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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Prognostics Health Management Model for LED Package Failure Under Contaminated Environment

The reliability consideration of LED products includes both luminous flux drop and color shift. Previous research either talks about luminous maintenance or color shift, because luminous flux degradation usually takes very long time to observe. In this paper, the impact of a VOC (volatile organic compound) contaminated luminous flux and color stability are examined. As a result, both luminous degradation and color shift had been recorded in a short time. Test samples are white, phosphor-converted, high-power LED packages. Absolute radiant flux is measured with integrating sphere system to calculate the luminous flux. Luminous flux degradation and color shift distance were plotted versus aging time to show the degradation pattern. A prognostic health management (PHM) method based on the state variables and state estimator have been proposed in this paper. In this PHM framework, unscented kalman filter (UKF) was deployed as the carrier of all states. During the estimation process, third order dynamic transfer function was used to implement the PHM framework. Both of the luminous flux and color shift distance have been used as the state variable with the same PHM framework to exam the robustness of the method. Predicted remaining useful life is calculated at every measurement point to compare with the tested remaining useful life. The result shows that state estimator can be used as the method for the PHM of LED degradation with respect to both luminous flux and color shift distance. The prediction of remaining useful life of LED package, made by the states estimator and data driven approach, falls in the acceptable error-bounds (20%) after a short training of the estimator.

Lall, Pradeep↗
DOE OSTI2014

Microstructure fabrication process induced modulations in CVD graphene

The systematic Raman spectroscopic study of a “mimicked” graphene device fabrication is presented. Upon photoresist baking, compressive stress is induced in the graphene which disappears after it is removed. The indirect irradiation from the electron beam (through the photoresist) does not significantly alter graphene characteristic Raman peaks indicating that graphene quality is preserved upon the exposure. The 2D peak shifts and the intensity ratio of 2D and G band, I(2D)/I(G), decreases upon direct metal deposition (Co and Py) suggesting that the electronic modulation occurs due to sp{sup 2} C-C bond weakening. In contrast, a thin metal oxide film deposited graphene does not show either the significant 2D and G peaks shift or I(2D)/I(G) decrease upon the metal deposition suggesting the oxide protect the graphene quality in the fabrication process.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Large polarization-dependent exciton optical Stark effect in lead iodide perovskites

A strong interaction of a semiconductor with a below-bandgap laser pulse causes a blue-shift of the bandgap transition energy, known as the optical Stark effect. The energy shift persists only during the pulse duration with an instantaneous response time. The optical Stark effect has practical relevance for applications, including quantum information processing and communication, and passively mode-locked femtosecond lasers. Here we demonstrate that solution-processable lead-halide perovskites exhibit a large optical Stark effect that is easily resolved at room temperature resulting from the sharp excitonic feature near the bandedge. We also demonstrate that a polarized pump pulse selectively shifts one spin state producing a spin splitting of the degenerate excitonic states. Such selective spin manipulation is an important prerequisite for spintronic applications. Lastly, our result implies that such hybrid semiconductors may have great potential for optoelectronic applications beyond photovoltaics.

14 SOLAR ENERGY↗
DOE OSTI2024

In situ Synchrotron X‐ray Metrology Boosted by Automated Data Analysis for Real‐time Monitoring of Cathode Calcination

Abstract Synchrotron X‐ray‐based in situ metrology is advantageous for monitoring the synthesis of battery materials, offering high throughput, high spatial and temporal resolution, and chemical sensitivity. However, the rapid generation of massive data poses a challenge to on‐site, on‐the‐fly analysis needed for real‐time process monitoring. Here, a weighted lagged cross‐correlation (WLCC) similarity approach is presented for automated data analysis, which merges with in situ synchrotron X‐ray diffraction metrology to monitor the calcination process of the archetypal nickel‐based cathode, LiNiO 2 . The WLCC approach, incorporating variables that account for peak shifts and width changes associated with structural transformations, enables rapid extraction of phase progression within 10 seconds from tens of diffraction patterns. Details are captured, from initial precursors to intermediates and the final layered LiNiO 2 , providing information for agile on‐site adjustments during experiments and complementing post hoc diffraction analysis by offering insights into early‐stage phase nucleation and growth. Expanding this data‐powered platform paves the way for real time calcination process monitoring and control, which is pivotal to quality control in battery cathode manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Source Characterization and Temporal Variation of Methane Seepage from Thermokarst Lakes on the Alaska North Slope in Response to Arctic Climate Change

