation and Waste Form Qualification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Um, Wooyong; Williams, B. D.; Snyder, Michelle M. V.

This report describes the results from liquid secondary waste (LSW) grout formulation and waste form qualification tests performed at Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions (WRPS) to evaluate new formulations for preparing a grout waste form with high-sulfate secondary waste simulants and the release of key constituents from these grout monoliths. Specific objectives of the LSW grout formulation and waste form qualification tests described in this report focused on five activities: 1.preparing new formulations for the LSW grout waste form with high-sulfate LSW simulants and solid characterization of the cured LSW grout waste form; 2.conducting themore » U.S. Environmental Protection Agency (EPA) Method 1313 leach test (EPA 2012) on the grout prepared with the new formulations, which solidify sulfate-rich Hanford Tank Waste Treatment and Immobilization Plant (WTP) off-gas condensate secondary waste simulant, using deionized water (DIW); 3.conducting the EPA Method 1315 leach tests (EPA 2013) on the grout monoliths made with the new dry blend formulations and three LSW simulants (242-A evaporator condensate, Environmental Restoration Disposal Facility (ERDF) leachate, and WTP off-gas condensate) using two leachants, DIW and simulated Hanford Integrated Disposal Facility (IDF) Site vadose zone pore water (VZPW); 4.estimating the 99Tc desorption K d (distribution coefficient) values for 99Tc transport in oxidizing conditions to support the IDF performance assessment (PA); 5.estimating the solubility of 99Tc(IV)-bearing solid phases for 99Tc transport in reducing conditions to support the IDF PA.« less

Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

DOEpatents

Schwartz, Michael; White, James H.; Sammells, Anthony F.

2005-09-27

This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

DOEpatents

Schwartz, Michael; White, James H.; Sammels, Anthony F.

2000-01-01

This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

The Structure and Properties of Plasma Sprayed Iron Oxide Doped Manganese Cobalt Oxide Spinel Coatings for SOFC Metallic Interconnectors

NASA Astrophysics Data System (ADS)

Puranen, Jouni; Lagerbom, Juha; Hyvärinen, Leo; Kylmälahti, Mikko; Himanen, Olli; Pihlatie, Mikko; Kiviaho, Jari; Vuoristo, Petri

2011-01-01

Manganese cobalt oxide spinel doped with Fe2O3 was studied as a protective coating on ferritic stainless steel interconnects. Chromium alloying causes problems at high operation temperatures in such oxidizing conditions where chromium compounds evaporate and poison the cathode active area, causing the degradation of the solid oxide fuel cell. In order to prevent chromium evaporation, these interconnectors need a protective coating to block the chromium evaporation and to maintain an adequate electrical conductivity. Thermal spraying is regarded as a promising way to produce dense and protective layers. In the present work, the ceramic Mn-Co-Fe oxide spinel coatings were produced by using the atmospheric plasma spray process. Coatings with low thickness and low amount of porosity were produced by optimizing deposition conditions. The original spinel structure decomposed because of the fast transformation of solid-liquid-solid states but was partially restored by using post-annealing treatment.

Tilts, dopants, vacancies and non-stoichiometry: Understanding and designing the properties of complex solid oxide perovskites from first principles

NASA Astrophysics Data System (ADS)

Bennett, Joseph W.

Perovskite oxides of formula ABO3 have a wide range of structural, electrical and mechanical properties, making them vital materials for many applications, such as catalysis, ultrasound machines and communication devices. Perovskite solid solutions with high piezoelectric response, such as ferroelectrics, are of particular interest as they can be employed as sensors in SONAR devices. Ferroelectric materials are unique in that their chemical and electrical properties can be non-invasively and reversibly changed, by switching the bulk polarization. This makes ferroelectrics useful for applications in non-volatile random access memory (NVRAM) devices. Perovskite solid solutions with a lower piezoelectric response than ferroelectrics are important for communication technology, as they function well as electroceramic capacitors. Also of interest is how these materials act as a component in a solid oxide fuel cell, as they can function as an efficient source of energy. Altering the chemical composition of these solid oxide materials offers an opportunity to change the desired properties of the final ceramic, adding a degree of flexibility that is advantageous for a variety of applications. These solid oxides are complex, sometimes disordered systems that are a challenge to study experimentally. However, as it is their complexity which produces favorable properties, highly accurate modeling which captures the essential features of the disordered structure is necessary to explain the behavior of current materials and predict favorable compositions for new materials. Methodological improvements and faster computer speeds have made first-principles and atomistic calculations a viable tool for understanding these complex systems. Offering a combination of accuracy and computational speed, the density functional theory (DFT) approach can reveal details about the microscopic structure and interactions of complex systems. Using DFT and a combination of principles from both inorganic chemistry and materials science, I have been able to gain insights into solid oxide perovskite-based systems.

Solid polymer electrolyte compositions

DOEpatents

Garbe, James E.; Atanasoski, Radoslav; Hamrock, Steven J.; Le, Dinh Ba

2001-01-01

An electrolyte composition is featured that includes a solid, ionically conductive polymer, organically modified oxide particles that include organic groups covalently bonded to the oxide particles, and an alkali metal salt. The electrolyte composition is free of lithiated zeolite. The invention also features cells that incorporate the electrolyte composition.

Fuel/oxidizer-rich high-pressure preburners. [staged-combustion rocket engine

NASA Technical Reports Server (NTRS)

Schoenman, L.

1981-01-01

The analyses, designs, fabrication, and cold-flow acceptance testing of LOX/RP-1 preburner components required for a high-pressure staged-combustion rocket engine are discussed. Separate designs of injectors, combustion chambers, turbine simulators, and hot-gas mixing devices are provided for fuel-rich and oxidizer-rich operation. The fuel-rich design addresses the problem of non-equilibrium LOX/RP-1 combustion. The development and use of a pseudo-kinetic combustion model for predicting operating efficiency, physical properties of the combustion products, and the potential for generating solid carbon is presented. The oxygen-rich design addresses the design criteria for the prevention of metal ignition. This is accomplished by the selection of materials and the generation of well-mixed gases. The combining of unique propellant injector element designs with secondary mixing devices is predicted to be the best approach.

Facile solid-state synthesis of oxidation-resistant metal nanoparticles at ambient conditions

NASA Astrophysics Data System (ADS)

Lee, Kyu Hyung; Jung, Hyuk Joon; Lee, Ju Hee; Kim, Kyungtae; Lee, Byeongno; Nam, Dohyun; Kim, Chung Man; Jung, Myung-Hwa; Hur, Nam Hwi

2018-05-01

A simple and scalable method for the synthesis of metal nanoparticles in the solid-state was developed, which can produce nanoparticles in the absence of solvents. Nanoparticles of coinage metals were synthesized by grinding solid hydrazine and the metal precursors in their acetates and oxides at 25 °C. The silver and gold acetates converted completely within 6 min into Ag and Au nanoparticles, respectively, while complete conversion of the copper acetate to the Cu sub-micrometer particles took about 2 h. Metal oxide precursors were also converted into metal nanoparticles by grinding alone. The resulting particles exhibit distinctive crystalline lattice fringes, indicating the formation of highly crystalline phases. The Cu sub-micrometer particles are better resistant to oxidation and exhibit higher conductivity compared to conventional Cu nanoparticles. This solid-state method was also applied for the synthesis of platinum group metals and intermetallic Cu3Au, which can be further extended to synthesize other metal nanoparticles.

Robust, functional nanocrystal solids by infilling with atomic layer deposition.

PubMed

Liu, Yao; Gibbs, Markelle; Perkins, Craig L; Tolentino, Jason; Zarghami, Mohammad H; Bustamante, Jorge; Law, Matt

2011-12-14

Thin films of colloidal semiconductor nanocrystals (NCs) are inherently metatstable materials prone to oxidative and photothermal degradation driven by their large surface-to-volume ratios and high surface energies. (1) The fabrication of practical electronic devices based on NC solids hinges on preventing oxidation, surface diffusion, ripening, sintering, and other unwanted physicochemical changes that can plague these materials. Here we use low-temperature atomic layer deposition (ALD) to infill conductive PbSe NC solids with metal oxides to produce inorganic nanocomposites in which the NCs are locked in place and protected against oxidative and photothermal damage. Infilling NC field-effect transistors and solar cells with amorphous alumina yields devices that operate with enhanced and stable performance for at least months in air. Furthermore, ALD infilling with ZnO lowers the height of the inter-NC tunnel barrier for electron transport, yielding PbSe NC films with electron mobilities of 1 cm2 V(-1) s(-1). Our ALD technique is a versatile means to fabricate robust NC solids for optoelectronic devices.

Thermodynamic analysis of Direct Urea Solid Oxide Fuel Cell in combined heat and power applications

NASA Astrophysics Data System (ADS)

Abraham, F.; Dincer, I.

2015-12-01

This paper presents a comprehensive steady state modelling and thermodynamic analysis of Direct Urea Solid Oxide Fuel Cell integrated with Gas Turbine power cycle (DU-SOFC/GT). The use of urea as direct fuel mitigates public health and safety risks associated with the use of hydrogen and ammonia. The integration scheme in this study covers both oxygen ion-conducting solid oxide fuel cells (SOFC-O) and hydrogen proton-conducting solid oxide fuel cells (SOFC-H). Parametric case studies are carried out to investigate the effects of design and operating parameters on the overall performance of the system. The results reveal that the fuel cell exhibited the highest level of exergy destruction among other system components. Furthermore, the SOFC-O based system offers better overall performance than that with the SOFC-H option mainly due to the detrimental reverse water-gas shift reaction at the SOFC anode as well as the unique configuration of the system.

Charge induced enhancement of adsorption for hydrogen storage materials

NASA Astrophysics Data System (ADS)

Sun, Xiang

2009-12-01

The rising concerns about environmental pollution and global warming have facilitated research interest in hydrogen energy as an alternative energy source. To apply hydrogen for transportations, several issues have to be solved, within which hydrogen storage is the most critical problem. Lots of materials and devices have been developed; however, none is able to meet the DOE storage target. The primary issue for hydrogen physisorption is a weak interaction between hydrogen and the surface of solid materials, resulting negligible adsorption at room temperature. To solve this issue, there is a need to increase the interaction between the hydrogen molecules and adsorbent surface. In this study, intrinsic electric dipole is investigated to enhance the adsorption energy. The results from the computer simulation of single ionic compounds with hydrogen molecules to form hydrogen clusters showed that electrical charge of substances plays an important role in generation of attractive interaction with hydrogen molecules. In order to further examine the effects of static interaction on hydrogen adsorption, activated carbon with a large surface area was impregnated with various ionic salts including LiCl, NaCl, KCl, KBr, and NiCl2 and their performance for hydrogen storage was evaluated by using a volumetric method. Corresponding computer simulations have been carried out by using DFT (Density Functional Theory) method combined with point charge arrays. Both experimental and computational results prove that the adsorption capacity of hydrogen and its interaction with the solid materials increased with electrical dipole moment. Besides the intrinsic dipole, an externally applied electric field could be another means to enhance hydrogen adsorption. Hydrogen adsorption under an applied electric field was examined by using porous nickel foil as electrodes. Electrical signals showed that adsorption capacity increased with the increasing of gas pressure and external electric voltage. Direct measurement of the amount of hydrogen adsorption was also carried out with porous nickel oxides and magnesium oxides using the piezoelectric material PMN-PT as the charge supplier due to the pressure. The adsorption enhancement from the PMN-PT generated charges is obvious at hydrogen pressure between 0 and 60 bars, where the hydrogen uptake is increased at about 35% for nickel oxide and 25% for magnesium oxide. Computer simulation reveals that under the external electric field, the electron cloud of hydrogen molecules is pulled over to the adsorbent site and can overlap with the adsorbent electrons, which in turn enhances the adsorption energy. Experiments were also carried out to examine the effects of hydrogen spillover with charge induced enhancement. The results show that the overall storage capacity in nickel oxide increased remarkably by a factor of 4.

Protective interlayer for high temperature solid electrolyte electrochemical cells

DOEpatents

Singh, Prabhakar; Vasilow, Theodore R.; Richards, Von L.

1996-01-01

The invention comprises of an electrically conducting doped or admixed cerium oxide composition with niobium oxide and/or tantalum oxide for electrochemical devices, characterized by the general formula: Nb.sub.x Ta.sub.y Ce.sub.1-x-y O.sub.2 where x is about 0.0 to 0.05, y is about 0.0 to 0.05, and x+y is about 0.02 to 0.05, and where x is preferably about 0.02 to 0.05 and y is 0, and a method of making the same. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell (10), characterized by a first electrode (12); an electrically conductive interlayer (14) of niobium and/or tantalum doped cerium oxide deposited over at least a first portion (R) of the first electrode; an interconnect (16) deposited over the interlayer; a solid electrolyte (18) deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode (20) deposited over the solid electrolyte. The interlayer (14) is characterized as being porous and selected from the group consisting of niobium doped cerium oxide, tantalum doped cerium oxide, and niobium and tantalum doped cerium oxide or admixtures of the same. The first electrode (12), an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer (18) is a dense yttria stabilized zirconium oxide, the interconnect layer (16) is a dense, doped lanthanum chromite, and the second electrode (20), a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell (10) can take on a plurality of shapes such as annular, planar, etc. and can be connected to a plurality of electrochemical cells in series and/or in parallel to generate electrical energy.

Silicon Nanostructures, Excitonic Interactions, Laser Consequences

DTIC Science & Technology

2008-07-11

etching using an anodized aluminum oxide membrane as mask. The results described here lay a solid foundation for the next phase of development aimed at...achieved though reactive-ion-etching using an anodized aluminum oxide membrane as mask. The results described here lay a solid foundation for the next...Materials, April 4, 2006 issue). 6. Aijun Yin, Marian Tzolov, David Cardimona and Jimmy Xu, "Fabrication of Highly Ordered Anodic Aluminum Oxide

Effect of proton-conduction in electrolyte on electric efficiency of multi-stage solid oxide fuel cells

PubMed Central

Matsuzaki, Yoshio; Tachikawa, Yuya; Somekawa, Takaaki; Hatae, Toru; Matsumoto, Hiroshige; Taniguchi, Shunsuke; Sasaki, Kazunari

2015-01-01

Solid oxide fuel cells (SOFCs) are promising electrochemical devices that enable the highest fuel-to-electricity conversion efficiencies under high operating temperatures. The concept of multi-stage electrochemical oxidation using SOFCs has been proposed and studied over the past several decades for further improving the electrical efficiency. However, the improvement is limited by fuel dilution downstream of the fuel flow. Therefore, evolved technologies are required to achieve considerably higher electrical efficiencies. Here we present an innovative concept for a critically-high fuel-to-electricity conversion efficiency of up to 85% based on the lower heating value (LHV), in which a high-temperature multi-stage electrochemical oxidation is combined with a proton-conducting solid electrolyte. Switching a solid electrolyte material from a conventional oxide-ion conducting material to a proton-conducting material under the high-temperature multi-stage electrochemical oxidation mechanism has proven to be highly advantageous for the electrical efficiency. The DC efficiency of 85% (LHV) corresponds to a net AC efficiency of approximately 76% (LHV), where the net AC efficiency refers to the transmission-end AC efficiency. This evolved concept will yield a considerably higher efficiency with a much smaller generation capacity than the state-of-the-art several tens-of-MW-class most advanced combined cycle (MACC). PMID:26218470

Effect of proton-conduction in electrolyte on electric efficiency of multi-stage solid oxide fuel cells.

PubMed

Matsuzaki, Yoshio; Tachikawa, Yuya; Somekawa, Takaaki; Hatae, Toru; Matsumoto, Hiroshige; Taniguchi, Shunsuke; Sasaki, Kazunari

2015-07-28

Solid oxide fuel cells (SOFCs) are promising electrochemical devices that enable the highest fuel-to-electricity conversion efficiencies under high operating temperatures. The concept of multi-stage electrochemical oxidation using SOFCs has been proposed and studied over the past several decades for further improving the electrical efficiency. However, the improvement is limited by fuel dilution downstream of the fuel flow. Therefore, evolved technologies are required to achieve considerably higher electrical efficiencies. Here we present an innovative concept for a critically-high fuel-to-electricity conversion efficiency of up to 85% based on the lower heating value (LHV), in which a high-temperature multi-stage electrochemical oxidation is combined with a proton-conducting solid electrolyte. Switching a solid electrolyte material from a conventional oxide-ion conducting material to a proton-conducting material under the high-temperature multi-stage electrochemical oxidation mechanism has proven to be highly advantageous for the electrical efficiency. The DC efficiency of 85% (LHV) corresponds to a net AC efficiency of approximately 76% (LHV), where the net AC efficiency refers to the transmission-end AC efficiency. This evolved concept will yield a considerably higher efficiency with a much smaller generation capacity than the state-of-the-art several tens-of-MW-class most advanced combined cycle (MACC).

Atomistic Simulation of Interfaces in Materials of Solid State Ionics

NASA Astrophysics Data System (ADS)

Ivanov-Schitz, A. K.; Mazo, G. N.

2018-01-01

The possibilities of describing correctly interfaces of different types in solids within a computer experiment using molecular statics simulation, molecular dynamics simulation, and quantum chemical calculations are discussed. Heterophase boundaries of various types, including grain boundaries and solid electrolyte‒solid electrolyte and ionic conductor‒electrode material interfaces, are considered. Specific microstructural features and mechanisms of the ion transport in real heterophase structures (cationic conductor‒metal anode and anionic conductor‒cathode) existing in solid state ionics devices (such as solid-state batteries and fuel cells) are discussed.

Stack configurations for tubular solid oxide fuel cells

DOEpatents

Armstrong, Timothy R.; Trammell, Michael P.; Marasco, Joseph A.

2010-08-31

A fuel cell unit includes an array of solid oxide fuel cell tubes having porous metallic exterior surfaces, interior fuel cell layers, and interior surfaces, each of the tubes having at least one open end; and, at least one header in operable communication with the array of solid oxide fuel cell tubes for directing a first reactive gas into contact with the porous metallic exterior surfaces and for directing a second reactive gas into contact with the interior surfaces, the header further including at least one busbar disposed in electrical contact with at least one surface selected from the group consisting of the porous metallic exterior surfaces and the interior surfaces.

Communication—Electrolysis at High Efficiency with Remarkable Hydrogen Production Rates

DOE PAGES

Wood, Anthony; He, Hongpeng; Joia, Tahir; ...

2016-01-20

Solid Oxide Electrolysis (SOE) can be used to produce hydrogen with very high efficiencies at remarkable hydrogen production rates. Through microstructural and compositional modification, conventional low cost Solid Oxide Fuel Cell (SOFC) materials have been used to create a Solid Oxide Electrolysis Cell (SOEC) that can achieve remarkable current density at cell voltages allowing higher conversion efficiency than current commercial electrolysers. Current densities in excess of 6 A/cm2 have been achieved at 800°C with a cell voltage of < 1.67 V. This cell shows a more than 3-fold increase in hydrogen production rate at higher efficiency than established commercial electrolysers.

Solid polymer electrolyte composite membrane comprising a porous support and a solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide

DOEpatents

Liu, Han; Mittelsteadt, Cortney K; Norman, Timothy J; Griffith, Arthur E; LaConti, Anthony B

2015-02-24

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a thin, rigid, dimensionally-stable, non-electrically-conducting support, the support having a plurality of cylindrical, straight-through pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores are unevenly distributed, with some or no pores located along the periphery and more pores located centrally. The pores are completely filled with a solid polymer electrolyte, the solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide. The solid polymer electrolyte may also be deposited over the top and/or bottom surfaces of the support.

PA Discussion Topics

DTIC Science & Technology

2011-02-04

Solid Oxide fuel cell and Lithium Ion battery (~150 watts) • Enables extended mission durations • 12 hours of full power; 30 hours of silent watch...Hybrid fuel cell system is designed to replace the existing lead-acid batteries with an upgraded Solid Oxide fuel cell and Lithium Ion battery (~250

Development Of A Solid Oxide Fuel Cell Stack By Delphi And Battelle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mukerjee, Subhasish; Shaffer, Steven J.; Zizelman, James

2003-01-20

Delphi and Battelle are developing a Solid Oxide Fuel Cell (SOFC) stack for transportation and residential applications. This paper describes the status of development of the Generation 2 stack and key progress made in addressing some of the challenges in this technology.

Reduction in the Band Gap of Manganese-Doped Zinc Oxide: Role of the Oxidation State

NASA Astrophysics Data System (ADS)

Sharma, Sonia; Ramesh, Pranith; Swaminathan, P.

2015-12-01

Manganese-doped zinc oxide powders were synthesized by solid state reaction of the respective oxides. The high-temperature conditions were chosen such that multiple valence states of manganese were doped in the host zinc oxide lattice. Structural characterization was carried out to confirm the doping and to find the maximum amount of manganese that can be incorporated. Diffuse reflectance spectroscopy was used to measure the optical band gap of the doped sample and the lowering with respect to pure ZnO was attributed to the presence of higher oxidation states of manganese. The presence of these oxidation states was confirmed using x-ray photoelectron spectroscopy. The study shows that a solid state reaction is a viable route for synthesizing doped metal oxides with desired optical properties.

Modified cermet fuel electrodes for solid oxide electrochemical cells

DOEpatents

Ruka, Roswell J.; Spengler, Charles J.

1991-01-01

An exterior porous electrode (10), bonded to a solid oxygen ion conducting electrolyte (13) which is in contact with an interior electrode (14), contains coarse metal particles (12) of nickel and/or cobalt, having diameters from 3 micrometers to 35 micrometers, where the coarse particles are coated with a separate, porous, multiphase layer (17) containing fine metal particles of nickel and/or cobalt (18), having diameters from 0.05 micrometers to 1.75 micrometers and conductive oxide (19) selected from cerium oxide, doped cerium oxide, strontium titanate, doped strontium titanate and mixtures thereof.

First principles calculations of thermal conductivity with out of equilibrium molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Puligheddu, Marcello; Gygi, Francois; Galli, Giulia

The prediction of the thermal properties of solids and liquids is central to numerous problems in condensed matter physics and materials science, including the study of thermal management of opto-electronic and energy conversion devices. We present a method to compute the thermal conductivity of solids by performing ab initio molecular dynamics at non equilibrium conditions. Our formulation is based on a generalization of the approach to equilibrium technique, using sinusoidal temperature gradients, and it only requires calculations of first principles trajectories and atomic forces. We discuss results and computational requirements for a representative, simple oxide, MgO, and compare with experiments and data obtained with classical potentials. This work was supported by MICCoM as part of the Computational Materials Science Program funded by the U.S. Department of Energy (DOE), Office of Science , Basic Energy Sciences (BES), Materials Sciences and Engineering Division under Grant DOE/BES 5J-30.

Global distribution of particle phase state in atmospheric secondary organic aerosols

NASA Astrophysics Data System (ADS)

Shiraiwa, Manabu; Li, Ying; Tsimpidi, Alexandra P.; Karydis, Vlassis A.; Berkemeier, Thomas; Pandis, Spyros N.; Lelieveld, Jos; Koop, Thomas; Pöschl, Ulrich

2017-04-01

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes and solid over dry lands. We find that in the middle and upper troposphere SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded in SOA.

Global distribution of particle phase state in atmospheric secondary organic aerosols.

PubMed

Shiraiwa, Manabu; Li, Ying; Tsimpidi, Alexandra P; Karydis, Vlassis A; Berkemeier, Thomas; Pandis, Spyros N; Lelieveld, Jos; Koop, Thomas; Pöschl, Ulrich

2017-04-21

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes and solid over dry lands. We find that in the middle and upper troposphere SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded in SOA.

Global distribution of particle phase state in atmospheric secondary organic aerosols

PubMed Central

Shiraiwa, Manabu; Li, Ying; Tsimpidi, Alexandra P.; Karydis, Vlassis A.; Berkemeier, Thomas; Pandis, Spyros N.; Lelieveld, Jos; Koop, Thomas; Pöschl, Ulrich

2017-01-01

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes and solid over dry lands. We find that in the middle and upper troposphere SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants and organic molecules could kinetically limit gas–particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded in SOA. PMID:28429776

Development of a miniature solid propellant rocket motor for use in plume simulation studies

NASA Technical Reports Server (NTRS)

Baran, W. J.

1974-01-01

A miniature solid propellant rocket motor has been developed to be used in a program to determine those parameters which must be duplicated in a cold gas flow to produce aerodynamic effects on an experimental model similar to those produced by hot, particle-laden exhaust plumes. Phenomena encountered during the testing of the miniature solid propellant motors included erosive propellant burning caused by high flow velocities parallel to the propellant surface, regressive propellant burning as a result of exposed propellant edges, the deposition of aluminum oxide on the nozzle surfaces sufficient to cause aerodynamic nozzle throat geometry changes, and thermal erosion of the nozzle throat at high chamber pressures. A series of tests was conducted to establish the stability of the rocket chamber pressure and the repeatibility of test conditions. Data are presented which define the tests selected to represent the final test matrix. Qualitative observations are also presented concerning the phenomena experienced based on the results of a large number or rocket tests not directly applicable to the final test matrix.

Polypyrrole-polyoxometalate/reduced graphene oxide ternary nanohybrids for flexible, all-solid-state supercapacitors.

PubMed

Chen, Yuyun; Han, Min; Tang, Yujia; Bao, Jianchun; Li, Shunli; Lan, Yaqian; Dai, Zhihui

2015-08-11

Novel polypyrrole-polyoxometalate/reduced graphene oxide ternary nanohybrids (TNHs) are synthesized via a one-pot redox relay strategy. The TNHs exhibit high areal specific capacitance (2.61 mF cm(-2)), and the fabricated solid device also exhibits good rate capability, excellent flexibility and mechanical stability.

Chemical compositions, methods of making the chemical compositions, and structures made from the chemical compositions

DOEpatents

Yang, Lei; Cheng, Zhe; Liu, Ze; Liu, Meilin

2015-01-13

Embodiments of the present disclosure include chemical compositions, structures, anodes, cathodes, electrolytes for solid oxide fuel cells, solid oxide fuel cells, fuel cells, fuel cell membranes, separation membranes, catalytic membranes, sensors, coatings for electrolytes, electrodes, membranes, and catalysts, and the like, are disclosed.

Metal current collect protected by oxide film

DOEpatents

Jacobson, Craig P.; Visco, Steven J.; DeJonghe, Lutgard C.

2004-05-25

Provided are low-cost, mechanically strong, highly electronically conductive current collects and associated structures for solid-state electrochemical devices, techniques for forming these structures, and devices incorporating the structures. The invention provides solid state electrochemical devices having as current interconnects a ferritic steel felt or screen coated with a protective oxide film.

Method of fabricating a monolithic solid oxide fuel cell

DOEpatents

Minh, N.Q.; Horne, C.R.

1994-03-01

In a two-step densifying process of making a monolithic solid oxide fuel cell, a limited number of anode-electrolyte-cathode cells separated by an interconnect layer are formed and partially densified. Subsequently, the partially densified cells are stacked and further densified to form a monolithic array. 10 figures.

Method of fabricating a monolithic solid oxide fuel cell

DOEpatents

Minh, Nguyen Q.; Horne, Craig R.

