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At least 55 records · Page 3

A Joint Experimental and Computational Study of the Negative Ion Photoelectron Spectroscopy of the 1-Phospha-2,3,4-triazolate Anion, HCPN 3 –

We report here the results of a combined experimental and computational study of the negative ion photoelectron spectroscopy (NIPES) of the recently synthesized, planar, aromatic, HCPN3– ion. The adiabatic electron detachment energy of HCPN3– (electron affinity of HCPN3•) was measured to be 3.555 ± 0.010 eV, a value that is intermediate between the electron detachment energies of the closely related (CH)2N3– and P2N3– ions. High level electronic structure calculations and Franck–Condon factor (FCF) simulations reveal that transitions from the ground state of the anion to two nearly degenerate, low-lying, electronic states, of the neutral HCPN3• radical are responsible for the congested peaks at low binding energies in the NIPE spectrum. The best fit of the simulated NIPE spectrum to the experimental spectrum indicates that the ground state of HCPN3• is a 5π-electron 2A" π radical state, with a 6π-electron, 2A', σ radical state being at most ~1.0 kcal/mol higher in energy. This assignment contrasts with our recent finding that the ground state of P2N3• is a 6π-electron σ radical state

Environmental Molecular Sciences Laboratory↗

Gas-phase negative ion photoelectron spectroscopy and reactivity of phenylacetylide

Arylacetylides such as phenylacetylide (PhCC–, 1) are important nucleophiles used in synthetic chemistry yet rarely have they been studied as bare carbanions. In this work, the phenylacetylide anion was formed via electrospray ionization (ESI) or multistage mass spectrometry (MSn) experiments and subsequently examined in the gas phase by negative ion photoelectron spectroscopy (NIPES), ion-molecule reactions (IMR), alongside theoretical calculations to probe its fundamental structure and reactivity. Photoelectron spectra of PhCC– (1) revealed vertical (VDE) and adiabatic detachment energies (ADE), both of 3.220 eV. The latter value is also the electron affinity (EA) of the phenylethynyl radical (PhCC•) from which a bond dissociation energy (BDE) of phenylacetylene (PhCCH) was derived to be ca. 131.3 ± 1.7 kcal mol-1 using a gas-phase thermochemical cycle. Detachment of an electron from PhCC– at 266 nm likely results in resonant autodetachment, supported by Franck-Condon Factor (FCF) simulations. The phenylacetylide anion reacts with methyl iodide (CH3I) and allyl iodide (C3H5I) via SN2 nucleophilic displacement with measured rate coefficients of 4.29 and 3.66 × 10-10 cm3 molecule-1 s-1, respectively. The mechanisms associated with these displacement reactions are explained and understood in terms of the reaction kinetics, natural bond orbital (NBO) theory, and Density Functional Theory (DFT) calculations.

Ma, Howard Z.↗

Two-Level Convergence Theory for Multigrid Reduction in Time (MGRIT)

Here we develop a two-grid convergence theory for the parallel-in-time scheme known as multigrid reduction in time (MGRIT), as it is implemented in the open-source package [XBraid: Parallel Multigrid in Time, http://llnl.gov/casc/xbraid]. MGRIT is a scalable and multilevel approach to parallel-in-time simulations that nonintrusively uses existing time-stepping schemes, and in a specific two-level setting it is equivalent to the widely known parareal algorithm. The goal of this paper is twofold. First, we present a two-level MGRIT convergence analysis for linear problems where the spatial discretization matrix can be diagonalized, and then apply this analysis to our two basic model problems, the heat equation and the advection equation. One important assumption is that the coarse and fine time-grid propagators can be diagaonalized by the same set of eigenvectors, which is often the case when the same spatial discretization operator is used on the coarse and fine time grids. In many cases, the MGRIT algorithm is guaranteed to converge, and we demonstrate numerically that the theoretically predicted convergence rates are sharp in practice for our model problems. Second, we explore how the convergence of MGRIT compares to the stability of the chosen time-stepping scheme. In particular, we demonstrate that a stable time-stepping scheme does not necessarily imply convergence of MGRIT, although MGRIT with FCF-relaxation always converges for the diffusion dominated problems considered here.