The goals of this research were to characterize the source, magnitude and temporal variability of methane seepage from thermokarst lakes (TKL) within the Alaska North Slope gas hydrate province, assess the vulnerability of these areas to ongoing and future arctic climate change and determine if gas hydrate dissociation resulting from permafrost melting is contributing to the current lake emissions. Analyses were focused on four main lake locations referred to in this report: Lake Qalluuraq (referred to as Lake Q) and Lake Teshekpuk (both on Alaska's North Slope) and Lake Killarney and Goldstream Bill Lake (both in Alaska's interior). From analyses of gases coming from lakes in Alaska, we showed that ecological seeps are common in Alaska and they account for a larger source of atmospheric methane today than geologic subcap seeps. Emissions from the geologic source could increase with potential implications for climate warming feedbacks. Our analyses of TKL sites showing gas ebullition were complemented with geophysical surveys, providing important insight about the distribution of shallow gas in the sediments and the lake bottom manifestation of seepage (e.g., pockmarks). In Lake Q, Chirp data were limited in their capacity to image deeper sediments and did not capture the thaw bulb. The failure to capture the thaw bulb at Lake Q may in part be related to the fact that the present day lake is a remnant of an older, larger, and now-partially drained lake. These suggestions are consistent with our analyses of a dated core of sediment from the lake that shows that a wetland has been present at the site of Lake Q since approximately 12,000 thousand years ago. Chemical analyses of the core indicate that the availability of methane at the site has changed during the past and is correlated with past environmental changes (i.e. temperature and hydrology) in the Arctic. Discovery of methane seeps in Lake Teshekpuk in the northernmost part of the lake during 2009 reconnaissance surveys provided a strong impetus to visit this area in 2010. The seismic methods applied in Lake Teshekpuk were able to image pockmarks, widespread shallow gas in the sediments, and the relationship among different sediment packages on the lake's bottom, but even boomer seismics did not detect permafrost beneath the northern part of the lake. By characterizing the biogeochemistry of shallow TKL with methane seeps we showed that the radical seasonal shifts in ice cover and temperature. These seasonal environmental differences result in distinct consumption and production processes of biologically-relevant compounds. The combined effects of temperature, ice-volume and other lithological factors linked to seepage from the lake are manifest in the distribution of sedimentary methane in Lake Q during ice-covered and ice-free conditions. The biogeochemistry results illustrated very active methanotrophy in TKLs. Substantial effort was subsequently made to characterize the nature of methanotrophic communities in TKLs. We applied stable isotope probing approaches to genetically characterize the methanotrophs most active in utilizing methane in TKLs. Our study is the first to identify methane oxidizing organisms active in arctic TKLs, and revealing that type I methanotrophs and type II methanotrophs are abundant and active in assimilating methane in TKLs. These organisms play an important role in limiting the flux of methane from these sites. Our investigations indicate that as temperatures increase in the Arctic, oxidation rates and active methanotrophic populations will also shift. Whether these changes can offset predicted increases in methanogenesis is an important question underlying models of future methane flux and resultant climate change. Overall our findings indicate that TKLs and their ability to act as both source and sink of methane are exceedingly sensitive to environmental change.

03 NATURAL GAS↗
DOE OSTI2010

The role of absorption in Raman amplification in warm plasma

Raman backscattering in plasma is subject to--collisional and collisionless--absorption of the interacting waves. A model for studying its role over a wide parameter range is developed by coupling the envelope equations for pump, probe, and plasma waves with those describing heating of the plasma. The latter is treated as a warm fluid, making the model useful for moderate temperatures and field amplitudes. The main effect is the time-dependent Bohm-Gross shift of the Langmuir resonance frequency, which can either enhance or suppress amplification; this can be further controlled by varying the frequency of the pump. Anisotropy in the collisional processes for longitudinal and transverse waves leads to temperature anisotropy at high field amplitudes. Direct Landau damping of the plasma wave, as well as its contribution to the frequency shift, can be neglected due to rapid saturation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

An experimental and modeling study of the application of membrane contactor reactors to methanol synthesis using pure CO 2 feeds