1994-01-01

In a two-step densifying process of making a monolithic solid oxide fuel cell, a limited number of anode-electrolyte-cathode cells separated by an interconnect layer are formed and partially densified. Subsequently, the partially densified cells are stacked and further densified to form a monolithic array.

Study of low-temperature active rare-earth oxide catalysts for automotive exhaust clean-up.

DOT National Transportation Integrated Search

2014-02-01

We report a facile onepot synthesis of CexZr1-xO2 (0x1) solid solution nanocrystals using hydrothermal reactions. A direct formation of oxide solid solutions in aqueous solution under pressure at low temperatures was clearly revealed by X-ra...

Analysis of the Hazardous Material Reutilization Facilities at SUBASE Bangor and NS San Diego

DTIC Science & Technology

1990-12-01

soprene * styrene methyl acrylate methyl methacrylate *turpentine? varnish 9 GROUP IV: OXIDES AND PEROXIDE -rORKING COMPOUNDS a) Gases b) Liquids...lead fluorine GROUP XV: POISON a GROUP XVI: OXIDIZERS .a) Solid a) Solid phosphorus red ammonium nitrate phosphorus white/, ammonium perchlorate yellow

In operando spectroscopic studies of high temperature electrocatalysts used for energy conversion

NASA Astrophysics Data System (ADS)

McIntyre, Melissa Dawn

Solid-state electrochemical cells are efficient energy conversion devices that can be used for clean energy production or for removing air pollutants from exhaust gas emitted by combustion processes. For example, solid oxide fuel cells generate electricity with low emissions from a variety of fuel sources; solid oxide electrolysis cells produce zero-emission H2 fuel; and solid-state DeNOx cells remove NOx gases from diesel exhaust. In order to maintain high conversion efficiencies, these systems typically operate at temperatures ≥ 500°C. The high operating temperatures, however, accelerate chemical and mechanical cell degradation. To improve device durability, a mechanistic understanding of the surface chemistry occurring at the cell electrodes (anode and cathode) is critical in terms of refining cell design, material selection and operation protocols. The studies presented herein utilized in operando Raman spectroscopy coupled with electrochemical measurements to directly correlate molecular/material changes with device performance in solid oxide cells under various operating conditions. Because excessive carbon accumulation with carbon-based fuels destroys anodes, the first three studies investigated strategies for mitigating carbon accumulation on Ni cermet anodes. Results from the first two studies showed that low amounts of solid carbon stabilized the electrical output and improved performance of solid oxide fuel cells operating with syn-gas (H 2/CO fuel mixture). The third study revealed that infiltrating anodes with Sn or BaO suppressed carbon accumulation with CH4 fuel and that H2O was the most effective reforming agent facilitating carbon removal. The last two studies explored how secondary phases formed in traditional solid oxide cell materials doped with metal oxides improve electrochemical performance. Results from the fourth study suggest that the mixed ion-electron conducting Zr5Ti7O24 secondary phase can expand the electrochemically active region and increase electrochemical activity in cermet electrodes. The final study of lanthanum strontium manganite cathodes infiltrated with BaO revealed the reversible decomposition/formation of a Ba3Mn2O8 secondary phase under applied potentials and proposed mechanisms for the enhanced electrocatalytic oxygen reduction associated with this compound under polarizing conditions. Collectively, these studies demonstrate that mechanistic information obtained from molecular/material specific techniques coupled with electrochemical measurements can be used to help optimize materials and operating conditions in solid-state electrochemical cells.

CoxFe1-x oxide coatings on metallic interconnects for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shen, Fengyu; Lu, Kathy

2016-10-01

In order to improve the performance of Cr-containing steel as an interconnect material for solid oxide fuel cells, CoFe alloy coatings with Co:Fe ratios of 9:1, 8:2, 7:3, 6:4, and 5:5 are deposited by electrodeposition and then oxidized to CoxFe1-x oxide coatings with a thickness of ∼6 μm as protective layers on the interconnect. The area specific resistance of the coated interconnect increases with the Fe content. Higher Co content oxide coatings are more effective in limiting the growth of the chromia scale while all coatings are effective in inhibiting Cr diffusion and evaporation. With the Co0.8Fe0.2 oxide coated interconnect, the electrochemical performance of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode is improved. Only 1.54 atomic percentage of Cr is detected on the surface of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode while no Cr is detected 0.66 μm or more into the cathode. CoxFe1-x oxide coatings are promising candidates for solid oxide fuel cell interconnects with the advantage of using existing cathode species for compatibility and performance enhancement.

Development of a household waste treatment subsystem, volume 1. [with water conservation features

NASA Technical Reports Server (NTRS)

Gresko, T. M.; Murray, R. W.

1973-01-01

The domestic waste treatment subsystem was developed to process the daily liquid and non-metallic solid wastes provided by a family of four people. The subsystem was designed to be connected to the sewer line of a household which contained water conservation features. The system consisted of an evaporation technique to separate liquids from solids, an incineration technique for solids reduction, and a catalytic oxidizer for eliminating noxious gases from evaporation and incineration processes. All wastes were passed through a grinder which masticated the solids and deposited them in a settling tank. The liquids were transferred through a cleanable filter into a holding tank. From here the liquids were sprayed into an evaporator and a spray chamber where evaporation occurred. The resulting vapors were processed by catalytic oxidation. Water and latent energy were recovered in a combination evaporator/condenser heat exchanger. The solids were conveyed into an incinerator and reduced to ash while the incineration gases were passed through the catalytic oxidizer along with the processed water vapor.

Sintered Cathodes for All-Solid-State Structural Lithium-Ion Batteries

NASA Technical Reports Server (NTRS)

Huddleston, William; Dynys, Frederick; Sehirlioglu, Alp

2017-01-01

All-solid-state structural lithium ion batteries serve as both structural load-bearing components and as electrical energy storage devices to achieve system level weight savings in aerospace and other transportation applications. This multifunctional design goal is critical for the realization of next generation hybrid or all-electric propulsion systems. Additionally, transitioning to solid state technology improves upon battery safety from previous volatile architectures. This research established baseline solid state processing conditions and performance benchmarks for intercalation-type layered oxide materials for multifunctional application. Under consideration were lithium cobalt oxide and lithium nickel manganese cobalt oxide. Pertinent characteristics such as electrical conductivity, strength, chemical stability, and microstructure were characterized for future application in all-solid-state structural battery cathodes. The study includes characterization by XRD, ICP, SEM, ring-on-ring mechanical testing, and electrical impedance spectroscopy to elucidate optimal processing parameters, material characteristics, and multifunctional performance benchmarks. These findings provide initial conditions for implementing existing cathode materials in load bearing applications.

Modeling and simulation of Li-ion conduction in poly(ethylene oxide)

NASA Astrophysics Data System (ADS)

Gitelman, L.; Israeli, M.; Averbuch, A.; Nathan, M.; Schuss, Z.; Golodnitsky, D.

2007-12-01

Polyethylene oxide (PEO) containing a lithium salt (e.g., LiI) serves as a solid polymer electrolyte (SPE) in thin-film batteries and its ionic conductivity is a key parameter of their performance. We model and simulate Li + ion conduction in a single PEO molecule. Our simplified stochastic model of ionic motion is based on an analogy between protein channels of biological membranes that conduct Na +, K +, and other ions, and the PEO helical chain that conducts Li + ions. In contrast with protein channels and salt solutions, the PEO is both the channel and the solvent for the lithium salt (e.g., LiI). The mobile ions are treated as charged spherical Brownian particles. We simulate Smoluchowski dynamics in channels with a radius of ca. 0.1 nm and study the effect of stretching and temperature on ion conductivity. We assume that each helix (molecule) forms a random angle with the axis between these electrodes and the polymeric film is composed of many uniformly distributed oriented boxes that include molecules with the same direction. We further assume that mechanical stretching aligns the molecular structures in each box along the axis of stretching (intra-box alignment). Our model thus predicts the PEO conductivity as a function of the stretching, the salt concentration and the temperature. The computed enhancement of the ionic conductivity in the stretch direction is in good agreement with experimental results. The simulation results are also in qualitative agreement with recent theoretical and experimental results.

Fluid, solid and fluid-structure interaction simulations on patient-based abdominal aortic aneurysm models.

PubMed

Kelly, Sinead; O'Rourke, Malachy

2012-04-01

This article describes the use of fluid, solid and fluid-structure interaction simulations on three patient-based abdominal aortic aneurysm geometries. All simulations were carried out using OpenFOAM, which uses the finite volume method to solve both fluid and solid equations. Initially a fluid-only simulation was carried out on a single patient-based geometry and results from this simulation were compared with experimental results. There was good qualitative and quantitative agreement between the experimental and numerical results, suggesting that OpenFOAM is capable of predicting the main features of unsteady flow through a complex patient-based abdominal aortic aneurysm geometry. The intraluminal thrombus and arterial wall were then included, and solid stress and fluid-structure interaction simulations were performed on this, and two other patient-based abdominal aortic aneurysm geometries. It was found that the solid stress simulations resulted in an under-estimation of the maximum stress by up to 5.9% when compared with the fluid-structure interaction simulations. In the fluid-structure interaction simulations, flow induced pressure within the aneurysm was found to be up to 4.8% higher than the value of peak systolic pressure imposed in the solid stress simulations, which is likely to be the cause of the variation in the stress results. In comparing the results from the initial fluid-only simulation with results from the fluid-structure interaction simulation on the same patient, it was found that wall shear stress values varied by up to 35% between the two simulation methods. It was concluded that solid stress simulations are adequate to predict the maximum stress in an aneurysm wall, while fluid-structure interaction simulations should be performed if accurate prediction of the fluid wall shear stress is necessary. Therefore, the decision to perform fluid-structure interaction simulations should be based on the particular variables of interest in a given study.

Oxygen scrubbing and sensing in plant growth chambers using solid oxide electrolyzers

NASA Technical Reports Server (NTRS)

Sridhar, K. R.; MacElroy, Robert D.

1997-01-01

The maintenance of optimal levels of oxygen in the gaseous environment of a plant growth chamber during light and dark periods is an essential criterion for the correct growth of plants. The use of solid oxide electrolyzers to control the oxygen levels by removing the excess gaseous oxygen during periods of illumination and full-scale photosynthesis is described. A part of the oxygen removed can be stored and supplied back to the plants during dark periods. The excess oxygen can be used by the crew. The electrolizer can be additionally used in its open circuit mode, to sense the oxygen concentrations in the plant chamber. The solid oxide electrolysis process is described.

Tubular solid oxide fuel cells with porous metal supports and ceramic interconnections

DOEpatents

Huang, Kevin [Export, PA; Ruka, Roswell J [Pittsburgh, PA

2012-05-08

An intermediate temperature solid oxide fuel cell structure capable of operating at from 600.degree. C. to 800.degree. C. having a very thin porous hollow elongated metallic support tube having a thickness from 0.10 mm to 1.0 mm, preferably 0.10 mm to 0.35 mm, a porosity of from 25 vol. % to 50 vol. % and a tensile strength from 700 GPa to 900 GPa, which metallic tube supports a reduced thickness air electrode having a thickness from 0.010 mm to 0.2 mm, a solid oxide electrolyte, a cermet fuel electrode, a ceramic interconnection and an electrically conductive cell to cell contact layer.

Tuneable diode laser gas analyser for methane measurements on a large scale solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Lengden, Michael; Cunningham, Robert; Johnstone, Walter

2011-10-01

A new in-line, real time gas analyser is described that uses tuneable diode laser spectroscopy (TDLS) for the measurement of methane in solid oxide fuel cells. The sensor has been tested on an operating solid oxide fuel cell (SOFC) in order to prove the fast response and accuracy of the technology as compared to a gas chromatograph. The advantages of using a TDLS system for process control in a large-scale, distributed power SOFC unit are described. In future work, the addition of new laser sources and wavelength modulation will allow the simultaneous measurement of methane, water vapour, carbon-dioxide and carbon-monoxide concentrations.

Solid oxide fuel cell power plant with an anode recycle loop turbocharger

DOEpatents

Saito, Kazuo; Skiba, Tommy; Patel, Kirtikumar H.

2015-07-14

An anode exhaust recycle turbocharger (100) has a turbocharger turbine (102) secured in fluid communication with a compressed oxidant stream within an oxidant inlet line (218) downstream from a compressed oxidant supply (104), and the anode exhaust recycle turbocharger (100) also includes a turbocharger compressor (106) mechanically linked to the turbocharger turbine (102) and secured in fluid communication with a flow of anode exhaust passing through an anode exhaust recycle loop (238) of the solid oxide fuel cell power plant (200). All or a portion of compressed oxidant within an oxidant inlet line (218) drives the turbocharger turbine (102) to thereby compress the anode exhaust stream in the recycle loop (238). A high-temperature, automotive-type turbocharger (100) replaces a recycle loop blower-compressor (52).

Solid oxide fuel cell power plant with an anode recycle loop turbocharger

DOEpatents

Saito, Kazuo; Skiba, Tommy; Patel, Kirtikumar H.

2016-09-27

An anode exhaust recycle turbocharger (100) has a turbocharger turbine (102) secured in fluid communication with a compressed oxidant stream within an oxidant inlet line (218) downstream from a compressed oxidant supply (104), and the anode exhaust recycle turbocharger (100) also includes a turbocharger compressor (106) mechanically linked to the turbocharger turbine (102) and secured in fluid communication with a flow of anode exhaust passing through an anode exhaust recycle loop (238) of the solid oxide fuel cell power plant (200). All or a portion of compressed oxidant within an oxidant inlet line (218) drives the turbocharger turbine (102) to thereby compress the anode exhaust stream in the recycle loop (238). A high-temperature, automotive-type turbocharger (100) replaces a recycle loop blower-compressor (52).

Conversion of organic solids to hydrocarbons

DOEpatents

Greenbaum, E.

1995-05-23

A method of converting organic solids to liquid and gaseous hydrocarbons includes impregnating an organic solid with photosensitizing ions and exposing the impregnated solid to light in a non-oxidizing atmosphere for a time sufficient to photocatalytically reduce the solid to at least one of a liquid and a gaseous hydrocarbon. 5 Figs.

Conversion of organic solids to hydrocarbons

DOEpatents

Greenbaum, Elias

1995-01-01

A method of converting organic solids to liquid and gaseous hydrocarbons includes impregnating an organic solid with photosensitizing ions and exposing the impregnated solid to light in a non-oxidizing atmosphere for a time sufficient to photocatalytically reduce the solid to at least one of a liquid and a gaseous hydrocarbon.

Mixing and combustion enhancement of Turbocharged Solid Propellant Ramjet

NASA Astrophysics Data System (ADS)

Liu, Shichang; Li, Jiang; Zhu, Gen; Wang, Wei; Liu, Yang

2018-02-01

Turbocharged Solid Propellant Ramjet is a new concept engine that combines the advantages of both solid rocket ramjet and Air Turbo Rocket, with a wide operation envelope and high performance. There are three streams of the air, turbine-driving gas and augment gas to mix and combust in the afterburner, and the coaxial intake mode of the afterburner is disadvantageous to the mixing and combustion. Therefore, it is necessary to carry out mixing and combustion enhancement research. In this study, the numerical model of Turbocharged Solid Propellant Ramjet three-dimensional combustion flow field is established, and the numerical simulation of the mixing and combustion enhancement scheme is conducted from the aspects of head region intake mode to injection method in afterburner. The results show that by driving the compressed air to deflect inward and the turbine-driving gas to maintain strong rotation, radial and tangential momentum exchange of the two streams can be enhanced, thereby improving the efficiency of mixing and combustion in the afterburner. The method of injecting augment gas in the transverse direction and making sure the injection location is as close as possible to the head region is beneficial to improve the combustion efficiency. The outer combustion flow field of the afterburner is an oxidizer-rich environment, while the inner is a fuel-rich environment. To improve the efficiency of mixing and combustion, it is necessary to control the injection velocity of the augment gas to keep it in the oxygen-rich zone of the outer region. The numerical simulation for different flight conditions shows that the optimal mixing and combustion enhancement scheme can obtain high combustion efficiency and have excellent applicability in a wide working range.

Electrochemical catalyst recovery method

DOEpatents

Silva, L.J.; Bray, L.A.

1995-05-30

A method of recovering catalyst material from latent catalyst material solids includes: (a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; (b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; (c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and (d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications. 3 figs.

Electrochemical catalyst recovery method

DOEpatents

Silva, Laura J.; Bray, Lane A.

1995-01-01

A method of recovering catalyst material from latent catalyst material solids includes: a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications.

Biomass torrefaction characteristics in inert and oxidative atmospheres at various superficial velocities.

PubMed

Chen, Wei-Hsin; Lu, Ke-Miao; Liu, Shih-Hsien; Tsai, Chi-Ming; Lee, Wen-Jhy; Lin, Ta-Chang

2013-10-01

The reaction characteristics of four biomass materials (i.e. oil palm fiber, coconut fiber, eucalyptus, and Cryptomeria japonica) with non-oxidative and oxidative torrefaction at various superficial velocities are investigated where nitrogen and air are used as carrier gases. Three torrefaction temperatures of 250, 300, and 350 °C are considered. At a given temperature, the solid yield of biomass is not affected by N2 superficial velocity, revealing that the thermal degradation is controlled by heat and mass transfer in biomass. Increasing air superficial velocity decreases the solid yield, especially in oil palm fiber and coconut fiber, implying that the torrefaction reaction of biomass is dominated by surface oxidation. There exists an upper limit of air superficial velocity in the decrement of solid yield, suggesting that beyond this limit the thermal degradation of biomass is no longer governed by surface oxidation, but rather is controlled by internal mass transport. Copyright © 2013 Elsevier Ltd. All rights reserved.

Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

NASA Astrophysics Data System (ADS)

Yamaura, Kazunari

2016-04-01

High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO3, LiOsO3, and Na2OsO4, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal-insulator transition in NaOsO3, a ferroelectric-like transition in LiOsO3, and high-temperature ferrimagnetism driven by a local structural distortion in Ca2FeOsO6 may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices.

A continuum treatment of sliding in Eulerian simulations of solid-solid and solid-fluid interfaces

NASA Astrophysics Data System (ADS)

Subramaniam, Akshay; Ghaisas, Niranjan; Lele, Sanjiva

2017-11-01

A novel treatment of sliding is developed for use in an Eulerian framework for simulating elastic-plastic deformations of solids coupled with fluids. In this method, embedded interfacial boundary conditions for perfect sliding are imposed by enforcing the interface normal to be a principal direction of the Cauchy stress and appropriate consistency conditions ensure correct transmission and reflection of waves at the interface. This sliding treatment may be used either to simulate a solid-solid sliding interface or to incorporate an internal slip boundary condition at a solid-fluid interface. Sliding laws like the Coulomb friction law can also be incorporated with relative ease into this framework. Simulations of sliding interfaces are conducted using a 10th order compact finite difference scheme and a Localized Artificial Diffusivity (LAD) scheme for shock and interface capturing. 1D and 2D simulations are used to assess the accuracy of the sliding treatment. The Richmyer-Meshkov instability between copper and aluminum is simulated with this sliding treatment as a demonstration test case. Support for this work was provided through Grant B612155 from the Lawrence Livermore National Laboratory, US Department of Energy.

Density functional theory study of defect energies and space charge distribution at a solid-oxide electrolyte surface

NASA Astrophysics Data System (ADS)

Han, Chu; Bongiorno, Angelo

2014-03-01

Yttrium-doped barium zirconate (BZY) is a proton conducting electrolyte forming a class of novel materials for new generation of solid oxide fuel cells, for hydrogen separation and purification, and for electrolysis of water. Here we use density functional theory calculations to compute the energy of protons and oxygen vacancies at the surface and in the bulk of lightly Y-doped BZY materials. We found that protons are energetically more stable at the surface termination than in the bulk of BZY by about 1 eV. In contrast, doubly-positively charged oxygen vacancies are found to form iso-energetic defects at both the terminal surface layer and in the bulk of BZY, while in the sub-surface region the defect energy raises by about 1 eV with respect to the value in the bulk. The energetic behavior of protons and oxygen vacancies in the near surface region of BZY is attributed to the competition of strain and electrostatic effects. Lattice model representations of BZY surfaces are then used in combination with Monte Carlo simulations to solve the Poisson-Boltzmann equation and investigate the implication of the results above on the structure of the space charge region at the surface of BZY materials.

High-temperature electrolysis of synthetic seawater using solid oxide electrolyzer cells

NASA Astrophysics Data System (ADS)

Lim, Chee Kuan; Liu, Qinglin; Zhou, Juan; Sun, Qiang; Chan, Siew Hwa

2017-02-01

A Ni-YSZ/YSZ/LSCF-GDC solid oxide electrolyzer cell (SOEC) is used to investigate the effects of seawater electrolysis for hydrogen production through electrolyzing steam produced from simulated seawater bath. Steam electrolysis using an SOEC with its fuel electrode contaminated by sea salt is also investigated. Steam produced from seawater is found to be free of contaminants, which are present in the seawater. Similar electrochemical performance is observed from the polarization curves and impedance spectra when using steam produced from pure water and seawater. Their short-term degradation rates are similar, which are registered at 15% 1000 h-1 for both cases. For the case of direct sea salt contamination in an SOEC's fuel electrode, both the uncontaminated and contaminated cells exhibit rather similar performance as observed from the polarization curves and impedance spectra. The difference in ASR values from the polarization curves and impedance spectra between the uncontaminated and contaminated cell are all within a 10% range. Rather similar short-term degradation rates of 15% 1000 h-1 and 16% 1000 h-1 are recorded for the uncontaminated and contaminated cells, respectively. Post-mortem analysis shows that the sea salt impregnated into the cell has been vaporized at a typical SOEC operating temperature of 800 °C over the period of operation.

Numerical analysis on effect of aspect ratio of planar solid oxide fuel cell fueled with decomposed ammonia

NASA Astrophysics Data System (ADS)

Tan, Wee Choon; Iwai, Hiroshi; Kishimoto, Masashi; Brus, Grzegorz; Szmyd, Janusz S.; Yoshida, Hideo

2018-04-01

Planar solid oxide fuel cells (SOFCs) with decomposed ammonia are numerically studied to investigate the effect of the cell aspect ratio. The ammonia decomposer is assumed to be located next to the SOFCs, and the heat required for the endothermic decomposition reaction is supplied by the thermal radiation from the SOFCs. Cells with aspect ratios (ratios of the streamwise length to the spanwise width) between 0.130 and 7.68 are provided with the reactants at a constant mass flow rate. A parametric study is conducted by varying the cell temperature and fuel utility factor to investigate their effects on the cell performance in terms of the voltage efficiency. The effect of the heat supply to the ammonia decomposer is also studied. The developed model shows good agreement, in terms of the current-voltage curve, with the experimental data obtained from a short stack without parameter tuning. The simulation study reveals that the cell with the highest aspect ratio achieves the highest performance under furnace operation. On the other hand, the 0.750 aspect ratio cell with the highest voltage efficiency of 0.67 is capable of thermally sustaining the ammonia decomposers at a fuel utility of 0.80 using the thermal radiation from both sidewalls.

Anode regeneration following carbon depositions in an industrial-sized anode supported solid oxide fuel cell operating on synthetic diesel reformate

NASA Astrophysics Data System (ADS)

Subotić, Vanja; Schluckner, Christoph; Mathe, Jörg; Rechberger, Jürgen; Schroettner, Hartmuth; Hochenauer, Christoph

2015-11-01

Carbon deposition is a primary concern during operation of solid oxide fuel cells (SOFCs) fueled with carbon-containing fuels. It leads to cell degradation and thus reduces SOFC sustained operation and durability. This paper reports on an experimental investigation of carbon formation on the nickel/yttria-stabilized zirconia (Ni/YSZ) anode of an anode-supported SOFC and its regeneration. The cell was fueled with a synthetically produced diesel reformate to investigate and simulate the cell behavior under real operating conditions. For this purpose the cell was operated under load to determine the critical operating time. Rapid carbon generation, such as at open circuit voltage (OCV), can be prevented when the cell is under load. Carbon depositions were detected using scanning electron microscopy (SEM) and further analyzed by Raman spectroscopy. Industrial-size cells suitable for commercial applications were studied. This study proves the reversibility of carbon formation and the reproducibility of the regeneration process. It shows that carbon formations can be recognized and effectively, fully and cell-protecting regenerated. It indicates the excellent possibility of using SOFCs in the automotive industry as an auxiliary power unit (APU) or combined power-heat unit, operated with diesel reformate, without danger from cell degradation caused by carbon-containing fuels.

Kinetics of (reversible) internal reforming of methane in solid oxide fuel cells under stationary and APU conditions

NASA Astrophysics Data System (ADS)

Timmermann, H.; Sawady, W.; Reimert, R.; Ivers-Tiffée, E.

The internal reforming of methane in a solid oxide fuel cell (SOFC) is investigated and modeled for flow conditions relevant to operation. To this end, measurements are performed on anode-supported cells (ASC), thereby varying gas composition (y CO = 4-15%, yH2 = 5 - 17 % , yCO2 = 6 - 18 % , yH2O = 2 - 30 % , yCH4 = 0.1 - 20 %) and temperature (600-850 °C). In this way, operating conditions for both stationary applications (methane-rich pre-reformate) as well as for auxiliary power unit (APU) applications (diesel-POX reformate) are represented. The reforming reaction is monitored in five different positions alongside the anodic gas channel by means of gas chromatography. It is shown that methane is converted in the flow field for methane-rich gas compositions, whereas under operation with diesel reformate the direction of the reaction is reversed for temperatures below 675 °C, i.e. (exothermic) methanation occurs along the anode. Using a reaction model, a rate equation for reforming could be derived which is also valid in the case of methanation. By introducing this equation into the reaction model the methane conversion along a catalytically active Ni-YSZ cermet SOFC anode can be simulated for the operating conditions specified above.

Performance and economic assessments of a solid oxide fuel cell system with a two-step ethanol-steam-reforming process using CaO sorbent

NASA Astrophysics Data System (ADS)

Tippawan, Phanicha; Arpornwichanop, Amornchai

2016-02-01

The hydrogen production process is known to be important to a fuel cell system. In this study, a carbon-free hydrogen production process is proposed by using a two-step ethanol-steam-reforming procedure, which consists of ethanol dehydrogenation and steam reforming, as a fuel processor in the solid oxide fuel cell (SOFC) system. An addition of CaO in the reformer for CO2 capture is also considered to enhance the hydrogen production. The performance of the SOFC system is analyzed under thermally self-sufficient conditions in terms of the technical and economic aspects. The simulation results show that the two-step reforming process can be run in the operating window without carbon formation. The addition of CaO in the steam reformer, which runs at a steam-to-ethanol ratio of 5, temperature of 900 K and atmospheric pressure, minimizes the presence of CO2; 93% CO2 is removed from the steam-reforming environment. This factor causes an increase in the SOFC power density of 6.62%. Although the economic analysis shows that the proposed fuel processor provides a higher capital cost, it offers a reducing active area of the SOFC stack and the most favorable process economics in term of net cost saving.