97 MATHEMATICS AND COMPUTING↗

A literature review of pyroprocessing safeguards

Pyroprocessing is a promising technology for reprocessing used nuclear fuel (UNF) from light water reactors (LWR) and sodium fast reactors (SFR). With the advancement of fast reactors with projects from companies such as TerraPower, the prospects of pyroprocessing are more promising than ever before, as fast reactors can consume all actinides, not just uranium and plutonium. Before pyroprocessing can be implemented commercially, pre-existing safeguards used for aqueous reprocessing must be adapted for pyroprocessing. Safeguards, as determined by both the Nuclear Regulatory Commission (NRC) and the International Atomic Energy Agency (IAEA), are discussed in this review as guidelines for approaches used in both domestic and international reprocessing plants. The implementation of safeguards in aqueous reprocessing was then reviewed based on the experience from existing aqueous facilities. The experimental pyroprocessing facilities were identified as pyroprocessing plants in the design stage with one operating exception of the Fuel Conditioning Facility (FCF). The safeguard methods implemented or designed for each and the accompanying challenges of utilizing existing safeguards in pyroprocessing are considered and a summary of applicable approaches is included.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

ECAR-4310, Evaluation of the Inhalation Dose Consequences for the HALEU Environmental Assessment

The U. S. Department of Energy (DOE) proposes to expand the fuel fabrication capability at Idaho National Laboratory (INL) to produce needed quantities of High-Assay Low-Enriched Uranium (HALEU) fuel from down-blended EBR-II fuel processed at the Fuels Conditioning Facility (FCF) and stored at INL. The expansion of the fuel fabrication capability would include the purchase of new equipment and use of existing facilities at INL’s Materials Fuels Complex (MFC) and the Idaho Nuclear Technology and Engineering Center (INTEC). The purpose of this report is to document calculation of the estimated potential inhalation dose to members of the public and workers from accidental air emissions associated with production of HALEU fuel. This document supports the Environmental Assessment for Use of DOE-Owned HALEU Stored at Idaho National Laboratory.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

HALEU Decontamination Investigations for EBR-II Recovered Uranium. HALEU Drip Casting Results in the Fuel Conditioning Facility Cathode Processor

Many of the new advanced reactor designs being proposed by the nuclear private sector require uranium fuel enriched between 5 and 20%, otherwise known as High Assay Low Enriched Uranium (HALEU), to support their designs. There are currently no commercial facilities based in the United States which have the capability to produce this material, and as a result the nuclear industry has requested support from the Department of Energy (DOE) to meet this need. One approach being considered by DOE to respond to this demand is to recover highly enriched uranium from used nuclear fuels and downblend it to enrichments less than 20 % U-235. DOE’s past research related to liquid metal fast breeder reactors resulted in the irradiation of more than 3 metric tons (MT) of nuclear fuel composed of highly enriched metallic uranium which resides at the Idaho National Laboratory (INL). This inventory of used nuclear fuel is currently being conditioned using an electrometallurgical treatment process (EMT) to facilitate its eventual disposition to a geologic repository. As part of this treatment process, the highly enriched component of this used fuel is separated, recovered, downblended to <20% U-235, and stored as a metallic uranium ingot. The majority of this fuel was irradiated in the Experimental Breeder Reactor II (EBR-II) over the course of its 30 years of operation. This sodium cooled fast reactor utilized a core composed of highly enriched, sodium-bonded, metallic fuel to sustain or “drive” the reactor. This EBR-II driver fuel is currently being treated for sodium neutralization in the Fuel Conditioning Facility (FCF) at the Materials and Fuels Complex (MFC) and the metallic uranium recovered as a component of this process has been proposed as a potential source of supply of high assay low enriched uranium. The irradiation of the metallic uranium fuel results in the creation of fission products and some minor actinides which are not compatible with many reuse scenario’s, and introduces significant challenges associated with fabrication of new fuel elements using this material. However, it is believed that the current EMT process can be slightly enhanced to address these concerns and result in the recovery of a product that can be considered as a source of supply for HALEU applications. Based on this, DOE requested the INL research methods to enhance the EMT process to produce a recovered uranium material that has a lower contaminant level and lower radiological dose rate and could be utilized in glovebox based fuel fabrication scenarios. The report that follows documents the progress toward meeting this goal.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Multigrid-Reduction-in-Time for the Rotating Shallow Water Equations