We describe here a post-combustion CO 2 capture and utilization (CCU) technology that converts the CO 2 into methanol (MeOH), a valuable chemical, thus providing a way to monetize the carbon captured to offset process costs. Methanol synthesis (MeS) has been discussed recently for application to CCU, but thermodynamic limitations make it difficult to convert in a single pass a large CO 2 fraction. Conventional catalysts show slow kinetics in converting CO 2 -rich syngas (or pure CO 2 ) into MeOH. Our Group developed a novel MeS process, employing a membrane contactor reactor (MCR) system that attains carbon conversions significantly higher than equilibrium. Our focus here is to process pure CO 2 streams by combining the MCR with a separate reactor, which converts the CO 2 into a syngas via the reverse water gas shift (RWGS) reaction. In this preliminary effort, the RWGS reactor (RWGSR) is assumed to reach equilibrium. Additional MeS kinetic rate data are generated validating experimentally the ability of the MeS-MCR to process as a feed the RWGSR exit stream. The performance of the combined (RWGSR/MeS-MCR) system is then simulated using a recently developed MeS-MCR model. In conclusion, the findings are encouraging, and research is currently ongoing to experimentally validate the RWGSR/MeS-MCR system performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Characterization and Suppression of the Electromagnetic Interference Induced Phase Shift in the JLab FEL Photo - Injector Advanced Drive Laser System

The drive laser for the photo-cathode gun used in the JLab Free Electron Laser (FEL) facility had been experiencing various phase shifts on the order of tens of degrees (>20{sup o} at 1497 MHz or >40ps) when changing the Advanced Drive Laser (ADL) [2][3][4] micro-pulse frequencies. These phase shifts introduced multiple complications when trying to setup the accelerator for operation, ultimately inhibiting the robustness and overall performance of the FEL. Through rigorous phase measurements and systematic characterizations, we determined that the phase shifts could be attributed to electromagnetic interference (EMI) coupling into the ADL phase control loop, and subsequently resolved the issue of phase shift to within tenths of a degree (<0.5{sup o} at 1497 MHz or <1ps). The diagnostic method developed and the knowledge gained through the entire process will prove to be invaluable for future designs of similar systems.

43 PARTICLE ACCELERATORS↗
NASA NTRS2003

NASA GPM GV Science Requirements

An important scientific objective of the NASA portion of the GPM Mission is to generate quantitatively-based error characterization information along with the rainrate retrievals emanating from the GPM constellation of satellites. These data must serve four main purposes: (1) they must be of sufficient quality, uniformity, and timeliness to govern the observation weighting schemes used in the data assimilation modules of numerical weather prediction models; (2) they must extend over that portion of the globe accessible by the GPM core satellite to which the NASA GV program is focused - (approx.65 degree inclination); (3) they must have sufficient specificity to enable detection of physically-formulated microphysical and meteorological weaknesses in the standard physical level 2 rainrate algorithms to be used in the GPM Precipitation Processing System (PPS), i.e., algorithms which will have evolved from the TRMM standard physical level 2 algorithms; and (4) they must support the use of physical error modeling as a primary validation tool and as the eventual replacement of the conventional GV approach of statistically intercomparing surface rainrates fiom ground and satellite measurements. This approach to ground validation research represents a paradigm shift vis-&-vis the program developed for the TRMM mission, which conducted ground validation largely as a statistical intercomparison process between raingauge-derived or radar-derived rainrates and the TRMM satellite rainrate retrievals -- long after the original satellite retrievals were archived. This approach has been able to quantify averaged rainrate differences between the satellite algorithms and the ground instruments, but has not been able to explain causes of algorithm failures or produce error information directly compatible with the cost functions of data assimilation schemes. These schemes require periodic and near-realtime bias uncertainty (i.e., global space-time distributed conditional accuracy of the retrieved rainrates) and local error covariance structure (i.e., global space-time distributed error correlation information for the local 4-dimensional space-time domain -- or in simpler terms, the matrix form of precision error). This can only be accomplished by establishing a network of high quality-heavily instrumented supersites selectively distributed at a few oceanic, continental, and coastal sites. Economics and pragmatics dictate that the network must be made up of a relatively small number of sites (6-8) created through international cooperation. This presentation will address some of the details of the methodology behind the error characterization approach, some proposed solutions for expanding site-developed error properties to regional scales, a data processing and communications concept that would enable rapid implementation of algorithm improvement by the algorithm developers, and the likely available options for developing the supersite network.

Smith, E.↗
NASA NTRS2012

Fischer-Tropsch Catalyst for Aviation Fuel Production

As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to nonpetroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

DeLaRee, Ana B.↗
DOE OSTI2015

Disentangling Mechanisms That Mediate the Balance Between Stochastic and Deterministic Processes in Microbial Succession