Reforming results of a novel radial reactor for a solid oxide fuel cell system with anode off-gas recirculation

NASA Astrophysics Data System (ADS)

Bosch, Timo; Carré, Maxime; Heinzel, Angelika; Steffen, Michael; Lapicque, François

2017-12-01

A novel reactor of a natural gas (NG) fueled, 1 kW net power solid oxide fuel cell (SOFC) system with anode off-gas recirculation (AOGR) is experimentally investigated. The reactor operates as pre-reformer, is of the type radial reactor with centrifugal z-flow, has the shape of a hollow cylinder with a volume of approximately 1 L and is equipped with two different precious metal wire-mesh catalyst packages as well as with an internal electric heater. Reforming investigations of the reactor are done stand-alone but as if the reactor would operate within the total SOFC system with AOGR. For the tests presented here it is assumed that the SOFC system runs on pure CH4 instead of NG. The manuscript focuses on the various phases of reactor operation during the startup process of the SOFC system. Startup process reforming experiments cover reactor operation points at which it runs on an oxygen to carbon ratio at the reactor inlet (ϕRI) of 1.2 with air supplied, up to a ϕRI of 2.4 without air supplied. As confirmed by a Monte Carlo simulation, most of the measured outlet gas concentrations are in or close to equilibrium.

Effects of sol-gel synthesis on 5Fe-15Mn-40Zn-40Ti-O mixed oxide structure and its H2S removal efficiency from industrial gas streams.

PubMed

Polychronopoulou, Kyriaki; Efstathiou, Angelos M

2009-06-15

A novel Fe-Mn-Zn-Ti-O mixed metal oxide has been developed for efficient low-temperature (25-50 degrees C) removal of H2S from a gas mixture containing 600 ppm H2S, 25 vol% H2, 7.5 vol % CO2, and 1-3 vol% H2O that simulates typical conditions experienced at the outlet of a bioreactor loaded with sulfate metal reducing bacteria (SMRB) that converts toxic Cr6+ and As5+ present in ground and surface waters and soils into nontoxic elements. During the latter conversion H2S gas is produced and has to be treated. In the present work it is demonstrated for the first time that by using the sol-gel synthesis route at given experimental conditions (e.g., metal precursor salts, solvent system, and solution pH), optimum structural properties for the Fe-Mn-Zn-Ti-O solid can be obtained for maximization of H2S uptake. In particular, at 25 degrees C an H2S uptake (0.085 g H2S/g solid) larger by at least a factor of 3 compared to a commercial Ni-based H2S absorbent material was obtained.

On controllability and system constraints of the linear models of proton exchange membrane and solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Radisavljevic, Verica

2011-10-01

In this paper we first show that the linear models of proton exchange membrane (polymer electrolyte membrane, PEM) and solid oxide (SO) fuel cells, commonly used in power and energy literature, are not controllable. The source of uncontrollability is the equation for pressure of the water vapor that is only affected by the fuel cell current, which in fact is a disturbance in this system and cannot be controlled by the given model inputs: inlet molar flow rates of hydrogen and oxygen. Being uncontrollable these models are not good candidates for studying control of dynamic processes in PEM and SO fuel cells. However, due to their simplicity, they can be used in hybrid configurations with other energy producing devices such as photovoltaic (solar) cells, wind turbine, micro gas turbine, battery (ultra capacitor) to demonstrate some other phenomena, but not for control purposes unless the hybrid models formed in such hybrid configurations are controllable. Testing controllability of such hybrid models is mandatory. Secondly, we introduce some algebraic constraints that follow from the model dynamics and the Nernst open-loop fuel cell voltage formula. These constraints must be satisfied in simulation of considered fuel cell modes, for example, via MATLAB/Simulink or any other computer software package.

Robust adaptive control for a hybrid solid oxide fuel cell system

NASA Astrophysics Data System (ADS)

Snyder, Steven

2011-12-01

Solid oxide fuel cells (SOFCs) are electrochemical energy conversion devices. They offer a number of advantages beyond those of most other fuel cells due to their high operating temperature (800-1000°C), such as internal reforming, heat as a byproduct, and faster reaction kinetics without precious metal catalysts. Mitigating fuel starvation and improving load-following capabilities of SOFC systems are conflicting control objectives. However, this can be resolved by the hybridization of the system with an energy storage device, such as an ultra-capacitor. In this thesis, a steady-state property of the SOFC is combined with an input-shaping method in order to address the issue of fuel starvation. Simultaneously, an overall adaptive system control strategy is employed to manage the energy sharing between the elements as well as to maintain the state-of-charge of the energy storage device. The adaptive control method is robust to errors in the fuel cell's fuel supply system and guarantees that the fuel cell current and ultra-capacitor state-of-charge approach their target values and remain uniformly, ultimately bounded about these target values. Parameter saturation is employed to guarantee boundedness of the parameters. The controller is validated through hardware-in-the-loop experiments as well as computer simulations.

A non-Fourier approach towards the analysis of heat transfer enhancement with water based nanofluids through a channel

NASA Astrophysics Data System (ADS)

Dil, Taimoor; Khan, M. Sabeel

2018-05-01

In this article, a non-Fourier approach to model the heat transfer phenomenon in nanofluids having application to automotive industry is studied. In this respect, a recently proposed hyperbolic heat flux equation is embedded into the heat energy equation and thereby incorporating the effect of thermal relaxation time. Nanofluids are formed by considering copper oxide (CuO), Titanium dioxide (TiO2) and Aluminum oxide (Al2O3) nano-solid particles in the base fluid. The flow governing system of PDEs along with boundary conditions is transformed into its respective coupled system of nonlinear ODEs using suitable similarity functions. Runge-Kutta-Fehlberg (RK-5) numerical scheme embedded with shooting method is implemented and used to solve the obtained boundary value problem. Numerical simulations are performed and tabulated to analyze the influence of solid volume fraction on local coefficient of skin-friction and Nusselt number. A comparison is made between the results by Fourier and present heat flux model. We conclude that the presented new approach is more general and thus allows predicting the influence of thermal relaxation time on the heat transfer characteristics. Moreover, consideration of present model over the Fourier model helps to predict the actual temporal behavior of solution.

On-line experimental validation of a model-based diagnostic algorithm dedicated to a solid oxide fuel cell system

NASA Astrophysics Data System (ADS)

Polverino, Pierpaolo; Esposito, Angelo; Pianese, Cesare; Ludwig, Bastian; Iwanschitz, Boris; Mai, Andreas

2016-02-01

In the current energetic scenario, Solid Oxide Fuel Cells (SOFCs) exhibit appealing features which make them suitable for environmental-friendly power production, especially for stationary applications. An example is represented by micro-combined heat and power (μ-CHP) generation units based on SOFC stacks, which are able to produce electric and thermal power with high efficiency and low pollutant and greenhouse gases emissions. However, the main limitations to their diffusion into the mass market consist in high maintenance and production costs and short lifetime. To improve these aspects, the current research activity focuses on the development of robust and generalizable diagnostic techniques, aimed at detecting and isolating faults within the entire system (i.e. SOFC stack and balance of plant). Coupled with appropriate recovery strategies, diagnosis can prevent undesired system shutdowns during faulty conditions, with consequent lifetime increase and maintenance costs reduction. This paper deals with the on-line experimental validation of a model-based diagnostic algorithm applied to a pre-commercial SOFC system. The proposed algorithm exploits a Fault Signature Matrix based on a Fault Tree Analysis and improved through fault simulations. The algorithm is characterized on the considered system and it is validated by means of experimental induction of faulty states in controlled conditions.

Process for forming a homogeneous oxide solid phase of catalytically active material

DOEpatents

Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

1995-01-01

A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

Modeling and sensitivity analysis on the transport of aluminum oxide nanoparticles in saturated sand: effects of ionic strength, flow rate, and nanoparticle concentration.

PubMed

Rahman, Tanzina; Millwater, Harry; Shipley, Heather J

2014-11-15

Aluminum oxide nanoparticles have been widely used in various consumer products and there are growing concerns regarding their exposure in the environment. This study deals with the modeling, sensitivity analysis and uncertainty quantification of one-dimensional transport of nano-sized (~82 nm) aluminum oxide particles in saturated sand. The transport of aluminum oxide nanoparticles was modeled using a two-kinetic-site model with a blocking function. The modeling was done at different ionic strengths, flow rates, and nanoparticle concentrations. The two sites representing fast and slow attachments along with a blocking term yielded good agreement with the experimental results from the column studies of aluminum oxide nanoparticles. The same model was used to simulate breakthrough curves under different conditions using experimental data and calculated 95% confidence bounds of the generated breakthroughs. The sensitivity analysis results showed that slow attachment was the most sensitive parameter for high influent concentrations (e.g. 150 mg/L Al2O3) and the maximum solid phase retention capacity (related to blocking function) was the most sensitive parameter for low concentrations (e.g. 50 mg/L Al2O3). Copyright © 2014 Elsevier B.V. All rights reserved.

Sulfur Dioxide Capture by Heterogeneous Oxidation on Hydroxylated Manganese Dioxide.

PubMed

Wu, Haodong; Cai, Weimin; Long, Mingce; Wang, Hairui; Wang, Zhiping; Chen, Chen; Hu, Xiaofang; Yu, Xiaojuan

2016-06-07

Here we demonstrate that sulfur dioxide (SO2) is efficiently captured via heterogeneous oxidation into sulfate on the surface of hydroxylated manganese dioxide (MnO2). Lab-scale activity tests in a fluidized bed reactor showed that the removal efficiency for a simulated flue gas containing 5000 mg·Nm(-3) SO2 could reach nearly 100% with a GHSV (gas hourly space velocity) of 10000 h(-1). The mechanism was investigated using a combination of experimental characterizations and theoretical calculations. It was found that formation of surface bound sulfate proceeds via association of SO2 with terminal hydroxyls. Both H2O and O2 are essential for the generation of reactive terminal hydroxyls, and the indirect role of O2 in heterogeneous SO2 oxidation at low temperature was also revealed. We propose that the high reactivity of terminal hydroxyls is attributed to the proper surface configuration of MnO2 to adsorb water with degenerate energies for associative and dissociative states, and maintain rapid proton dynamics. Viability analyses suggest that the desulfurization method that is based on such a direct oxidation reaction at the gas/solid interface represents a promising approach for SO2 capture.

Synthesis and photocatalytic property of Zinc Oxide (ZnO) fine particle using flame spray pyrolysis method

NASA Astrophysics Data System (ADS)

Widiyandari, Hendri; Ayu Ketut Umiati, Ngurah; Dwi Herdianti, Rizki

2018-05-01

Advance oxidation process (AOP) using photocatalysis constitute a promising technology for the treatment of wastewaters containing non-easily removable organic compound. Zinc oxide (ZnO) is one of efficient photocatalyst materials. This research reported synthesis of ZnO fine particle from zinc nitrate hexahydrate using Flame Spray Pyrolysis (FSP) method. In this method, oxygen (O2) gas were used as oxidizer and LPG (liquid petroleum gas) were used as fuel. The effect of O2 gas flow rate during ZnO particle fabrication to the microstructure, optical and photocatalytic properties were systematically discussed. The photocatalytic activity of ZnO was tested for the degradation of amaranth dye with initial concentration of 10 ppm under irradiation of solar simulator. The rate of decrease in amaranth concentration was measured using UV-Visible spectrophotometer. The ZnO synthesized using FSP has a hexagonal crystalline structure. Scanning electron microscope images showed that ZnO has a spherical formed which was the mixture of solid and hollow particles. The optimum condition for amaranth degradation was shown by ZnO produced at a flow rate of 1.5 L/min which able to degrade amaranth dye up to 95,3 % at 75 minutes irradiation.

Solid oxide fuel cell generator

DOEpatents

Di Croce, A. Michael; Draper, Robert

1993-11-02

A solid oxide fuel cell generator has a plenum containing at least two rows of spaced apart, annular, axially elongated fuel cells. An electrical conductor extending between adjacent rows of fuel cells connects the fuel cells of one row in parallel with each other and in series with the fuel cells of the adjacent row.

Design of Hybrid Solid Polymer Electrolytes: Structure and Properties

NASA Technical Reports Server (NTRS)

Bronstein, Lyudmila M.; Karlinsey, Robert L.; Ritter, Kyle; Joo, Chan Gyu; Stein, Barry; Zwanziger, Josef W.

2003-01-01

This paper reports synthesis, structure, and properties of novel hybrid solid polymer electrolytes (SPE's) consisting of organically modified aluminosilica (OM-ALSi), formed within a poly(ethylene oxide)-in-salt (Li triflate) phase. To alter the structure and properties we fused functionalized silanes containing poly(ethylene oxide) (PEO) tails or CN groups.

Program of scientific investigations and development of solid-oxide fuel cells (SOFC) in VNIITF. Proposals on scientific and technical collaboration and SOFC commercialization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kleschev, Yu.N.; Chukharev, V.F.

1996-04-01

This paper describes proposals on scientific and technical collaborations pertaining to solid oxide fuel cell commercialization. Topics included for discussion are: materials research and manufacture; market estimation and cost; directions of collaboration; and project of proposals on joint enterprise creation.

Review of Fuel Cell Technologies for Military Land Vehicles

DTIC Science & Technology

2014-09-01

fuel cell technologies for APUs are Proton Exchange Membrane Fuel Cells ( PEMFC ), direct methanol fuel cells and Solid Oxide Fuel Cells (SOFC). The...6 4.2 Proton Exchange Membrane Fuel Cells ( PEMFC ...OEM Original Equipment Manufacturer PEM Proton Exchange Membrane PEMFC Proton Exchange Membrane Fuel Cell SOFC Solid Oxide Fuel Cell TRL Technical

Formation of Green Rust and Immobilization of Nickel in Response to Bacterial Reduction of Hydrous Ferric Oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parmar, N.; Gorby, Yuri A.; Beveridge, Terrance J.

This investigation documents the formation of Green Rust (GR) and immobilization of Ni2+ in response to bacterial reduction of hydrous ferric oxide (HFO) reduction experiments provided evidence that the solid-phase partitioning of Ni2+ in GR extended from equilibrium solid-solution behavior.

Solid oxide fuel cell generator

DOEpatents

Di Croce, A.M.; Draper, R.

1993-11-02

A solid oxide fuel cell generator has a plenum containing at least two rows of spaced apart, annular, axially elongated fuel cells. An electrical conductor extending between adjacent rows of fuel cells connects the fuel cells of one row in parallel with each other and in series with the fuel cells of the adjacent row. 5 figures.

Robust, functional nanocrystal solids by infilling with atomic layer deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yao; Gibbs, Markelle; Perkins, Craig L.

2011-12-14

Thin films of colloidal semiconductor nanocrystals (NCs) are inherently metatstable materials prone to oxidative and photothermal degradation driven by their large surface-to-volume ratios and high surface energies. The fabrication of practical electronic devices based on NC solids hinges on preventing oxidation, surface diffusion, ripening, sintering, and other unwanted physicochemical changes that can plague these materials. Here we use low-temperature atomic layer deposition (ALD) to infill conductive PbSe NC solids with metal oxides to produce inorganic nanocomposites in which the NCs are locked in place and protected against oxidative and photothermal damage. Infilling NC field-effect transistors and solar cells with amorphousmore » alumina yields devices that operate with enhanced and stable performance for at least months in air. Furthermore, ALD infilling with ZnO lowers the height of the inter-NC tunnel barrier for electron transport, yielding PbSe NC films with electron mobilities of 1 cm² V -1 s -1. Our ALD technique is a versatile means to fabricate robust NC solids for optoelectronic devices.« less

Hybrid Solid Oxide Fuel Cell/Gas Turbine System Design for High Altitude Long Endurance Aerospace Missions

NASA Technical Reports Server (NTRS)

Himansu, Ananda; Freeh, Joshua E.; Steffen, Christopher J., Jr.; Tornabene, Robert T.; Wang, Xiao-Yen J.

2006-01-01

A system level analysis, inclusive of mass, is carried out for a cryogenic hydrogen fueled hybrid solid oxide fuel cell and bottoming gas turbine (SOFC/GT) power system. The system is designed to provide primary or secondary electrical power for an unmanned aerial vehicle (UAV) over a high altitude, long endurance mission. The net power level and altitude are parametrically varied to examine their effect on total system mass. Some of the more important technology parameters, including turbomachinery efficiencies and the SOFC area specific resistance, are also studied for their effect on total system mass. Finally, two different solid oxide cell designs are compared to show the importance of the individual solid oxide cell design on the overall system. We show that for long mission durations of 10 days or more, the fuel mass savings resulting from the high efficiency of a SOFC/GT system more than offset the larger powerplant mass resulting from the low specific power of the SOFC/GT system. These missions therefore favor high efficiency, low power density systems, characteristics typical of fuel cell systems in general.

Method and apparatus for assembling solid oxide fuel cells

DOEpatents

Szreders, B.E.; Campanella, N.

1988-05-11

This invention relates generally to solid oxide fuel power generators and is particularly directed to improvements in the assembly and coupling of solid oxide fuel cell modules. A plurality of jet air tubes are supported and maintained in a spaced matrix array by a positioning/insertion assembly for insertion in respective tubes of a solid oxide fuel cell (SOFC) in the assembly of an SOFC module. The positioning/insertion assembly includes a plurality of generally planar, elongated, linear vanes which are pivotally mounted at each end thereof to a support frame. A rectangular compression assembly of adjustable size is adapted to receive and squeeze a matrix of SOFC tubes so as to compress the inter-tube nickel felt conductive pads which provide series/parallel electrical connection between adjacent SOFCs, with a series of increasingly larger retainer frames used to maintain larger matrices of SOFC tubes in position. Expansion of the SOFC module housing at the high operating temperatures of the SOFC is accommodated by conductive, flexible, resilient expansion, connector bars which provide support and electrical coupling at the top and bottom of the SOFC module housing. 17 figs.

Charging a Li-O₂ battery using a redox mediator.

PubMed

Chen, Yuhui; Freunberger, Stefan A; Peng, Zhangquan; Fontaine, Olivier; Bruce, Peter G

2013-06-01

The non-aqueous Li-air (O2) battery is receiving intense interest because its theoretical specific energy exceeds that of Li-ion batteries. Recharging the Li-O2 battery depends on oxidizing solid lithium peroxide (Li2O2), which is formed on discharge within the porous cathode. However, transporting charge between Li2O2 particles and the solid electrode surface is at best very difficult and leads to voltage polarization on charging, even at modest rates. This is a significant problem facing the non-aqueous Li-O2 battery. Here we show that incorporation of a redox mediator, tetrathiafulvalene (TTF), enables recharging at rates that are impossible for the cell in the absence of the mediator. On charging, TTF is oxidized to TTF(+) at the cathode surface; TTF(+) in turn oxidizes the solid Li2O2, which results in the regeneration of TTF. The mediator acts as an electron-hole transfer agent that permits efficient oxidation of solid Li2O2. The cell with the mediator demonstrated 100 charge/discharge cycles.

Lowering the temperature of solid oxide fuel cells.

PubMed

Wachsman, Eric D; Lee, Kang Taek

2011-11-18

Fuel cells are uniquely capable of overcoming combustion efficiency limitations (e.g., the Carnot cycle). However, the linking of fuel cells (an energy conversion device) and hydrogen (an energy carrier) has emphasized investment in proton-exchange membrane fuel cells as part of a larger hydrogen economy and thus relegated fuel cells to a future technology. In contrast, solid oxide fuel cells are capable of operating on conventional fuels (as well as hydrogen) today. The main issue for solid oxide fuel cells is high operating temperature (about 800°C) and the resulting materials and cost limitations and operating complexities (e.g., thermal cycling). Recent solid oxide fuel cells results have demonstrated extremely high power densities of about 2 watts per square centimeter at 650°C along with flexible fueling, thus enabling higher efficiency within the current fuel infrastructure. Newly developed, high-conductivity electrolytes and nanostructured electrode designs provide a path for further performance improvement at much lower temperatures, down to ~350°C, thus providing opportunity to transform the way we convert and store energy.

Rapid, cool sintering of wet processed yttria-stabilized zirconia ceramic electrolyte thin films.

PubMed

Park, Jun-Sik; Kim, Dug-Joong; Chung, Wan-Ho; Lim, Yonghyun; Kim, Hak-Sung; Kim, Young-Beom

2017-09-29

Here we report a photonic annealing process for yttria-stabilized zirconia films, which are one of the most well-known solid-state electrolytes for solid oxide fuel cells (SOFCs). Precursor films were coated using a wet-chemical method with a simple metal-organic precursor solution and directly annealed at standard pressure and temperature by two cycles of xenon flash lamp irradiation. The residual organics were almost completely decomposed in the first pre-annealing step, and the fluorite crystalline phases and good ionic conductivity were developed during the second annealing step. These films showed properties comparable to those of thermally annealed films. This process is much faster than conventional annealing processes (e.g. halogen furnaces); a few seconds compared to tens of hours, respectively. The significance of this work includes the treatment of solid-state electrolyte oxides for SOFCs and the demonstration of the feasibility of other oxide components for solid-state energy devices.

In situ remediation process using divalent metal cations

DOEpatents

Brady, Patrick V.; Khandaker, Nadim R.; Krumhansl, James L.; Teter, David M.

2004-12-14

An in situ process for treating ambient solid materials (e.g., soils, aquifer solids, sludges) by adding one or more divalent metal cations to the ambient solid material. The added divalent metal cations, such as Cu.sup.2+ or Zn.sup.2+, combine with metal oxide/hydroxides (e.g., ferric oxide/hydroxide or aluminum oxide/hydroxide) already present in the ambient solid material to form an effective sorbent material having a large number of positively-charged surface complexes that binds and immobilizes anionic contaminant species (e.g., arsenic or chromate). Divalent metal cations can be added, for example, by injecting an aqueous solution of CuSO.sub.4 into an aquifer contaminated with arsenic or chromate. Also, sludges can be stabilized against leaching of anionic contaminants through the addition of divalent metal cations. Also, an inexpensive sorbent material can be easily formed by mixing divalent metal cations with soil that has been removed from the ground.

Experimental insights into organic carbon oxidation potential during fluvial transport without floodplain storage

NASA Astrophysics Data System (ADS)

Scheingross, J. S.; Hovius, N.; Sachse, D.; Vieth-Hillebrand, A.; Turowski, J. M.; Hilton, R. G.

2016-12-01

Over geologic timescales, the exchange of organic carbon (OC) between the atmosphere, rock, and biosphere is thought to be a major control on global climate. CO2 flux estimates from oxidation of rock-derived OC and sequestration of biospheric OC during fluvial transit from source to sink are approximately the same order of magnitude or larger than those from silicate weathering. Despite field data showing loss of OC moving downstream in lowland rivers, it is unclear if losses occur primarily during active fluvial transport within the river, where OC is in continual motion within an aerated environment, or during longer periods when OC is temporarily stored in river floodplains which may be anoxic. This represents a major knowledge gap, as the unknown location of OC oxidation (i.e., river vs. floodplain) limits our ability to develop process-based models that can be employed to predict OC losses, constrain carbon budgets, and unravel links between climate, tectonics, and erosion. To fill this gap, we investigated the potential for OC oxidation in laboratory experiments simulating fluvial transport without floodplain storage. Mixtures of OC-rich and siliciclastic sediment were transported for distances of 2000 km in annular flumes while making time-series measurements of sediment TOC and water DOC concentrations. Initial results for transport of OC-rich soil show increasing DOC with transport distance to levels that represent a transfer of 2% of the total OC from the solid to the dissolved phase; however, we observed no detectable change in the solid-phase TOC. Similar results were obtained in a control experiment with identical sediment in still water. These preliminary results suggest minimal OC oxidation within our experiment, and, to the extent that such experiments represent natural transport through river systems, are consistent with the hypothesis that OC losses may occur primarily during floodplain storage rather than fluvial transport.

Atomistic study of ternary oxides as high-temperature solid lubricants

NASA Astrophysics Data System (ADS)

Gao, Hongyu

Friction and wear are important tribological phenomena tightly associated with the performance of tribological components/systems such as bearings and cutting machines. In the process of contact and sliding, friction and wear lead to energy loss, and high friction and wear typically result in shortened service lifetime. To reduce friction and wear, solid lubricants are generally used under conditions where traditional liquid lubricants cannot be applied. However, it is challenging to maintain the functionality of those materials when the working environment becomes severe. For instance, at elevated temperatures (i.e., above 400 °C), most traditional solid lubricants, such as MoS2 and graphite, will easily oxidize or lose lubricity due to irreversible chemical changes. For such conditions, it is necessary to identify materials that can remain thermally stable as well as lubricious over a wide range of temperatures. Among the currently available high-temperature solid lubricants, Ag-based ternary metal oxides have recently drawn attention due to their low friction and ability to resist oxidation. A recent experimental study showed that the Ag-Ta-O ternary exhibited an extremely low coefficient of friction (0.06) at 750 °C. To fully uncover the lubricious nature of this material as a high-temperature solid lubricant, a series of tribological investigations were carried out based on one promising candidate - silver tantalate (AgTaO3). The study was then extended to alternative materials, Cu-Ta-O ternaries, to accommodate a variety of application requirements. We aimed to understand, at an atomic level, the effects of physical and chemical properties on the thermal, mechanical and tribological behavior of these materials at high temperatures. Furthermore, we investigated potassium chloride films on a clean iron surface as a representative boundary lubricating system in a nonextreme environment. This investigation complemented the study of Ag/Cu-Ta-O and enhanced the understanding of lubricious mechanisms of solid lubricants in general. Molecular dynamics (MD) simulations was used as the primary tool in this research, complemented by density-functional theory and experiments from our colleagues. In this research, we first developed empirical potential parameters for AgTaO3 and later Cu- Ta-O ternaries using the modified embedded-atom method (MEAM) formalism. With those parameters, we explored the sliding mechanisms of AgTaO3, CuTaO3 and CuTa2O6 at elevated temperatures. Particularly on AgTaO3, we investigated the effects of applied loads as well as surface terminations on friction and wear as functions of temperature. In addition, to optimize the tribological performance of AgTaO3, film reconstruction mechanisms were investigated on Ta2O5/Ag films with varying amounts of Ag. For the potassium chloride-iron system, we studied the effect of contact pressure on interfacial structure, based on which the origin of the commonly observed pressure-dependent shear strengths was explored. We hope this research will benefit the design and development of solid lubricant materials for a wide range of applications.

PEP Run Report for Integrated Test A, Caustic Leaching in UFP-VSL-T01A, Oxidative Leaching in UFP-VSL-T02A

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guzman-Leong, Consuelo E.; Bredt, Ofelia P.; Burns, Carolyn A.

2009-12-04

Pacific Northwest National Laboratory (PNNL) was tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed and constructed and operated as part of a plan to respond to issue M12, “Undemonstrated Leaching Processes.”(a) The PEP, located in the Process Engineering Laboratory-West (PDLW) located in Richland, Washington, is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes.more » The PEP replicates the WTP leaching processes using prototypic equipment and control strategies. The PEP also includes non-prototypic ancillary equipment to support the core processing.« less

Local structure analysis on (La,Ba)(Ga,Mg)O3-δ by the pair distribution function method using a neutron source and density functional theory calculations

NASA Astrophysics Data System (ADS)

Kitamura, Naoto; Vogel, Sven C.; Idemoto, Yasushi

2013-06-01

In this work, we focused on La0.95Ba0.05Ga0.8Mg0.2O3-δ with the perovskite structure, and investigated the local structure around the oxygen vacancy by pair distribution function (PDF) method and density functional theory (DFT) calculation. By comparing the G(r) simulated based on the DFT calculation and the experimentally-observed G(r), it was suggested that the oxygen vacancy was trapped by Ba2+ at the La3+ site at least at room temperature. Such a defect association may be one of the reasons why the La0.95Ba0.05Ga0.8Mg0.2O3-δ showed lower oxide-ion conductivity than (La,Sr)(Ga,Mg)O3-δ which was widely-used as an electrolyte of the solid oxide fuel cell.