We consider multilevel time-parallel methods for the numerical solution of the rotating shallow water equations. In particular, the multigrid-reduction-in-time (MGRIT) algorithm is used for the parallel time integration. An asymptotic model is used at the coarse levels while the full model is employed at the finer levels. The asymptotic model is well-suited for highly oscillatory partial differential equations like the rotating shallow water equations because it can accurately and stably take the required large time-steps on coarse levels. Our work exploits the flexibility of the MGRIT algorithm in terms of the number of levels and relaxation schemes to show some computational benefits, especially with respect to FCF-relaxation and data reuse.

97 MATHEMATICS AND COMPUTING↗

Uranium Casting Pin Dissolution for Multi-element and Si Analysis

The purpose of this special instruction is to establish a standard method for the dissolution of uranium casting materials from FCF or HFEF. The Spent Fuel Treatment program requires the analysis of uranium casting pins in order to determine the level of impurities. The samples are dissolved in a laboratory hood for ICP-MS and ICP-OES analyses. The dissolution of the uranium will require the use of nitric and/or hydrochloric acid, with a trace amount of hydrofluoric acid as a dissolution catalyst. Two dissolution methods are provided to allow for the choice of the final dissolver matrix. A process blank should be performed along with samples.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Advanced Oxidation of Tartrazine and Brilliant Blue with Pulsed Ultraviolet Light Emitting Diodes

ABSTRACT: This study investigated the effect of ultraviolet light‐emitting diodes (UVLEDs) coupled with hydrogen peroxide as an advanced oxidation process (AOP) for the degradation of two test chemicals. Brilliant Blue FCF consistently exhibited greater degradation than tartrazine, with 83% degradation after 300 minutes at the 100% duty cycle compared with only 17% degradation of tartrazine under the same conditions. These differences are attributable to the structural properties of the compounds. Duty cycle was positively correlated with the first‐order rate constants (k) for both chemicals but, interestingly, negatively correlated with the normalized first‐order rate constants (k/duty cycle). Synergistic effects of both hydraulic mixing and LED duty cycle were manifested as novel oscillations in the effluent contaminant concentration. Further, LED output and efficiency were dependent upon duty cycle and less efficient over time perhaps due to heating effects on semiconductor performance.

Scott, Robert↗

Solid Inflammability Boundary at Low Speed (SIBAL)

This research program is concerned with the effect of low speed flow on the spreading and extinction processes of flames over solid fuels. We are particularly interested in the flammability boundary and the near-limit flame behavior in a microgravity environment. Primary attention is given to flame propagation in concurrent flow - the more hazardous situation from the point of view of fire safety. Both theoretical modeling and experimental research are in progress. This project passed the Science Concept Review (SCR) in 1996. As a result, the experiment continues on the flight definition path, and is currently scheduled to be performed in the Space Station Fluids and Combustion Facility (FCF).

Tien, James S.↗

Fluid Physical and Transport Phenomena Studies aboard the International Space Station: Planned Experiments

This paper provides an overview of the microgravity fluid physics and transport phenomena experiments planned for the International Spare Station. NASA's Office of Life and Microgravity Science and Applications has established a world-class research program in fluid physics and transport phenomena. This program combines the vast expertise of the world research community with NASA's unique microgravity facilities with the objectives of gaining new insight into fluid phenomena by removing the confounding effect of gravity. Due to its criticality to many terrestrial and space-based processes and phenomena, fluid physics and transport phenomena play a central role in the NASA's Microgravity Program. Through widely publicized research announcement and well established peer-reviews, the program has been able to attract a number of world-class researchers and acquired a critical mass of investigations that is now adding rapidly to this field. Currently there arc a total of 106 ground-based and 20 candidate flight principal investigators conducting research in four major thrust areas in the program: complex flows, multiphase flow and phase change, interfacial phenomena, and dynamics and instabilities. The International Space Station (ISS) to be launched in 1998, provides the microgravity research community with a unprecedented opportunity to conduct long-duration microgravity experiments which can be controlled and operated from the Principal Investigators' own laboratory. Frequent planned shuttle flights to the Station will provide opportunities to conduct many more experiments than were previously possible. NASA Lewis Research Center is in the process of designing a Fluids and Combustion Facility (FCF) to be located in the Laboratory Module of the ISS that will not only accommodate multiple users but, allow a broad range of fluid physics and transport phenomena experiments to be conducted in a cost effective manner.