Despite growing recognition that deterministic and stochastic factors simultaneously influence bacterial communities, little is known about mechanisms shifting their relative importance. To better understand underlying mechanisms, we developed a conceptual model linking ecosystem development during primary succession to shifts in the stochastic/deterministic balance. To evaluate the conceptual model we coupled spatiotemporal data on soil bacterial communities with environmental conditions spanning 105 years of salt marsh development. At the local scale there was a progression from stochasticity to determinism due to Na accumulation with increasing ecosystem age, supporting a main element of the conceptual model. At the regional-scale, soil organic matter (SOM) governed the relative influence of stochasticity and the type of deterministic ecological selection, suggesting scale-dependency in how deterministic ecological selection is imposed. Analysis of a new ecological simulation model supported these conceptual inferences. Looking forward, we propose an extended conceptual model that integrates primary and secondary succession in microbial systems.

bacterial succession↗
DOE OSTI2020

Generalised hyper-Ramsey spectroscopy of two-level atoms in an optically dense medium

The peculiarities of Ramsey resonance and its sensitivity to the light shift from an optically dense medium of cold atoms are investigated. Different composite pulse protocols for clock spectroscopy, including hyper-Ramsey, modified and generalised hyper-Ramsey schemes, are compared. Error signals change significantly due to the processes of absorption and dispersion in the atomic medium. The dependence of the position of the central fringe resonance with a residual uncompensated light shift of the atomic transition is studied with the attenuation of the radiation intensity in the medium taken into account. It is shown that using a combination of generalised hyper-Ramsey error signals allows one to suppress the sensitivity to the light shift for any length of the medium. (laser cooling of atoms)

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Zeolite Membrane Reactor for Pre-Combustion Carbon Dioxide Capture (Final Scientific/Technical Report)

Water-gas shift (WGS) reaction followed by carbon dioxide (CO 2 ) separation is a critical step in the integrated gasification combined cycle (IGCC) process for fossil-fuel-fired electrical power generation with CO 2 capture. To intensify the IGCC process hydrogen-permselective zeolite membrane reactor offers promise to replace the conventional energy-intensive fixed-bed reactors and solvent-based CO 2 capture units. The objectives of this project were to develop a bench-scale zeolite membrane reactor (total membrane area: 932 cm 2 for a 21-tube membrane bundle) for the water-gas-shift reaction of raw syngas from an oxygen-blown coal-gasifier for H 2 production with simultaneous CO 2 separation at the capability of about 2 kilograms H 2 per day (equivalent to 2 kW IGCC power plant) and to demonstrate significant progress toward achieving overall performance goal of 90% CO 2 capture rate with 95% CO 2 purity at the cost of electricity 30% less than the baseline carbon capture approaches. This report summarizes results obtained in this project on scaling up the zeolite membrane reactor by a factor of 200 in membrane area, tests of the bench-scale zeolite membrane reactor for the water-gas-shift reaction at high temperature and high-pressure, and techno-economic analysis of the integration of the zeolite membrane reactor in IGCC power plant for the electrical generation with CO 2 capture. With effective pore modification by catalytic cracking deposition of MDES (methyldiethoxysilane), fabrication of MFI-type zeolite membranes was successfully scaled-up from a lab-scale disk type to bench-scale multiple-tube bundles on low-cost alumina supports. A Co-Mo based sour shift catalyst was evaluated and used in the zeolite membrane reactors for water-gas-shift reaction. The reaction kinetic and gas-permeation equations were developed and employed in mathematic models to guide/predict experiments/performance of zeolite membrane reactors for water-gas shift reaction. Multiple-tube zeolite membrane bundles and reactors were designed, fabricated and tested for gas separation and water-gas-shift reactions with real raw syngas from a coal-fired gasifier operated at high temperature and pressure. The zeolite membrane reactors demonstrated good long-term thermal and chemical stability and constant H 2 permeance (>300 GPU) together with a Knudsen selectivity (~4.7) for H 2 over CO 2 in the field test (cumulative time >28 hours) with high-sulfur coal-derived syngas. The zeolite-membrane-reactor integrated IGCC process was designed using the performance experimentally measured by the University of Cincinnati team with a single-tube zeolite membrane reactor that offers a CO conversion >98% with more than 90% of CO 2 and H 2 captured. With the above integrative approaches, a techno-economic analysis for a cost-benefit comparison was performed to uncover features that determine the power output, capital expenditure, operating expenditure, cost of electricity and cost of CO 2 capture in a 550-MW zeolite-membrane-reactor integrated IGCC process. The integration of the zeolite membrane reactor in IGCC could provide a significant reduction of 80% and 27% in the power consumption for Selexol™ Acid Gas Removal and CO 2 compression, respectively, which lowers the total auxiliary power consumption by 12.5%. However, the low pressure required at permeate stream for maintaining the driving force of hydrogen permeation through the zeolite membrane costs a huge power in permeate compressor, compensating the power consumption reduction achieved with the membrane reactor. Thus, for coal-fired IGCC for electricity generation with 90% CO 2 captured, the integration of the membrane reactor could provide a CO conversion ~99% and a significant drop in cost-of-electricity using zeolite membrane with H 2 permeance >600 GPU and the H 2 /CO 2 selectivity over 70.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2016