Oscillations in the permanganate oxidation of glycine in a stirred flow reactor.

PubMed

Poros, Eszter; Kurin-Csörgei, Krisztina; Szalai, István; Orbán, Miklós

2013-09-19

Oscillatory behavior is reported in the permanganate oxidation of glycine in the presence of Na2HPO4 in a stirred flow reactor. In near-neutral solutions, long-period sustained oscillations were recorded in the potential of a Pt electrode and in the light absorbance measured at λ = 418 and 545 nm, characteristic wavelengths for following the evolution of the intermediate [Mn(IV)] and reagent [MnO4(-) ] during the course of the reaction. No evidence of bistability was found. The chemical and physical backgrounds of the oscillatory phenomenon are discussed. In the oscillatory cycle, the positive feedback is attributed to the autocatalytic formation of a soluble Mn(IV) species, whereas the negative feedback arises from its removal from the solution in the form of solid MnO2. A simple model is suggested that qualitatively simulates the experimental observations in batch runs and the dynamics that appears in the flow system.

The main directions in technology investigation of soid oxide fuel cell in Russian Federal Research Center Institute of Physics & Power Engineering (IPPE)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ievleva, J.I.; Kolesnikov, V.P.; Mezhertisky, G.S.

1996-04-01

The main direction of science investigations for creation of efficient solid oxide fuel cells (SOFC) in IPPE are considered in this work. The development program of planar SOFC with thin-film electrolyte is shown. General design schemes of experimental SOFC units are presented. The flow design schemes of processes for initial materials and electrodes fabrication are shown. The results of investigations for creation thin-film solid oxide electrolyte at porous cathode by magnetron sputtering from complex metal target in oxidative environment are presented.

Effects of chemical composition of fly ash on efficiency of metal separation in ash-melting of municipal solid waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okada, Takashi, E-mail: t-okada@u-fukui.ac.jp; Tomikawa, Hiroki

2013-03-15

Highlights: ► Separation of Pb and Zn from Fe and Cu in ash-melting of municipal solid waste. ► Molar ratio of Cl to Na and K in fly ash affected the metal-separation efficiency. ► The low molar ratio and a non-oxidative atmosphere were better for the separation. - Abstract: In the process of metal separation by ash-melting, Fe and Cu in the incineration residue remain in the melting furnace as molten metal, whereas Pb and Zn in the residue are volatilized. This study investigated the effects of the chemical composition of incineration fly ash on the metal-separation efficiency of themore » ash-melting process. Incineration fly ash with different chemical compositions was melted with bottom ash in a lab-scale reactor, and the efficiency with which Pb and Zn were volatilized preventing the volatilization of Fe and Cu was evaluated. In addition, the behavior of these metals was simulated by thermodynamic equilibrium calculations. Depending on the exhaust gas treatment system used in the incinerator, the relationships among Na, K, and Cl concentrations in the incineration fly ash differed, which affected the efficiency of the metal separation. The amounts of Fe and Cu volatilized decreased by the decrease in the molar ratio of Cl to Na and K in the ash, promoting metal separation. The thermodynamic simulation predicted that the chlorination volatilization of Fe and Cu was prevented by the decrease in the molar ratio, as mentioned before. By melting incineration fly ash with the low molar ratio in a non-oxidative atmosphere, most of the Pb and Zn in the ash were volatilized leaving behind Fe and Cu.« less

Ion plasma deposition of oxide films with graded-stoichiometry composition: Experiment and simulation

NASA Astrophysics Data System (ADS)

Volpyas, V. A.; Tumarkin, A. V.; Mikhailov, A. K.; Kozyrev, A. B.; Platonov, R. A.

2016-07-01

A method of ion plasma deposition is proposed for obtaining thin multicomponent films with continuously graded composition in depth of the film. The desired composition-depth profile is obtained by varying the working gas pressure during deposition in the presence of an additional adsorbing screen in the drift space between a sputtered target and substrate. Efficiency of the proposed method is confirmed by Monte Carlo simulation of the deposition of thin films of Ba x Sr1- x TiO3 (BSTO) solid solution. It is demonstrated that, during sputtering of a Ba0.3Sr0.7TiO3 target, the parameter of composition stoichiometry in the growing BSTO film varies in the interval of x = 0.3-0.65 when the gas pressure is changed within 2-60 Pa.

Polymethylmethacrylate combustion in a narrow channel apparatus simulating a microgravity environment

NASA Astrophysics Data System (ADS)

Bornand, Garrett Randall

Fire safety is an important part of engineering when human lives are at stake. From everyday homes to spacecraft that can cost hundreds of millions of dollars. The research in this thesis attempts to provide scientific evidence that the apparatus in question successfully simulates microgravity and can possibly replace NASA's current test method for spacecraft fire safety. Flame spread tests were conducted with thermally thick and thermally thin polymethylmethacrylate (PMMA) samples to study flame spread behavior in response to environmental changes. The tests were conducted using the San Diego State University Narrow Channel Apparatus (SDSU NCA) as well as within the Microgravity Science Glovebox (MSG) on the International Space Station (ISS). The SDSU NCA can suppress buoyant flow in horizontally spreading flames, and is currently being investigated as a possible replacement or complement to NASA's current material flammability test standard for non-metallic solids, NASA-STD-(I)-6001B Test 1. The buoyant suppression attained in the NCA allows tests to be conducted in a simulated microgravity environment-a characteristic that NASA's Test 1 lacks since flames present in Test 1 are driven by buoyant flows. The SDSU NCA allows for tests to be conducted at various opposed flow oxidizer velocities, oxygen percent by volume, and total pressure to mimic various spacecraft and habitat atmospheres. Tests were conducted at 1 atm pressure, thin fuel thickness of 50 and 75 microns, thick fuel thickness ranging from 3 mm to 5.6 mm, opposed oxidizer velocity ranging from 10 to 25 cm/s, and oxygen concentration by volume at 21, 30, and 50 percent. The simulated microgravity flame spread results were then compared to true microgravity experiments including; testing conducted on the International Space Station (ISS) under the Burning and Suppression of Solids (BASS) research, NASA's 5.2 second Drop Tower, and Micro-Gravity Laboratory's (MGLAB) 4.5 second Drop Tower. Data was also compared to results found by Michigan State University's NCA. Flame spread results from the SDSU NCA compare closely to that of the other experimental techniques. Additionally, an infrared camera and species concentration sensors were added to the SDSU NCA and initial results are provided. Fire Dynamics Simulator (FDS) was used to model the combustion of PMMA within the SDSU NCA. Both thin and thick fuel beds were simulated and the numerical results were compared to experimental data. The simulation was then used to determine various results that cannot easily be found with experimentation, including how effectively the NCA simulates microgravity under certain environmental conditions, gas and fuel bed temperatures, heat fluxes, species concentrations, pyrolysis rate, and other various data. The simulation was found to give reasonable results and overall flame spread trends, but could be improved upon with further detailed kinetic parameter studies.

Optimized performance of quasi-solid-state DSSC with PEO-bismaleimide polymer blend electrolytes filled with a novel procedure.

PubMed

Lee, Dong Ha; Sun, Kyung Chul; Qadir, Muhammad Bilal; Jeong, Sung Hoon

2014-12-01

Dye-sensitized solar cell (DSSC) is an attractive renewable energy technology currently under intense investigation. Electrolyte plays an important role in the photovoltaic performance of the DSSCs and many efforts have been contributed to study different kinds of electrolytes with various characteristics such as liquid electrolytes, polymer electrolytes and so on. In this study, DSSC is developed by using quasi-solid electrolyte and a novel procedure is adopted for filling this electrolyte. The quasi-solid-state electrolyte was prepared by mixing Poly ethylene oxide (PEO) and bismaleimide together and constitution was taken as PEO (15 wt%) at various bismaleimide concentrations (1, 3, 5 wt%). The novel procedure of filling electrolyte consists of three major steps (first step: filling liquid electrolyte, second step: vaporization of liquid electrolyte, third step: refilling quasi-solid-state electrolyte). The electrochemical and photovoltaic performances of DSSCs with these electrolytes were also investigated. The electrochemical impedance spectroscopy (EIS) indicated that TiO2/Dye/electrolyte impedance is reduced and electron lifetime is increased, and consequently efficiency of cell has been improved after using this novel procedure. The photovoltaic power conversion efficiency of 6.39% has been achieved under AM 1.5 simulated sunlight (100 W/cm2) through this novel procedure and by using specified blend of polymers.

Evaluation of a pointwise microcirculation assessment method using liquid and multilayered tissue simulating phantoms

NASA Astrophysics Data System (ADS)

Fredriksson, Ingemar; Saager, Rolf B.; Durkin, Anthony J.; Strömberg, Tomas

2017-11-01

A fiber-optic probe-based instrument, designed for assessment of parameters related to microcirculation, red blood cell tissue fraction (fRBC), oxygen saturation (S), and speed resolved perfusion, has been evaluated using state-of-the-art tissue phantoms. The probe integrates diffuse reflectance spectroscopy (DRS) at two source-detector separations and laser Doppler flowmetry, using an inverse Monte Carlo method for identifying the parameters of a multilayered tissue model. Here, we characterize the accuracy of the DRS aspect of the instrument using (1) liquid blood phantoms containing yeast and (2) epidermis-dermis mimicking solid-layered phantoms fabricated from polydimethylsiloxane, titanium oxide, hemoglobin, and coffee. The root-mean-square (RMS) deviations for fRBC for the two liquid phantoms were 11% and 5.3%, respectively, and 11% for the solid phantoms with highest hemoglobin signatures. The RMS deviation for S was 5.2% and 2.9%, respectively, for the liquid phantoms, and 2.9% for the solid phantoms. RMS deviation for the reduced scattering coefficient (μs‧), for the solid phantoms was 15% (475 to 850 nm). For the liquid phantoms, the RMS deviation in average vessel diameter (D) was 1 μm. In conclusion, the skin microcirculation parameters fRBC and S, as well as, μs‧ and D are estimated with reasonable accuracy.

Quasi-solid state rechargeable Na-CO2 batteries with reduced graphene oxide Na anodes.

PubMed

Hu, Xiaofei; Li, Zifan; Zhao, Yaran; Sun, Jianchao; Zhao, Qing; Wang, Jianbin; Tao, Zhanliang; Chen, Jun

2017-02-01

Na-CO 2 batteries using earth-abundant Na and greenhouse gas CO 2 are promising tools for mobile and stationary energy storage, but they still pose safety risks from leakage of liquid electrolyte and instability of the Na metal anode. These issues result in extremely harsh operating conditions of Na-CO 2 batteries and increase the difficulty of scaling up this technology. We report the development of quasi-solid state Na-CO 2 batteries with high safety using composite polymer electrolyte (CPE) and reduced graphene oxide (rGO) Na anodes. The CPE of PVDF-HFP [poly(vinylidene fluoride- co -hexafluoropropylene)]-4% SiO 2 /NaClO 4 -TEGDME (tetraethylene glycol dimethyl ether) has high ion conductivity (1.0 mS cm -1 ), robust toughness, a nonflammable matrix, and strong electrolyte-locking ability. In addition, the rGO-Na anode presents fast and nondendritic Na + plating/stripping (5.7 to 16.5 mA cm -2 ). The improved kinetics and safety enable the constructed rGO-Na/CPE/CO 2 batteries to successfully cycle in wide CO 2 partial pressure window (5 to 100%, simulated car exhaust) and especially to run for 400 cycles at 500 mA g -1 with a fixed capacity of 1000 mA·hour g -1 in pure CO 2 . Furthermore, we scaled up the reversible capacity to 1.1 A·hour in pouch-type batteries (20 × 20 cm, 10 g, 232 Wh kg -1 ). This study makes quasi-solid state Na-CO 2 batteries an attractive prospect.

Quasi–solid state rechargeable Na-CO2 batteries with reduced graphene oxide Na anodes

PubMed Central

Hu, Xiaofei; Li, Zifan; Zhao, Yaran; Sun, Jianchao; Zhao, Qing; Wang, Jianbin; Tao, Zhanliang; Chen, Jun

2017-01-01

Na-CO2 batteries using earth-abundant Na and greenhouse gas CO2 are promising tools for mobile and stationary energy storage, but they still pose safety risks from leakage of liquid electrolyte and instability of the Na metal anode. These issues result in extremely harsh operating conditions of Na-CO2 batteries and increase the difficulty of scaling up this technology. We report the development of quasi–solid state Na-CO2 batteries with high safety using composite polymer electrolyte (CPE) and reduced graphene oxide (rGO) Na anodes. The CPE of PVDF-HFP [poly(vinylidene fluoride-co-hexafluoropropylene)]–4% SiO2/NaClO4–TEGDME (tetraethylene glycol dimethyl ether) has high ion conductivity (1.0 mS cm−1), robust toughness, a nonflammable matrix, and strong electrolyte-locking ability. In addition, the rGO-Na anode presents fast and nondendritic Na+ plating/stripping (5.7 to 16.5 mA cm−2). The improved kinetics and safety enable the constructed rGO-Na/CPE/CO2 batteries to successfully cycle in wide CO2 partial pressure window (5 to 100%, simulated car exhaust) and especially to run for 400 cycles at 500 mA g−1 with a fixed capacity of 1000 mA·hour g−1 in pure CO2. Furthermore, we scaled up the reversible capacity to 1.1 A·hour in pouch-type batteries (20 × 20 cm, 10 g, 232 Wh kg−1). This study makes quasi–solid state Na-CO2 batteries an attractive prospect. PMID:28164158

METHOD OF COMBINING HYDROGEN AND OXYGEN

DOEpatents

McBride, J.P.

1962-02-27

A method is given for the catalytic recombination of radiolytic hydrogen and/or deulerium and oxygen resulting from the subjection or an aqueous thorium oxide or thorium oxide-uranium oxide slurry to ionizing radiation. An improved catalyst is prepared by providing paliadium nitrate in an aqueous thorium oxide sol at a concentration of at least 0.05 grams per gram of thorium oxide and contacting the sol with gaseous hydrogen to form flocculated solids. The solids are then recovered and added to the slurry to provide a palladium concentration of 100 to 1000 parts per million. Recombination is effected by the calalyst at a rate sufficient to support high nuclear reactor power densities. (AEC)

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, A.F.; Makowiecki, D.M.; Rambach, G.D.; Randich, E.

1998-05-19

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated. 8 figs.

Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

NASA Astrophysics Data System (ADS)

Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

2015-10-01

A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

One-step electrolytic preparation of Si-Fe alloys as anodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Hailong; Sun, Diankun; Song, Qiqi; Xie, Wenqi; Jiang, Xu; Zhang, Bo

2016-06-01

One-step electrolytic formation of uniform crystalline Si-Fe alloy particles was successfully demonstrated in direct electro-reduction of solid mixed oxides of SiO2 and Fe2O3 in molten CaCl2 at 900∘C. Upon constant voltage electrolysis of solid mixed oxides at 2.8V between solid oxide cathode and graphite anode for 5h, electrolytic Si-Fe with the same Si/Fe stoichimetry of the precursory oxides was generated. The firstly generated Fe could function as depolarizers to enhance reduction rate of SiO2, resulting in the enhanced reduction kinetics to the electrolysis of individual SiO2. When evaluated as anode for lithium ion batteries, the prepared SiFe electrode showed a reversible lithium storage capacity as high as 470mAh g-1 after 100 cycles at 200mA g-1, promising application in high-performance lithium ion batteries.

Scaling-Up Solid Oxide Membrane Electrolysis Technology for Magnesium Production

NASA Astrophysics Data System (ADS)

Pati, Soobhankar; Powell, Adam; Tucker, Steve; Derezinski, Steve

Metal Oxygen Separation Technologies, Inc. (MOxST) is actively developing Solid Oxide Membrane (SOM) electrolysis technology for production of magnesium directly from its oxide. The vital component of this technology is the oxygen ion-conducting solid zirconia electrolyte separating the molten flux (a mixture of salts and oxide) and the inert anode. The zirconia not only protects the anode from the flux but also prevents anode gas back-reaction, increasing the efficiency. This makes it possible to produce low-cost high-purity magnesium and high-purity oxygen as a byproduct with no direct greenhouse gas emissions. In this paper we discuss the design modifications made to address the scaling-up challenges, particularly for producing magnesium in liquid form. The key accomplishment to date is the successful development of a prototype capable of producing few kilograms of magnesium per day. We will also describe the prerequisite properties of an inert anode and suitable materials for the same.

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, Alan F.; Makowiecki, Daniel M.; Rambach, Glenn D.; Randich, Erik

1999-01-01

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated.

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, Alan F.; Makowiecki, Daniel M.; Rambach, Glenn D.; Randich, Erik

1998-01-01

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated.

Application of the monolithic solid oxide fuel cell to space power systems

NASA Astrophysics Data System (ADS)

Myles, Kevin M.; Bhattacharyya, Samit K.

1991-01-01

The monolithic solid-oxide fuel cell (MSOFC) is a promising electrochemical power generation device that is currently under development at Argonne National Laboratory. The extremely high power density of the MSOFC leads to MSOFC systems that have sufficiently high energy densities that they are excellent candidates for a number of space missions. The fuel cell can also be operated in reverse, if it can be coupled to an external power source, to regenerate the fuel and oxidant from the water product. This feature further enhances the potential mission applications of the MSOFC. In this paper, the current status of the fuel cell development is presented—the focus being on fabrication and currently achievable performance. In addition, a specific example of a space power system, featuring a liquid metal cooled fast spectrum nuclear reactor and a monolithic solid oxide fuel cell, is presented to demonstrate the features of an integrated system.

Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.

A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 withmore » solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.« less

Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

PubMed

Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

2017-10-04

We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10 -3 S cm -1 ) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g -1 at 0.1 A g -1 ), better rate capability (64% capacity retention until 20 A g -1 ), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg -1 at 1 A g -1 ) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

High conducting oxide--sulfide composite lithium superionic conductor

DOEpatents

Liang, Chengdu; Rangasamy, Ezhiylmurugan; Dudney, Nancy J.; Keum, Jong Kahk; Rondinone, Adam Justin

2017-01-17

A solid electrolyte for a lithium-sulfur battery includes particles of a lithium ion conducting oxide composition embedded within a lithium ion conducting sulfide composition. The lithium ion conducting oxide composition can be Li.sub.7La.sub.3Zr.sub.2O.sub.12 (LLZO). The lithium ion conducting sulfide composition can be .beta.-Li.sub.3PS.sub.4 (LPS). A lithium ion battery and a method of making a solid electrolyte for a lithium ion battery are also disclosed.

Identification of a Methane Oxidation Intermediate on Solid Oxide Fuel Cell Anode Surfaces with Fourier Transform Infrared Emission.

PubMed

Pomfret, Michael B; Steinhurst, Daniel A; Owrutsky, Jeffrey C

2013-04-18

Fuel interactions on solid oxide fuel cell (SOFC) anodes are studied with in situ Fourier transform infrared emission spectroscopy (FTIRES). SOFCs are operated at 800 °C with CH4 as a representative hydrocarbon fuel. IR signatures of gas-phase oxidation products, CO2(g) and CO(g), are observed while cells are under load. A broad feature at 2295 cm(-1) is assigned to CO2 adsorbed on Ni as a CH4 oxidation intermediate during cell operation and while carbon deposits are electrochemically oxidized after CH4 operation. Electrochemical control provides confirmation of the assignment of adsorbed CO2. FTIRES has been demonstrated as a viable technique for the identification of fuel oxidation intermediates and products in working SOFCs, allowing for the elucidation of the mechanisms of fuel chemistry.

Composite anode La0.8Sr0.2MnO3 impregnated with cobalt oxide for steam electrolysis

NASA Astrophysics Data System (ADS)

Li, Shisong; Cheng, Jigui; Xie, Kui; Li, Peipei; Wu, Yucheng

2013-12-01

Oxygen-ion conducting solid oxide electrolyzer (SOE) has attracted a great deal of interest because it converts electrical energy into chemical energy directly. The oxygen evolution reaction (OER) is occurred at the anode of solid oxide electrolyzer as the O2- being oxidized and form O2 gas, which is considered as one of the major cause of overpotentials in steam electrolyzers. This paper investigates the electrolysis of steam based on cobalt oxide impregnated La0.8Sr0.2MnO3 (LSM) composite anode in an oxide-ion-conducting solid oxide electrolyzer. The conductivity of LSM is studied versus temperature and oxygen partial pressure and correlated to the electrochemical properties of the composite electrodes in symmetric cells at 800 °C. Different contents of Co3O4 (wt.1%, 2%, 4%, 6%, 8%, 10%) were impregnated into LSM electrode and it was found that the polarization resistance (Rp) of symmetric cells gradually improved from 1.16 Ω•cm2 (LSM) to 0.24 Ω•cm2 (wt.10%Co3O4-LSM). Steam electrolysis based on LSM and wt.6%Co3O4-LSM anode electrolyzers are tested at 800°C and the AC impedance spectroscopy results indicated that the Rp of high frequency process significantly decreased from1.1 Ω•cm2 (LSM) to 0.5 Ω•cm2 (wt.6%Co3O4-LSM) under 1.8V electrolysis voltage and the Rp of low frequency process decreased from 14.9 Ω•cm2 to 5.7 Ω•cm2. Electrochemical catalyst Co3O4 can efficiently improve the electrode and enhance the performance of high temperature solid oxide electrolyzer.

Highlights from Faraday Discussion 182: Solid Oxide Electrolysis: Fuels and Feedstocks from Water and Air, York, UK, July 2015.

PubMed

Stefan, Elena; Norby, Truls

2016-01-31

The rising importance of converting high peak electricity from renewables to fuels has urged field specialists to organize this Faraday Discussion on Solid Oxide Electrolysis. The topic is of essential interest in order to achieve a greater utilization of renewable energy and storage at higher densities.

Solid Oxide Fuel Cell Seal Development at NASA Glenn Research Center

NASA Technical Reports Server (NTRS)

Steinetz, Bruce M.; Bansal, Narottam P.; Dynys, Fred W.; Lang, Jerry; Daniels, Christopher C.; Palko, Joeseph L.; Choi, S. R.

2004-01-01

Researchers at NASA GRC are confronting the seal durability challenges of Solid Oxide Fuel Cells by pursuing an integrated and multidisciplinary development effort incorporating thermo-structural analyses, advanced materials, experimentation, and novel seal design concepts. The successful development of durable hermetic SOFC seals is essential to reliably producing the high power densities required for aerospace applications.

Viscous sealing glass compositions for solid oxide fuel cells

DOEpatents

Kim, Cheol Woon; Brow, Richard K.

2016-12-27

A sealant for forming a seal between at least two solid oxide fuel cell components wherein the sealant comprises a glass material comprising B.sub.2O.sub.3 as a principal glass former, BaO, and other components and wherein the glass material is substantially alkali-free and contains less than 30% crystalline material.

Ni modified ceramic anodes for direct-methane solid oxide fuel cells

DOEpatents

Xiao, Guoliang; Chen, Fanglin

2016-01-19

In accordance with certain embodiments of the present disclosure, a method for fabricating a solid oxide fuel cell is described. The method includes synthesizing a composition having a perovskite present therein. The method further includes applying the composition on an electrolyte support to form an anode and applying Ni to the composition on the anode.

Co-flow anode/cathode supply heat exchanger for a solid-oxide fuel cell assembly

DOEpatents

Haltiner, Jr., Karl J.; Kelly, Sean M.

2005-11-22

In a solid-oxide fuel cell assembly, a co-flow heat exchanger is provided in the flow paths of the reformate gas and the cathode air ahead of the fuel cell stack, the reformate gas being on one side of the exchanger and the cathode air being on the other. The reformate gas is at a substantially higher temperature than is desired in the stack, and the cathode gas is substantially cooler than desired. In the co-flow heat exchanger, the temperatures of the reformate and cathode streams converge to nearly the same temperature at the outlet of the exchanger. Preferably, the heat exchanger is formed within an integrated component manifold (ICM) for a solid-oxide fuel cell assembly.

Brazing of Stainless Steel to Yttria-Stabilized Zirconia Using Gold-Based Brazes for Solid Oxide Fuel Cell Applications

NASA Technical Reports Server (NTRS)

Singh, M.; Shpargel, T. P.; Asthana, R.

2007-01-01

Two gold-base active metal brazes (gold-ABA and gold-ABA-V) were evaluated for oxidation resistance to 850 C, and used to join yttria-stabilized zirconia (YSZ) to a corrosion-resistant ferritic stainless steel for possible use in solid oxide fuel cells. Thermogravimetric analysis and optical microscopy and scanning electron microscopy coupled with energy-dispersive spectroscopy were used to evaluate the braze oxidation behavior, and microstructure and composition of the YSZ/braze/steel joints. Both gold-ABA and gold-ABA-V exhibited nearly linear oxidation kinetics at 850 C, with gold-ABA-V showing faster oxidation than gold-ABA. Both brazes produced metallurgically sound YSZ/steel joints due to chemical interactions of Ti and V with the YSZ and steel substrates.

Solid polymer MEMS-based fuel cells

DOEpatents

Jankowski, Alan F [Livermore, CA; Morse, Jeffrey D [Pleasant Hill, CA

2008-04-22

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Distinguishing solid bitumens formed by thermochemical sulfate reduction and thermal chemical alteration

USGS Publications Warehouse

Kelemen, S.R.; Walters, C.C.; Kwiatek, P.J.; Afeworki, M.; Sansone, M.; Freund, H.; Pottorf, R.J.; Machel, H.G.; Zhang, T.; Ellis, G.S.; Tang, Y.; Peters, K.E.

2008-01-01

Insoluble solid bitumens are organic residues that can form by the thermal chemical alteration (TCA) or thermochemical sulfate reduction (TSR) of migrated petroleum. TCA may actually encompass several low temperature processes, such as biodegradation and asphaltene precipitation, followed by thermal alteration. TSR is an abiotic redox reaction where petroleum is oxidized by sulfate. It is difficult to distinguish solid bitumens associated with TCA of petroleum from those associated with TSR when both processes occur at relatively high temperature. The focus of the present work was to characterize solid bitumen samples associated with TCA or TSR using X-ray photoelectron spectroscopy (XPS). XPS is a surface analysis conducted on either isolated or in situ (>25 ??m diameter) solid bitumen that can provide the relative abundance and chemical speciation of carbon, organic and inorganic heteroatoms (NSO). In this study, naturally occurring solid bitumens from three locations, Nisku Fm. Brazeau River area (TSR-related), LaBarge Field Madison Fm. (TSR-related), and the Alaskan Brooks range (TCA-related), are compared to organic solids generated during laboratory simulation of the TSR and TCA processes. The abundance and chemical nature of organic nitrogen and sulfur in solid bitumens can be understood in terms of the nature of (1) petroleum precursor molecules, (2) the concentration of nitrogen by way of thermal stress and (3) the mode of sulfur incorporation. TCA solid bitumens originate from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. Organic sulfur in TCA organic solids remains fairly constant with increasing maturation (3.5 to ???17 sulfur per 100 carbons) into aromatic structures and to the low levels of nitrogen in their hydrocarbon precursors. Hence, XPS results provide organic chemical composition information that helps to distinguish whether solid bitumen, either in situ or removed and concentrated from the rock matrix, was formed via the TCA or TRS process. ?? 2008 Elsevier Ltd.