Singh, Bhim S.↗

Smoldering, Transition and Flaming in Microgravity

A research project is underway to study smolder and the transition to flaming in microgravity. The Microgravity Smoldering Combustion (MSC) flight project is an ongoing research project to provide a better understanding of the controlling mechanisms of smoldering combustion. The Smoldering Transition and Flaming (STAF) project is a recently established research program that will utilize the Fluids and Combustion Facility (FCF) of the ISS to examine the transition from smolder to flaming in microgravity. In forced flow smolder experiments ambient pressure in the MSC chamber rises, thus motivating the need to understand the effects of pressure on smoldering combustion. Further, the STAF experiment has constraints on experimental scale and testing at elevated pressure may be a mechanism to reduce the sample size by enhancing the smolder reaction. In the work we are reporting here, a series of ground-based tests determine the effects of pressure on smoldering combustion. These tests are compared with data obtained from experiments conducted aboard the Space Shuttle in flights STS-69 and STS-77. Measurements of one-dimensional smolder propagation velocity are made by thermocouple probing and a non-intrusive Ultrasound Imaging System (UIS)]. Thermocouples are also used to obtain reaction temperatures and the UIS is used to determine permeabilities of the fuel in real-time.

Fernandez-Pello, A. C.↗

Multi-User Hardware Solutions to Combustion Science ISS Research

In response to the budget environment and to expand on the International Space Station (ISS) Fluids and Combustion Facility (FCF) Combustion Integrated Rack (CIR), common hardware approach, the NASA Combustion Science Program shifted focus in 1999 from single investigator PI (Principal Investigator)-specific hardware to multi-user 'Minifacilities'. These mini-facilities would take the CIR common hardware philosophy to the next level. The approach that was developed re-arranged all the investigations in the program into sub-fields of research. Then common requirements within these subfields were used to develop a common system that would then be complemented by a few PI-specific components. The sub-fields of research selected were droplet combustion, solids and fire safety, and gaseous fuels. From these research areas three mini-facilities have sprung: the Multi-user Droplet Combustion Apparatus (MDCA) for droplet research, Flow Enclosure for Novel Investigations in Combustion of Solids (FEANICS) for solids and fire safety, and the Multi-user Gaseous Fuels Apparatus (MGFA) for gaseous fuels. These mini-facilities will develop common Chamber Insert Assemblies (CIA) and diagnostics for the respective investigators complementing the capability provided by CIR. Presently there are four investigators for MDCA, six for FEANICS, and four for MGFA. The goal of these multi-user facilities is to drive the cost per PI down after the initial development investment is made. Each of these mini-facilities will become a fixture of future Combustion Science NASA Research Announcements (NRAs), enabling investigators to propose against an existing capability. Additionally, an investigation is provided the opportunity to enhance the existing capability to bridge the gap between the capability and their specific science requirements. This multi-user development approach will enable the Combustion Science Program to drive cost per investigation down while drastically reducing the time required to go from selection to space flight.

Otero, Angel M.↗

The Light Microscopy Module: An On-Orbit Multi-User Microscope Facility

The Light Microscopy Module (LMM) is planned as a remotely controllable on-orbit microscope subrack facility, allowing flexible scheduling and operation of fluids and biology experiments within the Fluids and Combustion Facility (FCF) Fluids Integrated Rack (FIR) on the International Space Station (ISS). The LMM will be the first integrated payload with the FIR to conduct four fluid physics experiments. A description of the LMM diagnostic capabilities, including video microscopy, interferometry, laser tweezers, confocal, and spectrophotometry, will be provided.