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

USGS Publications Warehouse

Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C.

2010-01-01

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

Thermodynamic modeling of non-ideal mineral-fluid equilibria in the system Si-Al-Fe-Mg-Ca-Na-K-H-O-Cl at elevated temperatures and pressures: Implications for hydrothermal mass transfer in granitic rocks

NASA Astrophysics Data System (ADS)

Dolejš, David; Wagner, Thomas

2008-01-01

We present the results of thermodynamic modeling of fluid-rock interaction in the system Si-Al-Fe-Mg-Ca-Na-H-O-Cl using the GEM-Selektor Gibbs free energy minimization code. Combination of non-ideal mixing properties in solids with multicomponent aqueous fluids represents a substantial improvement and it provides increased accuracy over existing modeling strategies. Application to the 10-component system allows us to link fluid composition and speciation with whole-rock mineralogy, mass and volume changes. We have simulated granite-fluid interaction over a wide range of conditions (200-600 °C, 100 MPa, 0-5 m Cl and fluid/rock ratios of 10-2-104) in order to explore composition of magmatic fluids of variable salinity, temperature effects on fluid composition and speciation and to simulate several paths of alteration zoning. At low fluid/rock ratios (f/r) the fluid composition is buffered by the silicate-oxide assemblage and remains close to invariant. This behavior extends to a f/r of 0.1 which exceeds the amount of exsolved magmatic fluids controlled by water solubility in silicate melts. With increasing peraluminosity of the parental granite, the Na-, K- and Fe-bearing fluids become more acidic and the oxidation state increases as a consequence of hydrogen and ferrous iron transfer to the fluid. With decreasing temperature, saline fluids become more Ca- and Na-rich, change from weakly acidic to alkaline, and become significantly more oxidizing. Large variations in Ca/Fe and Ca/Mg ratios in the fluid are a potential geothermometer. The mineral assemblage changes from cordierite-biotite granites through two-mica granites to chlorite-, epidote- and zeolite-bearing rocks. We have carried out three rock-titration simulations: (1) reaction with the 2 m NaCl fluid leads to albitization, chloritization and desilication, reproducing essential features observed in episyenites, (2) infiltration of a high-temperature fluid into the granite at 400 °C leads to hydrolytic alteration commencing with alkali-feldspar breakdown and leading to potassic, phyllic and argillic assemblages; this is associated with reduction and iron metasomatism as observed in nature and (3) interaction with a multicomponent fluid at 600 °C produces sodic-calcic metasomatism. Na, Ca and Fe are the most mobile elements whereas immobility of Al is limited by f/r ∼ 400. All simulations predict a volume decrease by 3.4-5.4%, i.e., porosity formation at f/r < 30. At higher fluid/rock ratios simulation (2) produces a substantial volume increase (59%) due to mineral precipitation, whereas simulation (3) predicts a volume decrease by 49% at the advanced albitization-desilication stage. Volume changes closely correlate with mass changes of SiO2 and are related to silica solubility in fluids. The combined effects of oxygen fugacity, fluid acidity and pH for breakdown of aqueous metal complexes and precipitation of ore minerals were evaluated by means of reduced activity products. Sharp increases in saturation indexes for oxidative breakdown occur at each alteration zone whereas reductive breakdown or involvement of other chloride complexes favor precipitation at high fluid/rock ratios only. Calculations of multicomponent aqueous-solid equilibria at high temperatures and pressures are able to accurately predict rock mineralogy and fluid chemistry and are applicable to diverse reactive flow processes in the Earth's crust.

Controlled growth of semiconductor crystals

DOEpatents

Bourret-Courchesne, Edith D.

1992-01-01

A method for growth of III-V, II-VI and related semiconductor single crystals that suppresses random nucleation and sticking of the semiconductor melt at the crucible walls. Small pieces of an oxide of boron B.sub.x O.sub.y are dispersed throughout the comminuted solid semiconductor charge in the crucible, with the oxide of boron preferably having water content of at least 600 ppm. The crucible temperature is first raised to a temperature greater than the melt temperature T.sub.m1 of the oxide of boron (T.sub.m1 =723.degree. K. for boron oxide B.sub.2 O.sub.3), and the oxide of boron is allowed to melt and form a reasonably uniform liquid layer between the crucible walls and bottom surfaces and the still-solid semiconductor charge. The temperature is then raised to approximately the melt temperature T.sub.m2 of the semiconductor charge material, and crystal growth proceeds by a liquid encapsulated, vertical gradient freeze process. About half of the crystals grown have a dislocation density of less than 1000/cm.sup.2. If the oxide of boron has water content less than 600 ppm, the crucible material should include boron nitride, a layer of the inner surface of the crucible should be oxidized before the oxide of boron in the crucible charge is melted, and the sum of thicknesses of the solid boron oxide layer and liquid boron oxide layer should be at least 50 .mu.m.

Controlled growth of semiconductor crystals

DOEpatents

Bourret-Courchesne, E.D.

1992-07-21

A method is disclosed for growth of III-V, II-VI and related semiconductor single crystals that suppresses random nucleation and sticking of the semiconductor melt at the crucible walls. Small pieces of an oxide of boron B[sub x]O[sub y] are dispersed throughout the comminuted solid semiconductor charge in the crucible, with the oxide of boron preferably having water content of at least 600 ppm. The crucible temperature is first raised to a temperature greater than the melt temperature T[sub m1] of the oxide of boron (T[sub m1]=723 K for boron oxide B[sub 2]O[sub 3]), and the oxide of boron is allowed to melt and form a reasonably uniform liquid layer between the crucible walls and bottom surfaces and the still-solid semiconductor charge. The temperature is then raised to approximately the melt temperature T[sub m2] of the semiconductor charge material, and crystal growth proceeds by a liquid encapsulated, vertical gradient freeze process. About half of the crystals grown have a dislocation density of less than 1000/cm[sup 2]. If the oxide of boron has water content less than 600 ppm, the crucible material should include boron nitride, a layer of the inner surface of the crucible should be oxidized before the oxide of boron in the crucible charge is melted, and the sum of thicknesses of the solid boron oxide layer and liquid boron oxide layer should be at least 50 [mu]m. 7 figs.

Effects of fuel processing methods on industrial scale biogas-fuelled solid oxide fuel cell system for operating in wastewater treatment plants

NASA Astrophysics Data System (ADS)

Farhad, Siamak; Yoo, Yeong; Hamdullahpur, Feridun

The performance of three solid oxide fuel cell (SOFC) systems, fuelled by biogas produced through anaerobic digestion (AD) process, for heat and electricity generation in wastewater treatment plants (WWTPs) is studied. Each system has a different fuel processing method to prevent carbon deposition over the anode catalyst under biogas fuelling. Anode gas recirculation (AGR), steam reforming (SR), and partial oxidation (POX) are the methods employed in systems I-III, respectively. A planar SOFC stack used in these systems is based on the anode-supported cells with Ni-YSZ anode, YSZ electrolyte and YSZ-LSM cathode, operated at 800 °C. A computer code has been developed for the simulation of the planar SOFC in cell, stack and system levels and applied for the performance prediction of the SOFC systems. The key operational parameters affecting the performance of the SOFC systems are identified. The effect of these parameters on the electrical and CHP efficiencies, the generated electricity and heat, the total exergy destruction, and the number of cells in SOFC stack of the systems are studied. The results show that among the SOFC systems investigated in this study, the AGR and SR fuel processor-based systems with electrical efficiency of 45.1% and 43%, respectively, are suitable to be applied in WWTPs. If the entire biogas produced in a WWTP is used in the AGR or SR fuel processor-based SOFC system, the electricity and heat required to operate the WWTP can be completely self-supplied and the extra electricity generated can be sold to the electrical grid.

Interfacial Tension in the CaO-Al2O3-SiO2-(MgO) Liquid Slag-Solid Oxide Systems

NASA Astrophysics Data System (ADS)

Abdeyazdan, Hamed; Monaghan, Brian J.; Longbottom, Raymond J.; Rhamdhani, M. Akbar; Dogan, Neslihan; Chapman, Michael W.

2017-08-01

Interfacial phenomenon is critical in metal processing and refining. While it is known to be important, there are little data available for key oxide systems in the literature. In this study, the interfacial tension ( σ LS) of liquid slag on solid oxides (alumina, spinel, and calcium aluminate), for a range of slags in the CaO-Al2O3-SiO2-(MgO) system at 1773 K (1500 °C), has been evaluated. The results show that basic ladle-type slags exhibit lower σ LS with oxide phases examined compared to that of acid tundish-type slags. Also, within the slag types (acid and base), σ LS was observed to decrease with increasing slag basicity. A correlation between σ LS and slag structure was observed, i.e., σ LS was found to decrease linearly with increasing of slag optical basicity (Λ) and decrease logarithmically with decreasing of slag viscosity from acid to base slags. This indicated a higher σ LS as the ions in the slag become larger and more complex. Through a work of adhesion ( W) analysis, it was shown that basic ladle slags with lower σ LS result in a greater W, i.e., form a stronger bond with the solid oxide phases examined. This indicates that all other factors being equal, the efficiency of inclusion removal from steel of inclusions of similar phase to these solid oxides would be greater.

Comparison of Cross Flow Filtration Performance for Manganese Oxide/Sludge Mixtures and Monosodium Titanate/Sludge Mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poirier, M.R.

2002-06-07

Personnel performed engineering-scale tests at the Filtration Research Engineering Demonstration (FRED) to determine crossflow filter performance with a 5.6 M sodium solution containing varying concentrations of sludge and sodium permanganate. The work represents another in a series of collaborative efforts between the University of South Carolina and the Savannah River Technology Center in support of the process development efforts for the Savannah River Site. The current tests investigated filter performance with slurry containing simulated Tank 40H Sludge and sodium permanganate at concentrations between 0.070 weight percent and 3.04 weight percent insoluble solids.

A fully coupled 3D transport model in SPH for multi-species reaction-diffusion systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adami, Stefan; Hu, X. Y.; Adams, N. A.

2011-08-23

Abstract—In this paper we present a fully generalized transport model for multiple species in complex two and threedimensional geometries. Based on previous work [1] we have extended our interfacial reaction-diffusion model to handle arbitrary numbers of species allowing for coupled reaction models. Each species is tracked independently and we consider different physics of a species with respect to the bulk phases in contact. We use our SPH model to simulate the reaction-diffusion problem on a pore-scale level of a solid oxide fuel cell (SOFC) with special emphasize on the effect of surface diffusion.

Sandblasting nozzle

NASA Technical Reports Server (NTRS)

Perkins, G. S.; Pawlik, E. V.; Phillips, W. M. (Inventor)

1981-01-01

A nozzle for use with abrasive and/or corrosive materials is formed of sintered ceramic compositions having high temperature oxidation resistance, high hardness and high abrasion and corrosion resistance. The ceramic may be a binary solid solution of a ceramic oxide and silicon nitride, and preferably a ternary solid solution of a ceramic oxide, silicon nitride and aluminum nitride. The ceramic oxide is selected from a group consisting of Al2O3, Y2O3 and Cr2O3, or mixtures of those compounds. Titanium carbide particles are dispersed in the ceramic mixture before sintering. The nozzles are encased for protection from external forces while in use by a metal or plastic casing.

Direct electrochemical reduction of solid uranium oxide in molten fluoride salts

NASA Astrophysics Data System (ADS)

Gibilaro, Mathieu; Cassayre, Laurent; Lemoine, Olivier; Massot, Laurent; Dugne, Olivier; Malmbeck, Rikard; Chamelot, Pierre

2011-07-01

The direct electrochemical reduction of UO 2 solid pellets was carried out in LiF-CaF 2 (+2 mass.% Li 2O) at 850 °C. An inert gold anode was used instead of the usual reactive sacrificial carbon anode. In this case, oxidation of oxide ions present in the melt yields O 2 gas evolution on the anode. Electrochemical characterisations of UO 2 pellets were performed by linear sweep voltammetry at 10 mV/s and reduction waves associated to oxide direct reduction were observed at a potential 150 mV more positive in comparison to the solvent reduction. Subsequent, galvanostatic electrolyses runs were carried out and products were characterised by SEM-EDX, EPMA/WDS, XRD and microhardness measurements. In one of the runs, uranium oxide was partially reduced and three phases were observed: nonreduced UO 2 in the centre, pure metallic uranium on the external layer and an intermediate phase representing the initial stage of reduction taking place at the grain boundaries. In another run, the UO 2 sample was fully reduced. Due to oxygen removal, the U matrix had a typical coral-like structure which is characteristic of the pattern observed after the electroreduction of solid oxides.

Solid oxide fuel cell generator with removable modular fuel cell stack configurations

DOEpatents

Gillett, J.E.; Dederer, J.T.; Zafred, P.R.; Collie, J.C.

1998-04-21

A high temperature solid oxide fuel cell generator produces electrical power from oxidation of hydrocarbon fuel gases such as natural gas, or conditioned fuel gases, such as carbon monoxide or hydrogen, with oxidant gases, such as air or oxygen. This electrochemical reaction occurs in a plurality of electrically connected solid oxide fuel cells bundled and arrayed in a unitary modular fuel cell stack disposed in a compartment in the generator container. The use of a unitary modular fuel cell stack in a generator is similar in concept to that of a removable battery. The fuel cell stack is provided in a pre-assembled self-supporting configuration where the fuel cells are mounted to a common structural base having surrounding side walls defining a chamber. Associated generator equipment may also be mounted to the fuel cell stack configuration to be integral therewith, such as a fuel and oxidant supply and distribution systems, fuel reformation systems, fuel cell support systems, combustion, exhaust and spent fuel recirculation systems, and the like. The pre-assembled self-supporting fuel cell stack arrangement allows for easier assembly, installation, maintenance, better structural support and longer life of the fuel cells contained in the fuel cell stack. 8 figs.

Solid oxide fuel cell generator with removable modular fuel cell stack configurations

DOEpatents

Gillett, James E.; Dederer, Jeffrey T.; Zafred, Paolo R.; Collie, Jeffrey C.

1998-01-01

A high temperature solid oxide fuel cell generator produces electrical power from oxidation of hydrocarbon fuel gases such as natural gas, or conditioned fuel gases, such as carbon monoxide or hydrogen, with oxidant gases, such as air or oxygen. This electrochemical reaction occurs in a plurality of electrically connected solid oxide fuel cells bundled and arrayed in a unitary modular fuel cell stack disposed in a compartment in the generator container. The use of a unitary modular fuel cell stack in a generator is similar in concept to that of a removable battery. The fuel cell stack is provided in a pre-assembled self-supporting configuration where the fuel cells are mounted to a common structural base having surrounding side walls defining a chamber. Associated generator equipment may also be mounted to the fuel cell stack configuration to be integral therewith, such as a fuel and oxidant supply and distribution systems, fuel reformation systems, fuel cell support systems, combustion, exhaust and spent fuel recirculation systems, and the like. The pre-assembled self-supporting fuel cell stack arrangement allows for easier assembly, installation, maintenance, better structural support and longer life of the fuel cells contained in the fuel cell stack.

Oxidation reactions of solid carbonaceous and resinous substances in supercritical water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koda, S.

Recent kinetic studies, particularly those by means of shadowgraphy and X-ray radiography, for supercritical water oxidation of solid carbonaceous and resinous substances have revealed the importance of the O{sub 2} mass transfer process over the intrinsic surface reaction at higher temperatures. The mass transfer processes, internal and external one, should be incorporated in designing SCWO processes for solid substances and related processes such as catalytic SCWO. Some model calculation efforts of late are briefly described. Finally, fundamental information required for future development is itemed.

Hybrid rockets - Combining the best of liquids and solids

NASA Technical Reports Server (NTRS)

Cook, Jerry R.; Goldberg, Ben E.; Estey, Paul N.; Wiley, Dan R.

1992-01-01

Hybrid rockets employing liquid oxidizer and solid fuel grain answers to cost, safety, reliability, and environmental impact concerns that have become as prominent as performance in recent years. The oxidizer-free grain has limited sensitivity to grain anomalies, such as bond-line separations, which can cause catastrophic failures in solid rocket motors. An account is presently given of the development effort associated with the AMROC commercial hybrid booster and component testing efforts at NASA-Marshall. These hybrid rockets can be fired, terminated, inspected, evaluated, and restarted for additional testing.

Application of advanced oxidation processes for cleaning of industrial water generated in wet dedusting of shaft furnace gases.

PubMed

Czaplicka, Marianna; Kurowski, Ryszard; Jaworek, Katarzyna; Bratek, Łukasz

2013-01-01

The paper presents results of studies into advanced oxidation processes in 03 and 03/UV systems. An advanced oxidation process (AOP) was conducted to reduce the load of impurities in circulating waters from wet de-dusting of shaft furnace gases. Besides inorganic impurities, i.e. mainly arsenic compounds (16 g As L(-1) on average), lead, zinc, chlorides and sulphates, the waters also contain some organic material. The organic material is composed of a complex mixture that contains, amongst others, aliphatic compounds, phenol and its derivatives, pyridine bases, including pyridine, and its derivatives. The test results show degradation of organic and inorganic compounds during ozonation and photo-oxidation processes. Analysis of the solutions from the processes demonstrated that the complex organic material in the industrial water was oxidized in ozonation and in photo-oxidation, which resulted in formation of aldehydes and carboxylic acids. Kinetic degradation of selected pollutants is presented. Obtained results indicated that the O3/UV process is more effective in degradation of organic matter than ozonation. Depending on the process type, precipitation of the solid phase was observed. The efficiency of solid-phase formation was higher in photo-oxidation with ozone. It was found that the precipitated solid phase is composed mainly of arsenic, iron and oxygen.

Sub-grid drag model for immersed vertical cylinders in fluidized beds

DOE PAGES

Verma, Vikrant; Li, Tingwen; Dietiker, Jean -Francois; ...

2017-01-03

Immersed vertical cylinders are often used as heat exchanger in gas-solid fluidized beds. Computational Fluid Dynamics (CFD) simulations are computationally expensive for large scale systems with bundles of cylinders. Therefore sub-grid models are required to facilitate simulations on a coarse grid, where internal cylinders are treated as a porous medium. The influence of cylinders on the gas-solid flow tends to enhance segregation and affect the gas-solid drag. A correction to gas-solid drag must be modeled using a suitable sub-grid constitutive relationship. In the past, Sarkar et al. have developed a sub-grid drag model for horizontal cylinder arrays based on 2Dmore » simulations. However, the effect of a vertical cylinder arrangement was not considered due to computational complexities. In this study, highly resolved 3D simulations with vertical cylinders were performed in small periodic domains. These simulations were filtered to construct a sub-grid drag model which can then be implemented in coarse-grid simulations. Gas-solid drag was filtered for different solids fractions and a significant reduction in drag was identified when compared with simulation without cylinders and simulation with horizontal cylinders. Slip velocities significantly increase when vertical cylinders are present. Lastly, vertical suspension drag due to vertical cylinders is insignificant however substantial horizontal suspension drag is observed which is consistent to the finding for horizontal cylinders.« less

Analysis of mixed model in gear transmission based on ADAMS

NASA Astrophysics Data System (ADS)

Li, Xiufeng; Wang, Yabin

2012-09-01

The traditional method of mechanical gear driving simulation includes gear pair method and solid to solid contact method. The former has higher solving efficiency but lower results accuracy; the latter usually obtains higher precision of results while the calculation process is complex, also it is not easy to converge. Currently, most of the researches are focused on the description of geometric models and the definition of boundary conditions. However, none of them can solve the problems fundamentally. To improve the simulation efficiency while ensure the results with high accuracy, a mixed model method which uses gear tooth profiles to take the place of the solid gear to simulate gear movement is presented under these circumstances. In the process of modeling, build the solid models of the mechanism in the SolidWorks firstly; Then collect the point coordinates of outline curves of the gear using SolidWorks API and create fit curves in Adams based on the point coordinates; Next, adjust the position of those fitting curves according to the position of the contact area; Finally, define the loading conditions, boundary conditions and simulation parameters. The method provides gear shape information by tooth profile curves; simulates the mesh process through tooth profile curve to curve contact and offer mass as well as inertia data via solid gear models. This simulation process combines the two models to complete the gear driving analysis. In order to verify the validity of the method presented, both theoretical derivation and numerical simulation on a runaway escapement are conducted. The results show that the computational efficiency of the mixed model method is 1.4 times over the traditional method which contains solid to solid contact. Meanwhile, the simulation results are more closely to theoretical calculations. Consequently, mixed model method has a high application value regarding to the study of the dynamics of gear mechanism.

Development of advanced test methods for the improvement of production standards for ceramic powders used in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Ward, Brian

Solid oxide fuel cells (SOFCs) are energy conversion devices that use ceramic powders as a precursor material for their electrodes. Presently, powder manufacturers are encountering complications producing consistent precursor powders. Through various thermal, chemical and physical tests, such as DSC and XRD, a preliminary production standard will be developed.

Solid oxide fuel cell systems with hot zones having improved reactant distribution

DOEpatents

Poshusta, Joseph C.; Booten, Charles W.; Martin, Jerry L.

2012-11-06

A Solid Oxide Fuel Cell (SOFC) system having a hot zone with a center cathode air feed tube for improved reactant distribution, a CPOX reactor attached at the anode feed end of the hot zone with a tail gas combustor at the opposing end for more uniform heat distribution, and a counter-flow heat exchanger for efficient heat retention.

Solid oxide fuel cell systems with hot zones having improved reactant distribution

DOEpatents

Poshusta, Joseph C; Booten, Charles W; Martin, Jerry L

2013-12-24

A Solid Oxide Fuel Cell (SOFC) system having a hot zone with a center cathode air feed tube for improved reactant distribution, a CPOX reactor attached at the anode feed end of the hot zone with a tail gas combustor at the opposing end for more uniform heat distribution, and a counter-flow heat exchanger for efficient heat retention.

Solid oxide fuel cell systems with hot zones having improved reactant distribution

DOEpatents

Poshusta, Joseph C.; Booten, Charles W.; Martin, Jerry L.

2016-05-17

A Solid Oxide Fuel Cell (SOFC) system having a hot zone with a center cathode air feed tube for improved reactant distribution, a CPOX reactor attached at the anode feed end of the hot zone with a tail gas combustor at the opposing end for more uniform heat distribution, and a counter-flow heat exchanger for efficient heat retention.

Reducing mode circulating fluid bed combustion

DOEpatents

Lin, Yung-Yi; Sadhukhan, Pasupati; Fraley, Lowell D.; Hsiao, Keh-Hsien

1986-01-01

A method for combustion of sulfur-containing fuel in a circulating fluid bed combustion system wherein the fuel is burned in a primary combustion zone under reducing conditions and sulfur captured as alkaline sulfide. The reducing gas formed is oxidized to combustion gas which is then separated from solids containing alkaline sulfide. The separated solids are then oxidized and recycled to the primary combustion zone.

Strain-tolerant ceramic coated seal

DOEpatents

Schienle, James L.; Strangman, Thomas E.

1994-01-01

A metallic regenerator seal is provided having multi-layer coating comprising a NiCrAlY bond layer, a yttria stabilized zirconia (YSZ) intermediate layer, and a ceramic high temperature solid lubricant surface layer comprising zinc oxide, calcium fluoride, and tin oxide. An array of discontinuous grooves is laser machined into the outer surface of the solid lubricant surface layer making the coating strain tolerant.

System for operating solid oxide fuel cell generator on diesel fuel

NASA Technical Reports Server (NTRS)

Singh, Prabhu (Inventor); George, Raymond A. (Inventor)

1997-01-01

A system is provided for operating a solid oxide fuel cell generator on diesel fuel. The system includes a hydrodesulfurizer which reduces the sulfur content of commercial and military grade diesel fuel to an acceptable level. Hydrogen which has been previously separated from the process stream is mixed with diesel fuel at low pressure. The diesel/hydrogen mixture is then pressurized and introduced into the hydrodesulfurizer. The hydrodesulfurizer comprises a metal oxide such as ZnO which reacts with hydrogen sulfide in the presence of a metal catalyst to form a metal sulfide and water. After desulfurization, the diesel fuel is reformed and delivered to a hydrogen separator which removes most of the hydrogen from the reformed fuel prior to introduction into a solid oxide fuel cell generator. The separated hydrogen is then selectively delivered to the diesel/hydrogen mixer or to a hydrogen storage unit. The hydrogen storage unit preferably comprises a metal hydride which stores hydrogen in solid form at low pressure. Hydrogen may be discharged from the metal hydride to the diesel/hydrogen mixture at low pressure upon demand, particularly during start-up and shut-down of the system.

Solid Oxide Fuel Cell Hybrid System for Distributed Power Generation

DOE Office of Scientific and Technical Information (OSTI.GOV)

David Deangelis; Rich Depuy; Debashis Dey

2004-09-30

This report summarizes the work performed by Hybrid Power Generation Systems, LLC (HPGS) during the April to October 2004 reporting period in Task 2.3 (SOFC Scaleup for Hybrid and Fuel Cell Systems) under Cooperative Agreement DE-FC26-01NT40779 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL), entitled ''Solid Oxide Fuel Cell Hybrid System for Distributed Power Generation''. This study analyzes the performance and economics of power generation systems for central power generation application based on Solid Oxide Fuel Cell (SOFC) technology and fueled by natural gas. The main objective of this task is to develop credible scale upmore » strategies for large solid oxide fuel cell-gas turbine systems. System concepts that integrate a SOFC with a gas turbine were developed and analyzed for plant sizes in excess of 20 MW. A 25 MW plant configuration was selected with projected system efficiency of over 65% and a factory cost of under $400/kW. The plant design is modular and can be scaled to both higher and lower plant power ratings. Technology gaps and required engineering development efforts were identified and evaluated.« less

Ionic Fluorine Chemistry.

DTIC Science & Technology

SOLID ROCKET OXIDIZERS, *LIQUID ROCKET OXIDIZERS, CHLORATES, FLUORIDES, ACETONES, CHLORINE COMPOUNDS, NITROSO COMPOUNDS, *HALOGEN COMPOUNDS, ADDITION REACTIONS, CESIUM COMPOUNDS, CHLORIDES, COMPLEX COMPOUNDS

Magnesium Recycling of Partially Oxidized, Mixed Magnesium-Aluminum Scrap through Combined Refining and Solid Oxide Membrane Electrolysis Processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiaofei Guan; Peter A. Zink; Uday B. Pal

2012-01-01

Pure magnesium (Mg) is recycled from 19g of partially oxidized 50.5wt.% Mg-Aluminum (Al) alloy. During the refining process, potentiodynamic scans (PDS) were performed to determine the electrorefining potential for magnesium. The PDS show that the electrorefining potential increases over time as the magnesium content inside the Mg-Al scrap decreases. Up to 100% percent of magnesium is refined from the Mg-Al scrap by a novel refining process of dissolving magnesium and its oxide into a flux followed by vapor phase removal of dissolved magnesium and subsequently condensing the magnesium vapor. The solid oxide membrane (SOM) electrolysis process is employed in themore » refining system to enable additional recycling of magnesium from magnesium oxide (MgO) in the partially oxidized Mg-Al scrap. The combination of the refining and SOM processes yields 7.4g of pure magnesium.« less

DSMC simulation of two-phase plume flow with UV radiation

NASA Astrophysics Data System (ADS)

Li, Jie; Liu, Ying; Wang, Ning; Jin, Ling

2014-12-01

Rarefied gas-particle two-phase plume in which the phase of particles is liquid or solid flows from a solid propellant rocket of hypersonic vehicle flying at high altitudes, the aluminum oxide particulates not only impact the rarefied gas flow properties, but also make a great difference to plume radiation signature, so the radiation prediction of the rarefied gas-particle two-phase plume flow is very important for space target detection of hypersonic vehicles. Accordingly, this project aims to study the rarefied gas-particle two-phase flow and ultraviolet radiation (UV) characteristics. Considering a two-way interphase coupling of momentum and energy, the direct simulation Monte Carlo (DSMC) method is developed for particle phase change and the particle flow, including particulate collision, coalescence as well as separation, and a Monte Carlo ray trace model is implemented for the particulate UV radiation. A program for the numerical simulation of the gas-particle two-phase flow and radiation in which the gas flow nonequilibrium is strong is implemented as well. Ultraviolet radiation characteristics of the particle phase is studied based on the calculation of the flow field coupled with the radiation calculation, the radiation model for different size particles is analyzed, focusing on the effects of particle emission, absorption, scattering as well as the searchlight emission of the nozzle. A new approach may be proposed to describe the rarefied gas-particle two-phase plume flow and radiation transfer characteristics in this project.

Experimental and simulation studies of iron oxides for geochemical fixation of CO2-SO2 gas mixtures

USGS Publications Warehouse

Garcia, Susana; Rosenbauer, Robert J.; Palandri, James; Maroto-Valer, M. Mercedes

2011-01-01

Iron-bearing minerals are reactive phases of the subsurface environment and could potentially trap CO2–SO2gas mixtures derived from fossil fuel combustion processes by their conversion to siderite (FeCO3) and dissolved sulfate. Changes in fluid and mineral compositions resulting from reactions, involving the co-injection of SO2 with CO2 were observed both theoretically and experimentally. Experiments were conducted with a natural hematite (α-Fe2O3) sample. A high pressure-high temperature apparatus was used to simulate conditions in geologic formations deeper than 800 m, where CO2 is in the supercritical state. Solid samples were allowed to react with a NaCl–NaOH brine and SO2-bearing CO2-dominated gas mixtures. The predicted equilibrium mineral assemblage at 100 °C and 250 bar became hematite, dawsonite (NaAl(OH)2CO3), siderite (FeCO3) and quartz (SiO2). Experimentally, siderite and dawsonite, derived from the presence of kaolinite (Al2Si2O5(OH)4) in the parent material, were present in residual solids at longer reaction time intervals, which agreed well with results from the modelling work.

Ferrate treatment for removing chromium from high-level radioactive tank waste.

PubMed

Sylvester, P; Rutherford, L A; Gonzalez-Martin, A; Kim, J; Rapko, B M; Lumetta, G J

2001-01-01

A method has been developed for removing chromium from alkaline high-level radioactive tank waste. Removing chromium from these wastes is critical in reducing the volume of waste requiring expensive immobilization and deep geologic disposition. The method developed is based on the oxidation of insoluble chromium(III) compounds to soluble chromate using ferrate. This method could be generally applicable to removing chromium from chromium-contaminated solids, when coupled with a subsequent reduction of the separated chromate back to chromium(III). The tests conducted with a simulated Hanford tank sludge indicate that the chromium removal with ferrate is more efficient at 5 M NaOH than at 3 M NaOH. Chromium removal increases with increasing Fe(VI)/Cr(II) molar ratio, but the chromium removal tends to level out for Fe(VI)/ Cr(III) greaterthan 10. Increasingtemperature leadsto better chromium removal, but higher temperatures also led to more rapid ferrate decomposition. Tests with radioactive Hanford tank waste generally confirmed the simulant results. In all cases examined, ferrate enhanced the chromium removal, with a typical removal of around 60-70% of the total chromium present in the washed sludge solids. The ferrate leachate solutions did not contain significant concentrations of transuranic elements, so these solutions could be disposed as low-activity waste.

A new model for two-dimensional numerical simulation of pseudo-2D gas-solids fluidized beds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Tingwen; Zhang, Yongmin

2013-10-11

Pseudo-two dimensional (pseudo-2D) fluidized beds, for which the thickness of the system is much smaller than the other two dimensions, is widely used to perform fundamental studies on bubble behavior, solids mixing, or clustering phenomenon in different gas-solids fluidization systems. The abundant data from such experimental systems are very useful for numerical model development and validation. However, it has been reported that two-dimensional (2D) computational fluid dynamic (CFD) simulations of pseudo-2D gas-solids fluidized beds usually predict poor quantitative agreement with the experimental data, especially for the solids velocity field. In this paper, a new model is proposed to improve themore » 2D numerical simulations of pseudo-2D gas-solids fluidized beds by properly accounting for the frictional effect of the front and back walls. Two previously reported pseudo-2D experimental systems were simulated with this model. Compared to the traditional 2D simulations, significant improvements in the numerical predictions have been observed and the predicted results are in better agreement with the available experimental data.« less

Nitrogen oxides emissions from the MILD combustion with the conditions of recirculation gas.

PubMed

Park, Min; Shim, Sung Hoon; Jeong, Sang Hyun; Oh, Kwang-Joong; Lee, Sang-Sup

2017-04-01

The nitrogen oxides (NO x ) reduction technology by combustion modification which has economic benefits as a method of controlling NO x emitted in the combustion process, has recently been receiving a lot of attention. Especially, the moderate or intense low oxygen dilution (MILD) combustion which applied high temperature flue gas recirculation has been confirmed for its effectiveness with regard to solid fuel as well. MILD combustion is affected by the flue gas recirculation ratio and the composition of recirculation gas, so its NO x reduction efficiency is determined by them. In order to investigate the influence of factors which determine the reduction efficiency of NO x in MILD coal combustion, this study changed the flow rate and concentration of nitrogen (N 2 ), carbon dioxide (CO 2 ) and steam (H 2 O) which simulate the recirculation gas during the MILD coal combustion using our lab-scale drop tube furnace and performed the combustion experiment. As a result, its influence by the composition of recirculation gas was insignificant and it was shown that flue gas recirculation ratio influences the change of NO x concentration greatly. We investigated the influence of factors determining the nitrogen oxides (NO x ) reduction efficiency in MILD coal combustion, which applied high-temperature flue gas recirculation. Using a lab-scale drop tube furnace and simulated recirculation gas, we conducted combustion testing changing the recirculation gas conditions. We found that the flue gas recirculation ratio influences the reduction of NO x emissions the most.

Generator configuration for solid oxide fuel cells

DOEpatents

Reichner, Philip

1989-01-01

Disclosed are improvements in a solid oxide fuel cell generator 1 having a multiplicity of electrically connected solid oxide fuel cells 2, where a fuel gas is passed over one side of said cells and an oxygen-containing gas is passed over the other side of said cells resulting in the generation of heat and electricity. The improvements comprise arranging the cells in the configuration of a circle, a spiral, or folded rows within a cylindrical generator, and modifying the flow rate, oxygen concentration, and/or temperature of the oxygen-containing gases that flow to those cells that are at the periphery of the generator relative to those cells that are at the center of the generator. In these ways, a more uniform temperature is obtained throughout the generator.

An afterburner-powered methane/steam reformer for a solid oxide fuel cells application

NASA Astrophysics Data System (ADS)

Mozdzierz, Marcin; Chalusiak, Maciej; Kimijima, Shinji; Szmyd, Janusz S.; Brus, Grzegorz

2018-04-01

Solid oxide fuel cell (SOFC) systems can be fueled by natural gas when the reforming reaction is conducted in a stack. Due to its maturity and safety, indirect internal reforming is usually used. A strong endothermic methane/steam reforming process needs a large amount of heat, and it is convenient to provide thermal energy by burning the remainders of fuel from a cell. In this work, the mathematical model of afterburner-powered methane/steam reformer is proposed. To analyze the effect of a fuel composition on SOFC performance, the zero-dimensional model of a fuel cell connected with a reformer is formulated. It is shown that the highest efficiency of a solid oxide fuel cell is achieved when the steam-to-methane ratio at the reforming reactor inlet is high.

Direct ethanol solid oxide fuel cell operating in gradual internal reforming

NASA Astrophysics Data System (ADS)

Nobrega, S. D.; Galesco, M. V.; Girona, K.; de Florio, D. Z.; Steil, M. C.; Georges, S.; Fonseca, F. C.

2012-09-01

An electrolyte supported solid oxide fuel cell (SOFC) using standard electrodes, doped-lanthanum manganite cathode and Ni-cermet anode, was operated with direct (anhydrous) ethanol for more than 100 h, delivering essentially the same power output as running on hydrogen. A ceria-based layer provides the catalytic activity for the gradual internal reforming, which uses the steam formed by the electrochemical oxidation of hydrogen for the decomposition of ethanol. Such a concept opens up the way for multi-fuel SOFCs using standard components and a catalytic layer.

Method of making sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

DOEpatents

Isenberg, Arnold O.

1989-01-01

An electrochemical apparatus is made containing an exterior electorde bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

DOEpatents

Isenberg, Arnold O.

1987-01-01

An electrochemical apparatus is made containing an exterior electrode bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

An Analysis of the Loads on and Dynamic Response of a Floating Flexible Tube in Waves and Currents

DTIC Science & Technology

2014-05-09

the tube about 4.57 meters. The CFD code associated with the SolidWorks Flow Simulation tool was applied for this application. Flow Simulation uses...Liquid-Filled Membrane Structure in Waves," Journal of Fluids and Structures, no. 9, pp. 937-956, 1995. [16] SolidWorks , " Flow Simulation 2012...influence of Reynolds number on the drag coefficient. Simulations were performed with the 100% full (solid) model with flow velocities that yielded

Investigation of solid organic waste processing by oxidative pyrolysis

NASA Astrophysics Data System (ADS)

Kolibaba, O. B.; Sokolsky, A. I.; Gabitov, R. N.

2017-11-01

A thermal analysis of a mixture of municipal solid waste (MSW) of the average morphological composition and its individual components was carried out in order to develop ways to improve the efficiency of its utilization for energy production in thermal reactors. Experimental studies were performed on a synchronous thermal analyzer NETZSCH STA 449 F3 Jupiter combined with a quadrupole mass spectrometer QMC 403. Based on the results of the experiments, the temperature ranges of the pyrolysis process were determined as well as the rate of decrease of the mass of the sample of solid waste during the drying and oxidative pyrolysis processes, the thermal effects accompanying these processes, as well as the composition and volumes of gases produced during oxidative pyrolysis of solid waste and its components in an atmosphere with oxygen content of 1%, 5%, and 10%. On the basis of experimental data the dependences of the yield of gas on the moisture content of MSW were obtained under different pyrolysis conditions under which a gas of various calorific values was produced.

Study of ceria-carbonate nanocomposite electrolytes for low-temperature solid oxide fuel cells.

PubMed

Fan, L; Wang, C; Di, J; Chen, M; Zheng, J; Zhu, B

2012-06-01

Composite and nanocomposite samarium doped ceria-carbonates powders were prepared by solid-state reaction, citric acid-nitrate combustion and modified nanocomposite approaches and used as electrolytes for low temperature solid oxide fuel cells. X-ray Diffraction, Scanning Electron Microscope, low-temperature Nitrogen Adsorption/desorption Experiments, Electrochemical Impedance Spectroscopy and fuel cell performance test were employed in characterization of these materials. All powders are nano-size particles with slight aggregation and carbonates are amorphous in composites. Nanocomposite electrolyte exhibits much lower impedance resistance and higher ionic conductivity than those of the other electrolytes at lower temperature. Fuel cell using the electrolyte prepared by modified nanocomposite approach exhibits the best performance in the whole operation temperature range and achieves a maximum power density of 839 mW cm(-2) at 600 degrees C with H2 as fuel. The excellent physical and electrochemical performances of nanocomposite electrolyte make it a promising candidate for low-temperature solid oxide fuel cells.

PREFACE: Liquid-solid interfaces: structure and dynamics from spectroscopy and simulations Liquid-solid interfaces: structure and dynamics from spectroscopy and simulations

NASA Astrophysics Data System (ADS)

Gaigeot, Marie-Pierre; Sulpizi, Marialore

2012-03-01

Liquid-solid interfaces play an important role in a number of phenomena encountered in biological, chemical and physical processes. Surface-induced changes of the material properties are not only important for the solid support but also for the liquid itself. In particular, it is now well established that water at the interface is substantially different from bulk water, even in the proximity of apparently inert surfaces such as a simple metal. The complex chemistry at liquid-solid interfaces is typically fundamental to heterogeneous catalysis and electrochemistry, and has become especially topical in connection with the search for new materials for energy production. A quite remarkable example is the development of cheap yet efficient solar cells, whose basic components are dye molecules grafted to the surface of an oxide material and in contact with an electrolytic solution. In life science, the most important liquid-solid interfaces are the water-cell-membrane interfaces. Phenomena occurring at the surface of phospholipid bilayers control the docking of proteins, the transmission of signals as well as transport of molecules in and out of the cell. Recently the development of bio-compatible materials has lead to research on the interface between bio-compatible material and lipid/proteins in aqueous solution. Gaining a microscopic insight into the processes occurring at liquid-solid interfaces is therefore fundamental to a wide range of disciplines. This special section collects some contributions to the CECAM Workshop 'Liquid/Solid interfaces: Structure and Dynamics from Spectroscopy and Simulations' which took place in Lausanne, Switzerland in June 2011. Our main aim was to bring together knowledge and expertise from different communities in order to advance our microscopic understanding of the structure and dynamics of liquids at interfaces. In particular, one of our ambitions was to foster discussion between the experimental and theoretical/computational communities. On the experimental side, surface specific techniques, such as non-linear optical spectroscopy (sum frequency generation spectroscopy (SFG) and second harmonic generation (SHG)), surface sensitive x-ray scattering, in situ scanning tunneling microscopy (STM) and infrared reflection absorption spectroscopy provide information on layers of nanometric thickness at the interface. On the other hand, it is quite clear that the experiments require theoretical modelling in order to dissect the experimental results and to rationalize the different factors that contribute to the interfacial properties. In this respect molecular dynamics simulations are a major tool. While many successes have already been achieved with molecular dynamics simulations based on empirical force fields, first principles molecular dynamics simulations are now emerging as the other major approach where structure and reactivity are treated in a consistent way. Recent progress within the past 3-5 years on efficient treatments of basis sets and long range interactions in density functional theory (DFT) indeed extend such simulation capabilities to hundreds and thousands of atoms, thus allowing realistic models for interfaces to be tackled, maintaining first principles quality. Most of these simulations bring information on the structural organization of the solvent in the interfacial region between the solid and the liquid, but very few investigate the supplementary challenge of extracting vibrational spectroscopic fingerprints of the interface and, in particular, the direct modeling of the vibrational sum frequency generation (VSFG) non-linear spectra. The present special section reports an interesting contribution from the group of R Y Shen who pioneered VSFG optical experiments. They show how VSFG measurements can be used to unravel the behavior of interfacial water on alumina Al2O3 as a function of pH. The groups of A Hodgson and C Busse respectively provide complementary experiments based on low energy electron diffraction (LEED), He atom scattering (HAS) and STM, to investigate the organization of water on metal, namely Pd(111) and Pt(111). Direct measurements of hyperpolarizabilities for non-linear spectroscopy can be made through hyper-Rayleigh scattering experiments, which are presented here by the group of P F Brevet on gold and silver nanoparticles. From the point of view of molecular dynamics simulations of interfaces, complementary levels of calculations are presented in this special section. The groups of K Leung, M-P Gaigeot, M Sulpizi and M Sprik provide theoretical investigations with DFT-based molecular dynamics simulations. Leung et al and Gaigeot et al address the hot topic issue of the reactivity of oxides surface sites and especially reliable methods to calculate pKas of these sites, with simulations taking into account both the solid and the liquid explicitly, and at the same first principles level of theory. Gaigeot, Sprik and Sulpizi furthermore combine the information on the structural organization of liquid water at the interface with quartz and alumina via pKa calculations and vibrational features (and their microscopic assignments). Mixed quantum/classical molecular dynamics (QM/MM) simulations are presented by Ishiyama and Morita for the investigation of another topical interface, i.e. the liquid-air interface. They provide the theoretical VSFG spectrum of the water-vapor interface and some understanding at the microscopic level of the experimental vibrational features. Molecular dynamics simulations based on empirical force fields have been applied to investigate hydrophobic interfaces by the groups of B Space and P Carloni. Carloni et al address salt effects at water-hydrophobic interfaces, investigating how the salts affect the structural organization of water at these interfaces. Space et al provide theoretical approximations to VSFG calculations in the special case of the carbon tetrachloride-water interface and the assignments of the experimental recorded signatures. 'More traditional' DFT static calculations can be applied to complex objects at interfaces, providing their vibrational spectra, and two papers in this special section illustrate such approaches. Ceccet et al extract first hyperpolarizability tensors from DFT calculations on aliphatic chains and simulate the related VSFG spectra. They also investigate the effect of different functionals on the final signatures. Liegeois et al investigate functionalized surfaces, mainly focusing on IR and Raman spectral features, and provide very precise vibrational assignments depending on chemisorption or physisorption of the adsorbed molecules. We are grateful to all the authors for their contributions to this special section and we hope that readers will enjoy this collection of papers and that they will find further motivation to investigate and understand the complex phenomena occurring at interfaces. Liquid-solid interfaces contents The interfacial structure of water/protonated α-Al2O3 (112¯0) as a function of pHJ Sung, Y R Shen and G A Waychunas Strain relief and disorder in commensurate water layers formed on Pd(111)F McBride, A Omer, C M Clay, L Cummings, G R Darling and A Hodgson H2O on Pt(111): structure and stability of the first wetting layer Sebastian Standop, Markus Morgenstern, Thomas Michely and Carsten Busse Effect of a thioalkane capping layer on the first hyperpolarizabilities of gold and silver nanoparticles Yara El Harfouch, Emmanuel Benichou, Franck Bertorelle, Isabelle Russier-Antoine, Christian Jonin, Noelle Lascoux and Pierre F Brevet Predicting the acidity constant of a goethite hydroxyl group from first principlesKevin Leung and Louise J Criscenti Oxide/water interfaces: how the surface chemistry modifies interfacial water properties Marie-Pierre Gaigeot, Michiel Sprik and Marialore Sulpizi Vibrational spectrum at a water surface: a hybrid quantum mechanics/molecular mechanics molecular dynamics approach Tatsuya Ishiyama, Hideaki Takahashi and Akihiro Morita A theoretical study of the sum frequency vibrational spectroscopy of the carbon tetrachloride/water interface Anthony J Green, Angela Perry, Preston B Moore and Brian Space Salt effects on water/hydrophobic liquid interfaces: a molecular dynamics study Chao Zhang and Paolo Carloni Density functional theory-based simulations of sum frequency generation spectra involving methyl stretching vibrations: effect of the molecular model on the deduced molecular orientation and comparison with an analytical approach F Cecchet, D Lis, Y Caudano, A A Mani, A Peremans, B Champagne and J Guthmuller Towards modelling the vibrational signatures of functionalized surfaces: carboxylic acids on H-Si(111) surfaces Conrard Giresse Tetsassi Feugmo, Benoît Champagne, Yves Caudano, Francesca Cecchet, Yves J Chabal and Vincent Liégeois

Oxidation behaviour and electrical properties of cobalt/cerium oxide composite coatings for solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Harthøj, Anders; Holt, Tobias; Møller, Per

2015-05-01

This work evaluates the performance of cobalt/cerium oxide (Co/CeO2) composite coatings and pure Co coatings to be used for solid oxide fuel cell (SOFC) interconnects. The coatings are electroplated on the ferritic stainless steels Crofer 22 APU and Crofer 22H. Coated and uncoated samples are exposed in air at 800 °C for 3000 h and oxidation rates are measured and oxide scale microstructures are investigated. Area-specific resistances (ASR) in air at 850 °C of coated and uncoated samples are also measured. A dual layered oxide scale formed on all coated samples. The outer layer consisted of Co, Mn, Fe and Cr oxide and the inner layer consisted of Cr oxide. The CeO2 was present as discrete particles in the outer oxide layer after exposure. The Cr oxide layer thicknesses and oxidations rates were significantly reduced for Co/CeO2 coated samples compared to for Co coated and uncoated samples. The ASR of all Crofer 22H samples increased significantly faster than of Crofer 22 APU samples which was likely due to the presence of SiO2 in the oxide/metal interface of Crofer 22H.

Electrochemical degradation, kinetics & performance studies of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Das, Debanjan

Linear and Non-linear electrochemical characterization techniques and equivalent circuit modelling were carried out on miniature and sub-commercial Solid Oxide Fuel Cell (SOFC) stacks as an in-situ diagnostic approach to evaluate and analyze their performance under the presence of simulated alternative fuel conditions. The main focus of the study was to track the change in cell behavior and response live, as the cell was generating power. Electrochemical Impedance Spectroscopy (EIS) was the most important linear AC technique used for the study. The distinct effects of inorganic components usually present in hydrocarbon fuel reformates on SOFC behavior have been determined, allowing identification of possible "fingerprint" impedance behavior corresponding to specific fuel conditions and reaction mechanisms. Critical electrochemical processes and degradation mechanisms which might affect cell performance were identified and quantified. Sulfur and siloxane cause the most prominent degradation and the associated electrochemical cell parameters such as Gerisher and Warburg elements are applied respectively for better understanding of the degradation processes. Electrochemical Frequency Modulation (EFM) was applied for kinetic studies in SOFCs for the very first time for estimating the exchange current density and transfer coefficients. EFM is a non-linear in-situ electrochemical technique conceptually different from EIS and is used extensively in corrosion work, but rarely used on fuel cells till now. EFM is based on exploring information obtained from non-linear higher harmonic contributions from potential perturbations of electrochemical systems, otherwise not obtained by EIS. The baseline fuel used was 3 % humidified hydrogen with a 5-cell SOFC sub-commercial planar stack to perform the analysis. Traditional methods such as EIS and Tafel analysis were carried out at similar operating conditions to verify and correlate with the EFM data and ensure the validity of the obtained information. The obtained values closely range from around 11 mA cm-2 - 16 mA cm -2 with reasonable repeatability and excellent accuracy. The potential advantages of EFM compared to traditional methods were realized and our primary aim at demonstrating this technique on a SOFC system are presented which can act as a starting point for future research efforts in this area. Finally, an approach based on in-situ State of Health tests by EIS was formulated and investigated to understand the most efficient fuel conditions for suitable long term operation of a solid oxide fuel cell stack under power generation conditions. The procedure helped to reflect the individual effects of three most important fuel characteristics CO/H2 volumetric ratio, S/C ratio and fuel utilization under the presence of a simulated alternative fuel at 0.4 A cm-2. Variation tests helped to identify corresponding electrochemical/chemical processes, narrow down the most optimum operating regimes considering practical behavior of simulated reformer-SOFC system arrangements. At the end, 8 different combinations of the optimized parameters were tested long term with the stack, and the most efficient blend was determined.

Simulation of hydrodynamics using large eddy simulation-second-order moment model in circulating fluidized beds

NASA Astrophysics Data System (ADS)

Juhui, Chen; Yanjia, Tang; Dan, Li; Pengfei, Xu; Huilin, Lu

2013-07-01

Flow behavior of gas and particles is predicted by the large eddy simulation of gas-second order moment of solid model (LES-SOM model) in the simulation of flow behavior in CFB. This study shows that the simulated solid volume fractions along height using a two-dimensional model are in agreement with experiments. The velocity, volume fraction and second-order moments of particles are computed. The second-order moments of clusters are calculated. The solid volume fraction, velocity and second order moments are compared at the three different model constants.

Charge and discharge characteristics of lithium-ion graphite electrodes in solid-state cells

NASA Astrophysics Data System (ADS)

Lemont, S.; Billaud, D.

Lithium ions have been electrochemically intercalated into graphite in solid-state cells operating with solid polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO 4). The working composite electrode is composed of active-divided natural graphite associated with P(EO) 8-LiClO 4 acting as a binder and a Li + ionic conductor. Intercalation and de-intercalation of Li + were performed using galvanostatic or voltammetry techniques. The curves obtained in our solid-state cells were compared with those performed in liquid ethylene carbonate-LiClO 4 electrolyte. It is shown that in solid-state cells, side reactions occur both in the reduction and in the oxidation processes which leads to some uncertainty in the determination of the maximum reversible capacity of the graphite material.

LABORATORY STUDY ON THE OXIDATION OF ARSENIC III TO ARSENIC V

EPA Science Inventory

A one-year laboratory study was performed to determine the ability of seven oxidants to oxidize As(III) to As(V). These included chlorine, permanganate, ozone, chlorine dioxide, monochloramine, a solid-phase oxidizing media, and 254 nm ultraviolet light. Chlorine and permanganate...

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity

DOEpatents

Skotheim, Terje

1986-01-01

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity

DOEpatents

Skotheim, T.

1984-09-28

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Nanoscale science and engineering forum (706c) design of solid lipid particles with iron oxide quantum dots for the delivery of therapeutic agents

USDA-ARS?s Scientific Manuscript database

Solid lipid particles provide a method to encapsulate and control the release of drugs in vivo but lack the imaging capability provided by CdS quantum dots. This shortcoming was addressed by combining these two technologies into a model system that uses iron oxide as a non-toxic imaging component in...

Plume Particle Collection and Sizing from Static Firing of Solid Rocket Motors

NASA Technical Reports Server (NTRS)

Sambamurthi, Jay K.

1995-01-01

Thermal radiation from the plume of any solid rocket motor, containing aluminum as one of the propellant ingredients, is mainly from the microscopic, hot aluminum oxide particles in the plume. The plume radiation to the base components of the flight vehicle is primarily determined by the plume flowfield properties, the size distribution of the plume particles, and their optical properties. The optimum design of a vehicle base thermal protection system is dependent on the ability to accurately predict this intense thermal radiation using validated theoretical models. This article describes a successful effort to collect reasonably clean plume particle samples from the static firing of the flight simulation motor (FSM-4) on March 10, 1994 at the T-24 test bed at the Thiokol space operations facility as well as three 18.3% scaled MNASA motors tested at NASA/MSFC. Prior attempts to collect plume particles from the full-scale motor firings have been unsuccessful due to the extremely hostile thermal and acoustic environment in the vicinity of the motor nozzle.

MODELLING OF FUEL BEHAVIOUR DURING LOSS-OF-COOLANT ACCIDENTS USING THE BISON CODE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pastore, G.; Novascone, S. R.; Williamson, R. L.