Motil, Susan M.↗

FEANICS: A Multi-User Facility For Conducting Solid Fuel Combustion Experiments On ISS

The Destiny Module on the International Space Station (ISS) will soon be home for the Fluids and Combustion Facility's (FCF) Combustion Integrated Rack (CIR), which is being developed at the NASA Glenn Research Center in Cleveland, Ohio. The CIR will be the platform for future microgravity combustion experiments. A multi-user mini-facility called FEANICS (Flow Enclosure Accommodating Novel Investigations in Combustion of Solids) will also be built at NASA Glenn. This mini-facility will be the primary means for conducting solid fuel combustion experiments in the CIR on ISS. The main focus of many of these solid combustion experiments will be to conduct basic and applied scientific investigations in fire-safety to support NASA's Bioastronautics Initiative. The FEANICS project team will work in conjunction with the CIR project team to develop upgradeable and reusable hardware to meet the science requirements of current and future investigators. Currently, there are six experiments that are candidates to use the FEANICS mini-facility. This paper will describe the capabilities of this mini-facility and the type of solid combustion testing and diagnostics that can be performed.

Frate, David T.↗

The Fluids and Combustion Facility

Microgravity is an environment with very weak gravitational effects. The Fluids and Combustion Facility (FCF) on the International Space Station (ISS) will support the study of fluid physics and combustion science in a long-duration microgravity environment. The Fluid Combustion Facility's design will permit both independent and remote control operations from the Telescience Support Center. The crew of the International Space Station will continue to insert and remove the experiment module, store and reload removable data storage and media data tapes, and reconfigure diagnostics on either side of the optics benches. Upon completion of the Fluids Combustion Facility, about ten experiments will be conducted within a ten-year period. Several different areas of fluid physics will be studied in the Fluids Combustion Facility. These areas include complex fluids, interfacial phenomena, dynamics and instabilities, and multiphase flows and phase change. Recently, emphasis has been placed in areas that relate directly to NASA missions including life support, power, propulsion, and thermal control systems. By 2006 or 2007, a Fluids Integrated Rack (FIR) and a Combustion Integrated Rack (CIR) will be installed inside the International Space Station. The Fluids Integrated Rack will contain all the hardware and software necessary to perform experiments in fluid physics. A wide range of experiments that meet the requirements of the international space station, including research from other specialties, will be considered. Experiments will be contained in subsystems such as the international standard payload rack, the active rack isolation system, the optics bench, environmental subsystem, electrical power control unit, the gas interface subsystem, and the command and data management subsystem. In conclusion, the Fluids and Combustion Facility will allow researchers to study fluid physics and combustion science in a long-duration microgravity environment. Additional information is included in the original extended abstract.

Kundu, Sampa↗

Flow Boiling and Condensation Experiment (FBCE): Capabilities and System Description

A high-level description of the Flow Boiling and Condensation Experiment (FBCE) system capabilities, design and interface characteristics is presented. Each of the eight FBCE modules are discussed as well as the mechanical, electrical, and software interfaces with the Fluid Combustion Facility’s (FCF) Fluid Integration Rack (FIR), where the experiment will be installed for International Space Station (ISS) operations.

Flow Boiling↗

Status Report on Advanced Reactor Fuels Hot Cell Furnace Testing

The Advanced Fuels Campaign is developing a series of out-of-pile steady state furnace tests on irradiated nuclear fuel pins in order to better characterize and understand isolated fuel performance phenomena. These tests will also provide valuable datasets for validation and improvement of modelling and simulation tools. The Blister Anneal Furnace (BAF) in the INL Hot Fuel Examination Facility (HFEF) has been identified as the ideal location for these tests, and, in order to perform them, a new fixture for the BAF has been designed and commissioned. This report summarizes the objectives, design, characteristics and status of this fixture. The design was finalized, materials procured and tested, and the assembly fixture is now fully fabricated in the mock-up shop of the Fuel Conditioning Facility (FCF) at MFC.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