2015-09-01

This work presents recent developments to extend the BISON code to enable fuel performance analysis during LOCAs. This newly developed capability accounts for the main physical phenomena involved, as well as the interactions among them and with the global fuel rod thermo-mechanical analysis. Specifically, new multiphysics models are incorporated in the code to describe (1) transient fission gas behaviour, (2) rapid steam-cladding oxidation, (3) Zircaloy solid-solid phase transition, (4) hydrogen generation and transport through the cladding, and (5) Zircaloy high-temperature non-linear mechanical behaviour and failure. Basic model characteristics are described, and a demonstration BISON analysis of a LWR fuel rodmore » undergoing a LOCA accident is presented. Also, as a first step of validation, the code with the new capability is applied to the simulation of experiments investigating cladding behaviour under LOCA conditions. The comparison of the results with the available experimental data of cladding failure due to burst is presented.« less

An Aurivillius Oxide Based Cathode with Excellent CO2 Tolerance for Intermediate-Temperature Solid Oxide Fuel Cells.

PubMed

Zhu, Yinlong; Zhou, Wei; Chen, Yubo; Shao, Zongping

2016-07-25

The Aurivillius oxide Bi2 Sr2 Nb2 MnO12-δ (BSNM) was used as a cobalt-free cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). To the best of our knowledge, the BSNM oxide is the only alkaline-earth-containing cathode material with complete CO2 tolerance that has been reported thus far. BSNM not only shows favorable activity in the oxygen reduction reaction (ORR) at intermediate temperatures but also exhibits a low thermal expansion coefficient, excellent structural stability, and good chemical compatibility with the electrolyte. These features highlight the potential of the new BSNM material as a highly promising cathode material for IT-SOFCs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extinguishment of a Diffusion Flame Over a PMMA Cylinder by Depressurization in Reduced-Gravity

NASA Technical Reports Server (NTRS)

Goldmeer, Jeffrey Scott

1996-01-01

Extinction of a diffusion flame burning over horizontal PMMA (Polymethyl methacrylate) cylinders in low-gravity was examined experimentally and via numerical simulations. Low-gravity conditions were obtained using the NASA Lewis Research Center's reduced-gravity aircraft. The effects of velocity and pressure on the visible flame were examined. The flammability of the burning solid was examined as a function of pressure and the solid-phase centerline temperature. As the solid temperature increased, the extinction pressure decreased, and with a centerline temperature of 525 K, the flame was sustained to 0.1 atmospheres before extinguishing. The numerical simulation iteratively coupled a two-dimensional quasi-steady, gas-phase model with a transient solid-phase model which included conductive heat transfer and surface regression. This model employed an energy balance at the gas/solid interface that included the energy conducted by the gas-phase to the gas/solid interface, Arrhenius pyrolysis kinetics, surface radiation, and the energy conducted into the solid. The ratio of the solid and gas-phase conductive fluxes Phi was a boundary condition for the gas-phase model at the solid-surface. Initial simulations modeled conditions similar to the low-gravity experiments and predicted low-pressure extinction limits consistent with the experimental limits. Other simulations examined the effects of velocity, depressurization rate and Phi on extinction.

Fiber lubrication: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Liu, Hongyi

Molecular and mesoscopic level description of friction and lubrication remains a challenge because of difficulties in the phenomenological understanding of to the behaviors of solid-liquid interfaces during sliding. Fortunately, there is the computational simulation approach opens an opportunity to predict and analyze interfacial phenomena, which were studied with molecular dynamics (MD) and mesoscopic dynamics (MesoDyn) simulations. Polypropylene (PP) and cellulose are two of most common polymers in textile fibers. Confined amorphous surface layers of PP and cellulose were built successfully with xenon crystals which were used to compact the polymers. The physical and surface properties of the PP and cellulose surface layers were investigated by MD simulations, including the density, cohesive energy, volumetric thermal expansion, and contact angle with water. The topology method was employed to predict the properties of poly(alkylene glycol) (PAG) diblock copolymers and Pluronic triblock copolymers used as lubricants on surfaces. Density, zero shear viscosity, shear module, cohesive energy and solubility parameter were predicted with each block copolymer. Molecular dynamics simulations were used to study the interaction energy per unit contact area of block copolymer melts with PP and cellulose surfaces. The interaction energy is defined as the ratio of interfacial interaction energy to the contact area. Both poly(proplene oxide) (PPO) and poly(ethylene oxide) (PEO) segments provided a lipophilic character to both PP and cellulose surfaces. The PPO/PEO ratio and the molecular weight were found to impact the interaction energy on both PP and cellulose surfaces. In aqueous solutions, the interaction energy is complicated due to the presence of water and the cross interactions between the multiple molecular components. The polymer-water-surface (PWS) calculation method was proposed to calculate such complex systems. In a contrast with a vacuum condition, the presence of water increases the attractive interaction energy of the diblock copolymer on the cellulose surface, compared with that on the PP surface. Water decreases the interaction energy of the triblock copolymer on the cellulose surface, compared with that on the PP surface. MesoDyn was adopted to investigate the self-assembled morphology of the triblock copolymer, in aqueous solution, confined and sheared at solid-liquid interfaces. In a bulk aqueous solution, when the polymer concentration reached 10% v/v, micelles were observed with PPO blocks in the core and PEO blocks in the shell of the micelles. At the concentrations of 25% and 50%, worm-like micelles and irregular cylinders were observed in solutions, respectively. The micelles were formed faster in aqueous solutions confined by cellulose surfaces than that in the bulk. The formed micelles were broken under shearing, which led to a depletion of polymers at the interfaces. During the shearing on the PP surfaces, the polymers were adsorbed on the surfaces protecting the PP surfaces. This simulation study in the fiber lubrication was in good agreement with the experimental results and so provided an approach to visualize the polymer configuration at the liquid-solid interface, predict the lubricant-surface systems, and theoretically guide the experiments of designing new/efficient lubricants for fibers.

An aeration control strategy for oxidation ditch processes based on online oxygen requirement estimation.

PubMed

Zhan, J X; Ikehata, M; Mayuzumi, M; Koizumi, E; Kawaguchi, Y; Hashimoto, T

2013-01-01

A feedforward-feedback aeration control strategy based on online oxygen requirements (OR) estimation is proposed for oxidation ditch (OD) processes, and it is further developed for intermittent aeration OD processes, which are the most popular type in Japan. For calculating OR, concentrations of influent biochemical oxygen demand (BOD) and total Kjeldahl nitrogen (TKN) are estimated online by the measurement of suspended solids (SS) and sometimes TKN is estimated by NH4-N. Mixed liquor suspended solids (MLSS) and temperature are used to estimate the required oxygen for endogenous respiration. A straightforward parameter named aeration coefficient, Ka, is introduced as the only parameter that can be tuned automatically by feedback control or manually by the operators. Simulation with an activated sludge model was performed in comparison to fixed-interval aeration and satisfying result of OR control strategy was obtained. The OR control strategy has been implemented at seven full-scale OD plants and improvements in nitrogen removal are obtained in all these plants. Among them, the results obtained in Yumoto wastewater treatment plant were presented, in which continuous aeration was applied previously. After implementing intermittent OR control, the total nitrogen concentration was reduced from more than 5 mg/L to under 2 mg/L, and the electricity consumption was reduced by 61.2% for aeration or 21.5% for the whole plant.

Promoting the ambient-condition stability of Zr-doped barium cerate: Toward robust solid oxide fuel cells and hydrogen separation in syngas

NASA Astrophysics Data System (ADS)

Yang, Ying; Zeng, Yimin; Amirkhiz, Babak S.; Luo, Jing-Li; Yan, Ning

2018-02-01

Increasing the stability of perovskite proton conductor against atmospheric CO2 and moisture attack at ambient conditions might be equally important as that at the elevated service temperatures. It can ease the transportation and storage of materials, potentially reducing the maintenance cost of the integral devices. In this work, we initially examined the surface degradation behaviors of various Zr-doped barium cerates (BaCe0.7Zr0.1Y0.1Me0.1O3) using XRD, SEM, STEM and electron energy loss spectroscopy. Though that the typical lanthanide (Y, Yb and Gd) and In incorporated Zr-doped cerates well resisted CO2-induced carbonation in air at elevated temperatures, they were unfortunately vulnerable at ambient conditions, suffering slow decompositions at the surface. Conversely, Sn doped samples (BCZYSn) were robust at both conditions yet showed high protonic conductivity. Thanks to that, the anode supported solid oxide fuel cells equipped with BCZYSn electrolyte delivered a maximum power density of 387 mW cm-2 at 600 °C in simulated coal-derived syngas. In the hydrogen permeation test using BCZYSn based membrane, the H2 flux reached 0.11 mL cm-2 min-1 at 850 °C when syngas was the feedstock. Both devices demonstrated excellent stability in the presence of CO2 in the syngas.

Stall/surge dynamics of a multi-stage air compressor in response to a load transient of a hybrid solid oxide fuel cell-gas turbine system

NASA Astrophysics Data System (ADS)

Azizi, Mohammad Ali; Brouwer, Jacob

2017-10-01

A better understanding of turbulent unsteady flows in gas turbine systems is necessary to design and control compressors for hybrid fuel cell-gas turbine systems. Compressor stall/surge analysis for a 4 MW hybrid solid oxide fuel cell-gas turbine system for locomotive applications is performed based upon a 1.7 MW multi-stage air compressor. Control strategies are applied to prevent operation of the hybrid SOFC-GT beyond the stall/surge lines of the compressor. Computational fluid dynamics tools are used to simulate the flow distribution and instabilities near the stall/surge line. The results show that a 1.7 MW system compressor like that of a Kawasaki gas turbine is an appropriate choice among the industrial compressors to be used in a 4 MW locomotive SOFC-GT with topping cycle design. The multi-stage radial design of the compressor enhances the ability of the compressor to maintain air flow rate during transient step-load changes. These transient step-load changes are exhibited in many potential applications for SOFC/GT systems. The compressor provides sustained air flow rate during the mild stall/surge event that occurs due to the transient step-load change that is applied, indicating that this type of compressor is well-suited for this hybrid application.

Self-healing atmospheric plasma sprayed Mn1.0Co1.9Fe0.1O4 protective interconnector coatings for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Grünwald, Nikolas; Sebold, Doris; Sohn, Yoo Jung; Menzler, Norbert Heribert; Vaßen, Robert

2017-09-01

Dense coatings on metallic interconnectors are necessary to suppress chromium poisoning of SOFC cathodes. Atmospherically plasma sprayed (APS) Mn1.0Co1.9Fe0.1O4 (MCF) protective layers demonstrated reduced chromium related degradation in laboratory and stack tests. Previous analyses revealed strong microstructural changes comparing the coating's as-sprayed and operated condition. This work concentrates on the layer-densification and crack-healing observed by annealing APS-MCF in air, which simulates the cathode operation conditions. The effect is described by a volume expansion induced by a phase transformation. Reducing conditions during the spray process lead to a deposition of the MCF in a metastable rock salt configuration. Annealing in air activates diffusion processes for a phase transformation to the low temperature stable spinel phase (T < 1050 °C). This transformation is connected to an oxygen incorporation which occurs at regions facing high oxygen partial pressures, as there are the sample surface, cracks and pore surfaces. Calculations reveal a volume expansion induced by the oxygen uptake which seals the cracks and densifies the coating. The process decelerates when the cracks are closed, as the gas route is blocked and further oxidation continues over solid state diffusion. The self-healing abilities of metastable APS coatings could be interesting for other applications.

Evaluation of a pilot-scale sewage biogas powered 2.8 kWe Solid Oxide Fuel Cell: Assessment of heat-to-power ratio and influence of oxygen content

NASA Astrophysics Data System (ADS)

de Arespacochaga, N.; Valderrama, C.; Peregrina, C.; Mesa, C.; Bouchy, L.; Cortina, J. L.

2015-12-01

Biogas from anaerobic digestion of organic matter is a promising renewable energy source and fuel cells appear as a breakthrough technology to improve the performance of the biogas-to-energy valorisation chain. The vast majority of studies addressing biogas energy recovery through Solid Oxide Fuel Cells published in recent years correspond to simulations and lab-scale performance with synthetic biogas. This paper assesses the pilot performance of a 2.8 kWe SOFC unit powered with cleaned sewage biogas for around 700 h in a Wastewater Treatment Plant. The biogas thorough treatment consisting of a biological desulphurisation with a biotrickling filter followed by a deep cleaning step based on adsorption is successful for removing sulphur compounds, siloxanes and hydrocarbons. The influence of the heat-to-power ratio on fuel cell performance is investigated operating the system at O/C ratio of 2, reforming temperature of 550 °C, stack temperature of 800 °C and at a constant voltage of 43 V. At optimized conditions for electrical production satisfying heat demand in the WWTP, system electrical and thermal efficiencies account for 34% and 28%. Cogeneration efficiency remains constant at around 59-62% for all the heat-to-power ratios tested. Furthermore, the impact of the oxygen content in the biogas is also studied.

The surface evolution of La0.4Sr0.6TiO3+δ anode in solid oxide fuel cells: Understanding the sulfur-promotion effect

NASA Astrophysics Data System (ADS)

Yan, Ning; Zanna, Sandrine; Klein, Lorena H.; Roushanafshar, Milad; Amirkhiz, Babak S.; Zeng, Yimin; Rothenberg, Gadi; Marcus, Philippe; Luo, Jing-Li

2017-03-01

The ideal solid oxide fuel cells (SOFCs) can be powered by readily available hydrocarbon fuels containing impurities. While this is commonly recognized as a key advantage of SOFC, it also, together with the elevated operating temperature, becomes the main barrier impeding the in-situ or operando investigations of the anode surface chemistry. Here, using a well-designed quenching experiment, we managed to characterize the near-surface structure of La0.4Sr0.6TiO3+δ (LST) anode in SOFCs fuelled by H2S-containing methane. This new method enabled us to clearly observe the surface amorphization and sulfidation of LST under simulated SOFC operating conditions. The ∼1 nm-thick two dimensional sulfur-adsorbed layer was on top of the disordered LST, containing -S, -SH and elemental sulfur species. In SOFC test, such "poisoned" anode showed increased performances: a ten-fold enhanced power density enhancement (up to 30 mW cm-2) and an improved open circuit voltage (from 0.69 V to 1.17 V). Moreover, its anodic polarization resistance in methane decreased to 21.53 Ω cm2, a difference of 95% compared with the sulfur-free anode. Control experiments confirmed that once the adsorbed sulfur species were removed electrochemically, methane conversion slowed down simultaneously till full stop.

Method and system for the removal of oxides of nitrogen and sulfur from combustion processes

DOEpatents

Walsh, John V.

1987-12-15

A process for removing oxide contaminants from combustion gas, and employing a solid electrolyte reactor, includes: (a) flowing the combustion gas into a zone containing a solid electrolyte and applying a voltage and at elevated temperature to thereby separate oxygen via the solid electrolyte, (b) removing oxygen from that zone in a first stream and removing hot effluent gas from that zone in a second stream, the effluent gas containing contaminant, (c) and pre-heating the combustion gas flowing to that zone by passing it in heat exchange relation with the hot effluent gas.

Self-propagating solar light reduction of graphite oxide in water

NASA Astrophysics Data System (ADS)

Todorova, N.; Giannakopoulou, T.; Boukos, N.; Vermisoglou, E.; Lekakou, C.; Trapalis, C.

2017-01-01

Graphite Oxide (GtO) is commonly used as an intermediate material for preparation of graphene in the form of reduced graphene oxide (rGO). Being a semiconductor with tunable band gap rGO is often coupled with various photocatalysts to enhance their visible light activity. The behavior of such rGO-based composites could be affected after prolonged exposure to solar light. In the present work, the alteration of the GtO properties under solar light irradiation is investigated. Water dispersions of GtO manufactured by oxidation of natural graphite via Hummers method were irradiated into solar light simulator for different periods of time without addition of catalysts or reductive agent. The FT-IR analysis of the treated dispersions revealed gradual reduction of the GtO with the increase of the irradiation time. The XRD, FT-IR and XPS analyses of the obtained solid materials confirmed the transition of GtO to rGO under solar light irradiation. The reduction of the GtO was also manifested by the CV measurements that revealed stepwise increase of the specific capacitance connected with the restoration of the sp2 domains. Photothermal self-propagating reduction of graphene oxide in aqueous media under solar light irradiation is suggested as a possible mechanism. The self-photoreduction of GtO utilizing solar light provides a green, sustainable route towards preparation of reduced graphene oxide. However, the instability of the GtO and partially reduced GO under irradiation should be considered when choosing the field of its application.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bundy, R.D.; Alderfer, R.B.

Bench-scale tests of the direct calcination process for Portsmouth were conducted using batch pot calcination of simulated and actual raffinate wastes. These studies included investigation of the evaporation step needed to concentrate the raffinate before calcination. Tests were conducted at calcination temperatures of 600, 700, 1000, and 1200/sup 0/F with two levels of evaporative concentration before calcination at 1000/sup 0/F. Evaporation only tests were also made. Performance of the bench-scale system was excellent. A calcination temperature of 715/sup 0/F indicated that 80 to 100% of the Tc was retained in the calcined solids, while all of the nitrates were decomposedmore » to oxides. With calcination temperatures of greater than or equal to 1000/sup 0/F, part of the Tc escaped from the calcination pot to the scrubber. Below 700/sup 0/F, not all of the nitrates were decomposed to oxides. Most of the U remained in the calcined solids for calcination temperatures of less than or equal to 1000/sup 0/F. The mass of solids remaining after calcination was 4 to 5% of the original raffinate for calcination temperatures from 700 to 1000/sup 0/F. Flow rate through the off-gas treatment system was variable. The water scrubber had a good removal efficiency for nitrate and most metals, but not for uranium. The trapping efficiency of the limestone trap for nitrate was low. Flowsheet studies indicate that enough U would pass through the scrubber and chemical traps to cause an unacceptably high release of radioactivity if the assay of the uranium exceeded 33%. A small HEPA filter after the limestone chemical traps is recommended to reduce U emissions. A flowsheet was developed for a full-scale process for the direct calcination of raffinate waste.« less

Assessment of solid/liquid equilibria in the (U, Zr)O2+y system

NASA Astrophysics Data System (ADS)

Mastromarino, S.; Seibert, A.; Hashem, E.; Ciccioli, A.; Prieur, D.; Scheinost, A.; Stohr, S.; Lajarge, P.; Boshoven, J.; Robba, D.; Ernstberger, M.; Bottomley, D.; Manara, D.

2017-10-01

Solid/liquid equilibria in the system UO2sbnd ZrO2 are revisited in this work by laser heating coupled with fast optical thermometry. Phase transition points newly measured under inert gas are in fair agreement with the early measurements performed by Wisnyi et al., in 1957, the only study available in the literature on the whole pseudo-binary system. In addition, a minimum melting point is identified here for compositions near (U0.6Zr0.4)O2+y, around 2800 K. The solidus line is rather flat on a broad range of compositions around the minimum. It increases for compositions closer to the pure end members, up to the melting point of pure UO2 (3130 K) on one side and pure ZrO2 (2970 K) on the other. Solid state phase transitions (cubic-tetragonal-monoclinic) have also been observed in the ZrO2-rich compositions X-ray diffraction. Investigations under 0.3 MPa air (0.063 MPa O2) revealed a significant decrease in the melting points down to 2500 K-2600 K for increasing uranium content (x(UO2)> 0.2). This was found to be related to further oxidation of uranium dioxide, confirmed by X-ray absorption spectroscopy. For example, a typical oxidised corium composition U0.6Zr0.4O2.13 was observed to solidify at a temperature as low as 2493 K. The current results are important for assessing the thermal stability of the system fuel - cladding in an oxide based nuclear reactor, and for simulating the system behaviour during a hypothetical severe accident.

Formation of self-organized nanoporous anodic oxide from metallic gallium.

PubMed

Pandey, Bipin; Thapa, Prem S; Higgins, Daniel A; Ito, Takashi

2012-09-25

This paper reports the formation of self-organized nanoporous gallium oxide by anodization of solid gallium metal. Because of its low melting point (ca. 30 °C), metallic gallium can be shaped into flexible structures, permitting the fabrication of nanoporous anodic oxide monoliths within confined spaces like the inside of a microchannel. Here, solid gallium films prepared on planar substrates were employed to investigate the effects of anodization voltage (1, 5, 10, 15 V) and H(2)SO(4) concentration (1, 2, 4, 6 M) on anodic oxide morphology. Self-organized nanopores aligned perpendicular to the film surface were obtained upon anodization of gallium films in ice-cooled 4 and 6 M aqueous H(2)SO(4) at 10 and 15 V. Nanopore formation could be recognized by an increase in anodic current after a current decrease reflecting barrier oxide formation. The average pore diameter was in the range of 18-40 nm with a narrow diameter distribution (relative standard deviation ca. 10-20%), and was larger at lower H(2)SO(4) concentration and higher applied voltage. The maximum thickness of nanoporous anodic oxide was ca. 2 μm. In addition, anodic formation of self-organized nanopores was demonstrated for a solid gallium monolith incorporated at the end of a glass capillary. Nanoporous anodic oxide monoliths formed from a fusible metal will lead to future development of unique devices for chemical sensing and catalysis.

Zinc oxide crystal whiskers as a novel sorbent for solid-phase extraction of flavonoids.

PubMed

Wang, Licheng; Shangguan, Yangnan; Hou, Xiudan; Jia, Yong; Liu, Shujuan; Sun, Yingxin; Guo, Yong

2017-08-15

As a novel solid-phase extraction material, zinc oxide crystal whiskers were used to extract flavonoid compounds and showed good extraction abilities. X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy and surface area/pore volume characterized the sorbent. The zinc oxide was packed into a solid-phase extraction micro-column and its extraction ability was evaluated by four model flavonoid compounds. The sample loading and elution parameters were optimized and the zinc oxide based analytical method for flavonoids was established. It showed that the method has wide linearities from 1 to 150μg/L and low limits of detection at 0.25μg/L. The relative standard deviations of a single column repeatability and column to column reproducibility were less than 6.8% and 10.6%. Several real samples were analyzed by the established method and satisfactory results were obtained. The interactions between flavonoids and zinc oxide were calculated and proved to be from the Van der Waals' forces between the 4p and 5d orbitals from zinc atom and the neighboring π orbitals from flavonoid phenyl groups. Moreover, the zinc oxide crystal whiskers showed good stability and could be reused more than 50 times under the operation conditions. This work proves that the zinc oxide crystal whiskers are a good candidate for flavonoids enrichment. Copyright © 2017. Published by Elsevier B.V.

Respiration of metal (hydr)oxides by Shewanella and Geobacter: a key role for multihaem c-type cytochromes

PubMed Central

Shi, Liang; Squier, Thomas C; Zachara, John M; Fredrickson, James K

2007-01-01

Dissimilatory reduction of metal (e.g. Fe, Mn) (hydr)oxides represents a challenge for microorganisms, as their cell envelopes are impermeable to metal (hydr)oxides that are poorly soluble in water. To overcome this physical barrier, the Gram-negative bacteria Shewanella oneidensis MR-1 and Geobacter sulfurreducens have developed electron transfer (ET) strategies that require multihaem c-type cytochromes (c-Cyts). In S. oneidensis MR-1, multihaem c-Cyts CymA and MtrA are believed to transfer electrons from the inner membrane quinone/quinol pool through the periplasm to the outer membrane. The type II secretion system of S. oneidensis MR-1 has been implicated in the reduction of metal (hydr)oxides, most likely by translocating decahaem c-Cyts MtrC and OmcA across outer membrane to the surface of bacterial cells where they form a protein complex. The extracellular MtrC and OmcA can directly reduce solid metal (hydr)oxides. Likewise, outer membrane multihaem c-Cyts OmcE and OmcS of G. sulfurreducens are suggested to transfer electrons from outer membrane to type IV pili that are hypothesized to relay the electrons to solid metal (hydr)oxides. Thus, multihaem c-Cyts play critical roles in S. oneidensis MR-1- and G. sulfurreducens-mediated dissimilatory reduction of solid metal (hydr)oxides by facilitating ET across the bacterial cell envelope. PMID:17581116

Molecular beam epitaxy growth of niobium oxides by solid/liquid state oxygen source and lithium assisted metal-halide chemistry

NASA Astrophysics Data System (ADS)

Tellekamp, M. Brooks; Greenlee, Jordan D.; Shank, Joshua C.; Doolittle, W. Alan

2015-09-01

In order to consistently grow high quality niobium oxides and lithium niobium oxides, a novel solid/liquid state oxygen source, LiClO4, has been implemented in a molecular beam epitaxy (MBE) system. LiClO4 is shown to decompose into both molecular and atomic oxygen upon heating. This allows oxidation rates similar to that of molecular oxygen but at a reduced overall beam flux, quantified by in situ Auger analysis. LiClO4 operation is decomposition limited to less than 400 °C, and other material limitations are identified. The design of a custom near-ambient NbCl5 effusion cell is presented, which improves both short and long term stability. Films of Nb oxidation state +2, +3, and +5 are grown using these new tools, including the multi-functional sub-oxide LiNbO2.

Ceramification: A plutonium immobilization process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rask, W.C.; Phillips, A.G.

1996-05-01

This paper describes a low temperature technique for stabilizing and immobilizing actinide compounds using a combination process/storage vessel of stainless steel, in which measured amounts of actinide nitrate solutions and actinide oxides (and/or residues) are systematically treated to yield a solid article. The chemical ceramic process is based on a coating technology that produces rare earth oxide coatings for defense applications involving plutonium. The final product of this application is a solid, coherent actinide oxide with process-generated encapsulation that has long-term environmental stability. Actinide compounds can be stabilized as pure materials for ease of re-use or as intimate mixtures withmore » additives such as rare earth oxides to increase their degree of proliferation resistance. Starting materials for the process can include nitrate solutions, powders, aggregates, sludges, incinerator ashes, and others. Agents such as cerium oxide or zirconium oxide may be added as powders or precursors to enhance the properties of the resulting solid product. Additives may be included to produce a final product suitable for use in nuclear fuel pellet production. The process is simple and reduces the time and expense for stabilizing plutonium compounds. It requires a very low equipment expenditure and can be readily implemented into existing gloveboxes. The process is easily conducted with less associated risk than proposed alternative technologies.« less

Nitrous Oxide/Paraffin Hybrid Rocket Engines

NASA Technical Reports Server (NTRS)

Zubrin, Robert; Snyder, Gary

2010-01-01

Nitrous oxide/paraffin (N2OP) hybrid rocket engines have been invented as alternatives to other rocket engines especially those that burn granular, rubbery solid fuels consisting largely of hydroxyl- terminated polybutadiene (HTPB). Originally intended for use in launching spacecraft, these engines would also be suitable for terrestrial use in rocket-assisted takeoff of small airplanes. The main novel features of these engines are (1) the use of reinforced paraffin as the fuel and (2) the use of nitrous oxide as the oxidizer. Hybrid (solid-fuel/fluid-oxidizer) rocket engines offer advantages of safety and simplicity over fluid-bipropellant (fluid-fuel/fluid-oxidizer) rocket en - gines, but the thrusts of HTPB-based hybrid rocket engines are limited by the low regression rates of the fuel grains. Paraffin used as a solid fuel has a regression rate about 4 times that of HTPB, but pure paraffin fuel grains soften when heated; hence, paraffin fuel grains can, potentially, slump during firing. In a hybrid engine of the present type, the paraffin is molded into a 3-volume-percent graphite sponge or similar carbon matrix, which supports the paraffin against slumping during firing. In addition, because the carbon matrix material burns along with the paraffin, engine performance is not appreciably degraded by use of the matrix.

Room-Temperature Performance of Poly(Ethylene Ether Carbonate)-Based Solid Polymer Electrolytes for All-Solid-State Lithium Batteries.

PubMed

Jung, Yun-Chae; Park, Myung-Soo; Kim, Duck-Hyun; Ue, Makoto; Eftekhari, Ali; Kim, Dong-Won

2017-12-13

Amorphous poly(ethylene ether carbonate) (PEEC), which is a copolymer of ethylene oxide and ethylene carbonate, was synthesized by ring-opening polymerization of ethylene carbonate. This route overcame the common issue of low conductivity of poly(ethylene oxide)(PEO)-based solid polymer electrolytes at low temperatures, and thus the solid polymer electrolyte could be successfully employed at the room temperature. Introducing the ethylene carbonate units into PEEC improved the ionic conductivity, electrochemical stability and lithium transference number compared with PEO. A cross-linked solid polymer electrolyte was synthesized by photo cross-linking reaction using PEEC and tetraethyleneglycol diacrylate as a cross-linking agent, in the form of a flexible thin film. The solid-state Li/LiNi 0.6 Co 0.2 Mn 0.2 O 2 cell assembled with solid polymer electrolyte based on cross-linked PEEC delivered a high initial discharge capacity of 141.4 mAh g -1 and exhibited good capacity retention at room temperature. These results demonstrate the feasibility of using this solid polymer electrolyte in all-solid-state lithium batteries that can operate at ambient temperatures.

Ignition kinetics of boron in primary combustion products of propellant based on its unique characteristics

NASA Astrophysics Data System (ADS)

Ao, Wen; Wang, Yang; Wu, Shixi

2017-07-01

Study on the boron-based primary combustion products can bridge the gap between primary combustion and secondary combustion in solid rocket ramjets. To clarify the initial state and ignition characteristics of boron particles in the after-burning chamber of solid rocket ramjets, the elemental, composition and morphology of the primary combustion products collected under gas generator chamber pressure of 0.2 MPa and 6 MPa were investigated by energy dispersive (EDS), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy with energy dispersive (SEM-EDS) individually. The ignition times of boron particles among the primary combustion products were determined using a high temperature tube furnace system. The BD model was adopted for numerical verification. The numerical solution procedure of boron ignition model in a real afterburner chamber was modified. The results show that the sum of B, C, O elements in the primary combustion products reaches approximately 90%. The primary combustion products are mainly consisted of B, C, and B2O3. Images of the primary combustion products present highly agglomeration, indicating an oxidation of boron surface. Numerous spherical carbon particles with a diameter around 100 nm are observed in the products. Three features of the boron in the primary combustion products are obtained, compared to virgin boron. First most of the boron lumps are covered by carbon particles on the surface. Second the mean particle size is five times larger than that of virgin boron. Third the overall initial oxide layer covered on boron surface increases its thickness by above 0.1 μm. The ignition time of boron in the primary combustion products reaches 20-30 ms under 1673-1873 K, which is quite different from virgin boron of 4 ms. Numerical calculation results show the key reason leading to such a long ignition time is the variation of the initial oxide layer thickness. In conclusion, the physicochemical properties of boron particles are found to differ with virgin boron after primary combustion process. The accurate evaluation of the initial oxide layer thickness and initial particle radius is a crucial procedure before the numerical calculation of boron ignition kinetics. Results of our study are expected to provide better insight in the simulation of solid rocket ramjets working process.

Hydrolysis of ferric chloride in solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lussiez, G.; Beckstead, L.

1996-11-01

The Detox{trademark} process uses concentrated ferric chloride and small amounts of catalysts to oxidize organic compounds. It is under consideration for oxidizing transuranic organic wastes. Although the solution is reused extensively, at some point it will reach the acceptable limit of radioactivity or maximum solubility of the radioisotopes. This solution could be cemented, but the volume would be increased substantially because of the poor compatibility of chlorides and cement. A process has been developed that recovers the chloride ions as HCl and either minimizes the volume of radioactive waste or permits recycling of the radioactive chlorides. The process involves amore » two-step hydrolysis at atmospheric pressure, or preferably under a slight vacuum, and relatively low temperature, about 200{degrees}C. During the first step of the process, hydrolysis occurs according to the reaction below: FeCl{sub 3 liquid} + H{sub 2}O {r_arrow} FeOCl{sub solid} + 2 HCl{sub gas} During the second step, the hot, solid, iron oxychloride is sprayed with water or placed in contact with steam, and hydrolysis proceeds to the iron oxide according to the following reaction: 2 FeOCl{sub solid} + H{sub 2}O {r_arrow} Fe{sub 2}O{sub 3 solid} + 2 HCl{sub gas}. The iron oxide, which contains radioisotopes, can then be disposed of by cementation or encapsulation. Alternately, these chlorides can be washed off of the solids and can then either be recycled or disposed of in some other way.« less

Properties of solid solutions, doped film, and nanocomposite structures based on zinc oxide

NASA Astrophysics Data System (ADS)

Lashkarev, G. V.; Shtepliuk, I. I.; Ievtushenko, A. I.; Khyzhun, O. Y.; Kartuzov, V. V.; Ovsiannikova, L. I.; Karpyna, V. A.; Myroniuk, D. V.; Khomyak, V. V.; Tkach, V. N.; Timofeeva, I. I.; Popovich, V. I.; Dranchuk, N. V.; Khranovskyy, V. D.; Demydiuk, P. V.

2015-02-01

A study of the properties of materials based on the wide bandgap zinc oxide semiconductor, which are promising for application in optoelectronics, photovoltaics and nanoplasmonics. The structural and optical properties of solid solution Zn1-xCdxO films with different cadmium content, are studied. The samples are grown using magnetron sputtering on sapphire backing. Low-temperature photoluminescence spectra revealed emission peaks associated with radiative recombination processes in those areas of the film that have varying amounts of cadmium. X-ray phase analysis showed the presence of a cadmium oxide cubic phase in these films. Theoretical studies of the solid solution thermodynamic properties allowed for a qualitative interpretation of the observed experimental phenomena. It is established that the growth of the homogeneous solid solution film is possible only at high temperatures, whereas regions of inhomogeneous composition can be narrowed through elastic deformation, caused by the mismatch of the film-backing lattice constants. The driving forces of the spinodal decomposition of the Zn1-xCdxO system are identified. Fullerene-like clusters of Znn-xCdxOn are used to calculate the bandgap and the cohesive energy of ZnCdO solid solutions. The properties of transparent conductive ZnO films, doped with Group III donor impurities (Al, Ga, In), are examined. It is shown that oxygen vacancies are responsible for the hole trap centers in the zinc oxide photoconductivity process. We also examine the photoluminescence properties of metal-ZnO nanocomposite structures, caused by surface plasmons.

Fabrication and characterization of solid oxide cells for energy conversion and storage

NASA Astrophysics Data System (ADS)

Yang, Chenghao

2011-12-01

There has been an increasing interest in clean and renewable energy generation for highlighted energy and environmental concerns. Solid oxide cells (SOCs) have been considered as one of the promising technologies, since they can be operated efficiently both in electrolysis mode by generating hydrogen through steam electrolysis and fuel cell mode by electrochemically combining fuel with oxidant. The present work is devoted to performing a fundamental study of SOC in both fuel cell mode for power generation and electrolysis mode for fuel production. The research work on SOCs that can be operated reversibly for power generation and fuel production has been conducted in the following six projects: (1) High performance solid oxide electrolysis cell (SOEC) Fabrication of novel structured SOEC oxygen electrode with the conventional and commercial solid oxide fuel cell materials by screen-printing and infiltration fabrication methods. The microstructure, electrochemical properties and durability of SOECs has been investigated. It was found that the LSM infiltrated cell has an area specific resistance (ASR) of 0.20 Ω cm2 at 900°C at open circuit voltage with 50% absolute humidity (AH), which is relatively lower than that of the cell with LSM-YSZ oxygen electrode made by a conventional mixing method. Electrolysis cell with LSM infiltrated oxygen electrode has demonstrated stable performance under electrolysis operation with 0.33 A/cm2 and 50 vol.% AH at 800°C. (2) Advanced performance high temperature micro-tubular solid oxide fuel cell (MT-SOFC) Phase-inversion, dip-coating, high temperature co-sintering process and impregnation method were used to fabricate micro-tubular solid oxide fuel cell. The micro-structure of the micro-tubular fuel cell will be investigated and the power output and thermal robustness has been evaluated. High performance and rapid start-up behavior have been achieved, indicates that the MT-SOFC developed in this work can be a promising technology for portable applications. (3) Promising intermediate temperature micro-tubular solid oxide fuel cells for portable power supply applications Maximum power densities of 0.5, 0.38 and 0.27 W/cm2 have been obtained using H2-15% H2O as fuel at 550, 600 and 650°C, respectively. Quick thermal cycles performed on the intermediate temperature MT-SOFC stability demonstrate that the cell has robust performance stability for portable applications. (4) Micro-tubular solid oxide cell (MT-SOC) for steam electrolysis The electrochemical properties of MT-SOC will be investigated in detail in electrolysis mode. The mechanism of the novel hydrogen electrode structure benefiting the cell performance will be demonstrated systematically. The high electrochemical performance of the MT-SOC in electrolysis mode indicates that MT-SOC can provide an efficient hydrogen generation process. (5) Micro-tubular solid oxide cell (MT-SOC) for steam and CO2 co-electrolysis The MT-SOC will be operated in co-electrolysis mode for steam and CO 2, which will provide an efficient approach to generate syngas (H2+CO) without consuming fossil fuels. This can potentially provide an alternative superior approach for carbon sequestration which has been a critical issue facing the sustainability of our society. (6) Steam and CO2 co-electrolysis using solid oxide cells fabricated by freeze-drying tape-casting Tri-layer scaffolds have been prepared by freeze-drying tape casting process and the electrode catalysts are obtained by infiltrating the porous electrode substrates. Button cells will be tested for co-electrolysis of steam and CO2. The mechanism and efficiency of steam and CO2 co-electrolysis will be systemically investigated. In conclusion, SOCs have been fabricated with conventional materials and evaluated, but their performance has been found to be limited in either SOFC or SOEC mode. The cell performance has been significantly improved by employing an infiltrated LSM-YSZ electrode, due to dramatically decreased polarization resistance. However, mass transport limitation has been observed, particularly in electrolysis mode. By utilizing micro-tubular SOCs with novel hydrogen electrode produced via a phase inversion method, mass transport limitation has been mitigated. Finally, mass transport has been further improved by using cells with electrodes fabricated through a freeze-drying tape-casting method. (Abstract shortened by UMI.)

Characterization of compressibility and compactibility of poly(ethylene oxide) polymers for modified release application by compaction simulator.

PubMed

Yang, L; Venkatesh, G; Fassihi, R

1996-10-01

Poly(ethylene oxide) polymers (PEO) appear to have great potential for controlled release applications. These polymers are hydrophilic with good water solubility, low toxicity, and high swelling capacity. As part of formulation optimization for a large-scale solid dosage form production, physicomechanical characterization of PEO was undertaken using a compaction simulator. Heckel plots for all PEOs were constructed, and yield pressures (Py) at different punch velocities were calculated from the linear portion of the plots. Low Py values, increase of Py with increasing punch speed, upward curvature of the plot, and strain rate sensitivity values indicate that the densification process and consolidation mechanism for PEOs of various molecular weights (0.2 x 10(6) to 7 x 10(6)) are identical and follow plastic deformation. PEOs have a high degree of crystallinity (57-85%) and show significant axial recovery (15-25%) upon decompression and ejection. The low Py values (58-78 MPa) and low mean compaction pressures demonstrate that volume reduction (compressibility) under pressure is excellent. However, due to viscoelastic behavior and large axial expansion, tablets of relatively low tensile strength are produced. These observations suggest the need to blend PEO with highly compactible excipients in order to produce tables on a high-speed production press.

Performance of Bi2O3/TiO2 prepared by sol-gel on p-Cresol degradation under solar and visible light.

PubMed

Vigil-Castillo, Héctor H; Hernández-Ramírez, Aracely; Guzmán-Mar, Jorge L; Ramos-Delgado, Norma A; Villanueva-Rodríguez, Minerva

2018-05-21

Photocatalytic degradation of p-Cresol was evaluated using the mixed oxide Bi 2 O 3 /TiO 2 (containing 2 and 20% wt. Bi 2 O 3 referred as TB2 and TB20) and was compared with bare TiO 2 under simulated solar radiation. Materials were prepared by the classic sol-gel method. All solids exhibited the anatase phase by X-ray diffraction (XRD) and Raman spectroscopy. The synthesized materials presented lower crystallite size and Eg value, and also higher surface area as Bi 2 O 3 amount was increased. Bi content was quantified showing near to 70% of theoretical values in TB2 and TB20. Bi 2 O 3 incorporation also was demonstrated by X-ray photoelectron spectroscopy (XPS). Characterization of mixed oxides suggests a homogeneous distribution of Bi 2 O 3 on TiO 2 surface. Photocatalytic tests were carried out using a catalyst loading of 1 g L -1 under simulated solar light and visible light. The incorporation of Bi 2 O 3 in TiO 2 improved the photocatalytic properties of the synthesized materials obtaining better results with TB20 than the unmodified TiO 2 under both radiation sources.

Molecular Dynamics Simulations of Poly(ethylene oxide) Grafted onto Silica Immersed in Melt of Homopolymers.

PubMed

Benková, Zuzana; Cordeiro, M Natália D S

2015-09-22

Tuning of surface properties plays an important role in applications ranging from material engineering to biomedicine/chemistry. The interactions of chains grafted to a solid support and exposed to a matrix of chemically identical chains represent an intriguing issue. In this work, the behavior of poly(ethylene oxide) (PEO) chains grafted irreversibly onto an amorphous silica and immersed in the matrix of free PEO chains of different polymerization degree is studied using molecular dynamics simulations. The density distributions of grafted and free PEO chains, the height of the grafted layer, overlap parameters, and orientation order parameters depend not only on the grafting density but also on the length of free chains which confirm the entropic nature of the interactions between the grafted and free chains. In order to achieve a complete expulsion of the free chains from the grafted layer, a grafting density as high as 3.5 nm(-2) is necessary. Free PEO chains of 9 monomers leave the grafted layer at lower grafting densities than the longer PEO chains of 18 monomers in contrast with the theoretical predictions. The height of the grafted layer evolves with the grafting density in the presence of free chains in qualitative agreement with the theoretical phase diagram.

Is Geometric Frustration-Induced Disorder a Recipe for High Ionic Conductivity?

PubMed

Düvel, Andre; Heitjans, Paul; Fedorov, Pavel; Scholz, Gudrun; Cibin, Giannantonio; Chadwick, Alan V; Pickup, David M; Ramos, Silvia; Sayle, Lewis W L; Sayle, Emma K L; Sayle, Thi X T; Sayle, Dean C

2017-04-26

Ionic conductivity is ubiquitous to many industrially important applications such as fuel cells, batteries, sensors, and catalysis. Tunable conductivity in these systems is therefore key to their commercial viability. Here, we show that geometric frustration can be exploited as a vehicle for conductivity tuning. In particular, we imposed geometric frustration upon a prototypical system, CaF 2 , by ball milling it with BaF 2 , to create nanostructured Ba 1-x Ca x F 2 solid solutions and increased its ionic conductivity by over 5 orders of magnitude. By mirroring each experiment with MD simulation, including "simulating synthesis", we reveal that geometric frustration confers, on a system at ambient temperature, structural and dynamical attributes that are typically associated with heating a material above its superionic transition temperature. These include structural disorder, excess volume, pseudovacancy arrays, and collective transport mechanisms; we show that the excess volume correlates with ionic conductivity for the Ba 1-x Ca x F 2 system. We also present evidence that geometric frustration-induced conductivity is a general phenomenon, which may help explain the high ionic conductivity in doped fluorite-structured oxides such as ceria and zirconia, with application for solid oxide fuel cells. A review on geometric frustration [ Nature 2015 , 521 , 303 ] remarks that classical crystallography is inadequate to describe systems with correlated disorder, but that correlated disorder has clear crystallographic signatures. Here, we identify two possible crystallographic signatures of geometric frustration: excess volume and correlated "snake-like" ionic transport; the latter infers correlated disorder. In particular, as one ion in the chain moves, all the other (correlated) ions in the chain move simultaneously. Critically, our simulations reveal snake-like chains, over 40 Å in length, which indicates long-range correlation in our disordered systems. Similarly, collective transport in glassy materials is well documented [for example, J. Chem. Phys. 2013 , 138 , 12A538 ]. Possible crystallographic nomenclatures, to be used to describe long-range order in disordered systems, may include, for example, the shape, length, and branching of the "snake" arrays. Such characterizations may ultimately provide insight and differences between long-range order in disordered, amorphous, or liquid states and processes such as ionic conductivity, melting, and crystallization.

A Study of Oxides for Solid Oxide Cells

NASA Astrophysics Data System (ADS)

Comets, Olivier

As the world energy consumption increases, it is a question of global health to increase energy production efficiency and to reduce CO2 emissions. In that respect, solid oxide cells are solid state devices that convert directly fuel into electricity, or vice versa. In fact, when run in fuel cell mode, such devices produce electricity with efficiency up to twice that of current natural gas power plants. However, systems equipped with them have only seen limited commercialization owing to issues of cost, durability, and performance. In this thesis, three different aspects of solid oxide cells are studied. First, the effects of stress on the properties of mixed ionic electronic conducting oxides are considered. Such oxides can be used as electrode materials, where they are often subject to large stresses, which can, in turn, affect their performance. Hence, understanding the relationship between stress and properties in such materials is crucial. Non-stoichiometry in strontium substituted lanthanum cobaltite is found to increase under tension and to decrease under compression. Then, degradation taking place when the cell is run in electrolysis mode is discussed. A high current allows for a high production rate of hydrogen gas. However, this can also lead to oxygen bubble nucleating in the electrolyte and subsequent degradation of the cell. The analysis conducted here shows that such nucleation phenomenon can be avoided by keeping the overpotential at the oxygen electrode below a critical value. Finally, the growth and coarsening of catalyst nanoparticles at the surface of an oxide is studied. Scientists have developed new oxides for anodes in which a catalyst material is dissolved and exsolves under operating conditions. As the performance of the cell is controlled by the surface area of the catalyst phase, understanding the kinetics of the growth is critical to predict the performance of the cell. An approach is developed to study the growth of one particle, in the limiting case where only bulk transport is allowed.

Predicting the constitutive behavior of semi-solids via a direct finite element simulation: application to AA5182

NASA Astrophysics Data System (ADS)

Phillion, A. B.; Cockcroft, S. L.; Lee, P. D.

2009-07-01

The methodology of direct finite element (FE) simulation was used to predict the semi-solid constitutive behavior of an industrially important aluminum-magnesium alloy, AA5182. Model microstructures were generated that detail key features of the as-cast semi-solid: equiaxed-globular grains of random size and shape, interconnected liquid films, and pores at the triple-junctions. Based on the results of over fifty different simulations, a model-based constitutive relationship which includes the effects of the key microstructure features—fraction solid, grain size and fraction porosity—was derived using regression analysis. This novel constitutive equation was then validated via comparison with both the FE simulations and experimental stress/strain data. Such an equation can now be used to incorporate the effects of microstructure on the bulk semi-solid flow stress within a macro- scale process model.

Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakamoto, Y.; Ishii, Y.; Kawasaki, S., E-mail: kawasaki.shinji@nitech.ac.jp

2016-07-06

Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

DEVELOPMENT OF AN INSOLUBLE SALT SIMULANT TO SUPPORT ENHANCED CHEMICAL CLEANING TESTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eibling, R

The closure process for high level waste tanks at the Savannah River Site will require dissolution of the crystallized salts that are currently stored in many of the tanks. The insoluble residue from salt dissolution is planned to be removed by an Enhanced Chemical Cleaning (ECC) process. Development of a chemical cleaning process requires an insoluble salt simulant to support evaluation tests of different cleaning methods. The Process Science and Engineering section of SRNL has been asked to develop an insoluble salt simulant for use in testing potential ECC processes (HLE-TTR-2007-017). An insoluble salt simulant has been developed based uponmore » the residues from salt dissolution of saltcake core samples from Tank 28F. The simulant was developed for use in testing SRS waste tank chemical cleaning methods. Based on the results of the simulant development process, the following observations were developed: (1) A composition based on the presence of 10.35 grams oxalate and 4.68 grams carbonate per 100 grams solids produces a sufficiently insoluble solids simulant. (2) Aluminum observed in the solids remaining from actual waste salt dissolution tests is probably precipitated from sodium aluminate due to the low hydroxide content of the saltcake. (3) In-situ generation of aluminum hydroxide (by use of aluminate as the Al source) appears to trap additional salts in the simulant in a manner similar to that expected for actual waste samples. (4) Alternative compositions are possible with higher oxalate levels and lower carbonate levels. (5) The maximum oxalate level is limited by the required Na content of the insoluble solids. (6) Periodic mixing may help to limit crystal growth in this type of salt simulant. (7) Long term storage of an insoluble salt simulant is likely to produce a material that can not be easily removed from the storage container. Production of a relatively fresh simulant is best if pumping the simulant is necessary for testing purposes. The insoluble salt simulant described in this report represents the initial attempt to represent the material which may be encountered during final waste removal and tank cleaning. The final selected simulant was produced by heating and evaporation of a salt slurry sample to remove excess water and promote formation and precipitation of solids with solubility characteristics which are consistent with actual tank insoluble salt samples. The exact anion composition of the final product solids is not explicitly known since the chemical components in the final product are distributed between the solid and liquid phases. By combining the liquid phase analyses and total solids analysis with mass balance requirements a calculated composition of assumed simple compounds was obtained and is shown in Table 0-1. Additional improvements to and further characterization of the insoluble salt simulant are possible. During the development of these simulants it was recognized that: (1) Additional waste characterization on the residues from salt dissolution tests with actual waste samples to determine the amount of species such as carbonate, oxalate and aluminosilicate would allow fewer assumptions to be made in constructing an insoluble salt simulant. (2) The tank history will impact the amount and type of insoluble solids that exist in the salt dissolution solids. Varying the method of simulant production (elevated temperature processing time, degree of evaporation, amount of mixing (shear) during preparation, etc.) should be tested.« less

Geochemical and microbiological responses to oxidant introduction into reduced subsurface sediment from the Hanford 300 Area, Washington.

PubMed

Percak-Dennett, Elizabeth M; Roden, Eric E

2014-08-19

Pliocene-aged reduced lacustrine sediment from below a subsurface redox transition zone at the 300 Area of the Hanford site (southeastern Washington) was used in a study of the geochemical response to introduction of oxygen or nitrate in the presence or absence of microbial activity. The sediments contained large quantities of reduced Fe in the form of Fe(II)-bearing phyllosilicates, together with smaller quantities of siderite and pyrite. A loss of ca. 50% of 0.5 M HCl-extractable Fe(II) [5-10 mmol Fe(II) L(-1)] and detectable generation of sulfate (ca. 0.2 mM, equivalent to 10% of the reduced inorganic sulfur pool) occurred in sterile aerobic reactors. In contrast, no systematic loss of Fe(II) or production of sulfate was observed in any of the other oxidant-amended sediment suspensions. Detectable Fe(II) accumulation and sulfate consumption occurred in non-sterile oxidant-free reactors. Together, these results indicate the potential for heterotrophic carbon metabolism in the reduced sediments, consistent with the proliferation of known heterotrophic taxa (e.g., Pseudomonadaceae, Burkholderiaceae, and Clostridiaceae) inferred from 16S rRNA gene pyrosequencing. Microbial carbon oxidation by heterotrophic communities is likely to play an important role in maintaining the redox boundary in situ, i.e., by modulating the impact of downward oxidant transport on Fe/S redox speciation. Diffusion-reaction simulations of oxygen and nitrate consumption coupled to solid-phase organic carbon oxidation indicate that heterotrophic consumption of oxidants could maintain the redox boundary at its current position over millennial time scales.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity and methods for manufacturing such blends

DOEpatents

Skotheim, T.

A polymer blend is disclosed of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

High temperature solid oxide regenerative fuel cell for solar photovoltaic energy storage

NASA Technical Reports Server (NTRS)

Bents, David J.

1987-01-01

A hydrogen-oxygen regenerative fuel cell (RFC) energy storage system based on high temperature solid oxide fuel cell (SOFC) technology is described. The reactants are stored as gases in lightweight insulated pressure vessels. The product water is stored as a liquid in saturated equilibrium with the fuel gas. The system functions as a secondary battery and is applicable to darkside energy storage for solar photovoltaics.

Monolithic solid oxide fuel cell development

NASA Technical Reports Server (NTRS)

Myles, K. M.; Mcpheeters, C. C.

1989-01-01

The feasibility of the monolithic solid oxide fuel cell (MSOFC) concept has been proven, and the performance has been dramatically improved. The differences in thermal expansion coefficients and firing shrinkages among the fuel cell materials have been minimized, thus allowing successful fabrication of the MSOFC with few defects. The MSOFC shows excellent promise for development into a practical power source for many applications from stationary power, to automobile propulsion, to space pulsed power.

Fuel electrode containing pre-sintered nickel/zirconia for a solid oxide fuel cell

DOEpatents

Ruka, Roswell J.; Vora, Shailesh D.

2001-01-01

A fuel cell structure (2) is provided, having a pre-sintered nickel-zirconia fuel electrode (6) and an air electrode (4), with a ceramic electrolyte (5) disposed between the electrodes, where the pre-sintered fuel electrode (6) contains particles selected from the group consisting of nickel oxide, cobalt and cerium dioxide particles and mixtures thereof, and titanium dioxide particles, within a matrix of yttria-stabilized zirconia and spaced-apart filamentary nickel strings having a chain structure, and where the fuel electrode can be sintered to provide an active solid oxide fuel cell.

Mössbauer study of modified iron-molybdenum catalysts for methanol oxidation

NASA Astrophysics Data System (ADS)

Ivanov, K. I.; Mitov, I. G.; Krustev, St. V.; Boyanov, B. S.

2010-03-01

The preparation and catalytic properties of mixed Fe-Mo-W catalysts toward methanol oxidation are investigated. Mössbauer spectroscopy, X-ray diffraction and chemical studies revealed the formation of two types of solid solutions with compositions Fe2(MoxW1-xO4)3 and (MoxW1-x)O3. The solid solutions formed are characterized by high activity and selectivity upon methanol oxidation and are of interest in view of their practical application. Sodium-doped iron-molybdenum catalysts are also investigated and the NaFe(MoO4)2 formation was established.

Recovery of iron oxide from coal fly ash

DOEpatents

Dobbins, Michael S.; Murtha, Marlyn J.

1983-05-31

A high quality iron oxide concentrate, suitable as a feed for blast and electric reduction furnaces is recovered from pulverized coal fly ash. The magnetic portion of the fly ash is separated and treated with a hot strong alkali solution which dissolves most of the silica and alumina in the fly ash, leaving a solid residue and forming a precipitate which is an acid soluble salt of aluminosilicate hydrate. The residue and precipitate are then treated with a strong mineral acid to dissolve the precipitate leaving a solid residue containing at least 90 weight percent iron oxide.