Aluminum Metal Dissolution for Mark-18A Target Processing

The Mark-18A Program was established to preserve the unique materials found in Mark-18A targets for future research and development activity within the Department of Energy or other U.S. government agencies. The Savannah River Site has 65 Mark-18A targets to be provided for the recovery of high valued isotopes. The majority of the recovery work will be performed in the Savannah River National Laboratory (SRNL) Shielded Cells due to dose concerns. The recovered product will be transported to the Oak Ridge National Laboratory (ORNL) for future research and development tasks. The Mark-18A target material will be removed from their current configuration, dissolved, chemically separated, and calcined to a stable oxide. The baseline flowsheet is patterned after the flowsheet ORNL has previously used to process both Mark-18A and Mark-42 targets. However, it is necessary for SRNL to adapt its facility and the ORNL flowsheet to identify process improvements to successfully recover the actinide materials within the constraints of the SRNL Shielded Cells. These studies evaluated and demonstrated a chemical method for cladding removal using a mixture of sodium nitrate (NaNO 3 ) and sodium hydroxide (NaOH). Experiments provided better insights into dissolution of the Mark-18A aluminum cladding. In particular, these studies measured the effects of temperature on dissolution rate, flammable gas generation, and nitrite formation. Using the lessons learned from batch dissolution testing at SRNL, a continuous dissolution flowsheet was successfully demonstrated using prototypic-shaped materials and chemically-conservative materials. The SRNL target dissolution flowsheet departs from the baseline ORNL flowsheet in small but significant ways as discussed in the following paragraphs. These flowsheet changes facilitate faster initial reaction rates at a given temperature, enable cladding removal at a lower process temperature, and yield a more uniform dissolution rate throughout cladding removal. Multiple tests indicate that the total time at the dissolution temperatures will be about six hours for one fourth of a target. The shorter dissolution time provides the benefit of a single-shift dissolver operation. Off gas sampling determined that the quantities of flammable hydrogen (H 2 ) and ammonia (NH 3 ) expected in the process off gas will meet allowable flammable gas generation rates for the Shielded Cells Facility. The SRNL approach enables NaOH to be added at a constant rate, which simplifies operations in the shielded cells. In all six continuous dissolution tests, the process was easy to control with minimal operator interface. Analyses of process solutions throughout the experiments provide a better understanding of system behavior. The data show consistent behavior across several similar but different test conditions. Between the batch-test and continuous-test data, if future changes to the flowsheet are required, sufficient data exist to adequately predict how the system will respond to those changes. Future work will focus on design, fabrication, and evaluation of a system for dissolution of one-fourth of a Mark-18A target, which will be full-scale operations for SRNL. Based on these results, the process parameters are adequately understood and the system can be operated safely.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Reversible Tuning of the Surface Plasmon Resonance of Indium Tin Oxide Nanocrystals by Gas-Phase Oxidation and Reduction

Heavily doped oxide nanocrystals exhibit a tunable localized surface plasmon resonance (LSPR) in the infrared, a property that is promising for applications in photonics, spectroscopy, and photochemistry. Nanocrystal carrier density and, thus, spectral response are adjustable via chemical reaction; yet, the fundamental processes that govern this behavior are poorly understood. In this work, we study the time dependence of the LSPR supported by indium tin oxide (ITO) nanocrystals during O 2 and N 2 annealing with in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). We show that the LSPR red-shifts upon oxidation in O 2 and blue-shifts to its original position upon reduction in N 2 . A reaction–diffusion model allows us to rationalize the underlying physicochemical processes and quantitatively connect nanocrystal redox chemistry, solid-state diffusion, carrier density, and the LSPR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Understanding Anomalous Gas-Phase Peak Shifts in Dip-and-Pull Ambient Pressure XPS Experiments

Dip-and-pull ambient pressure X-ray photoelectron spectroscopy (AP-XPS) holds promise to uncover elementary processes of (photo)electrochemistry. We show, however, that the sample for such experiments should preferably be nonporous and the potential on the surface homogeneous. We carried out dip-and-pull AP-XPS experiments on a hematite thin film sample under the photoelectrochemical oxygen evolution reaction (OER) and find unexpected O 1s core level shifts. Upon electrochemical biasing under simulated solar light illumination, the gas-phase water peak shifted more than the electrolyte peak. To uncover the origin of the unexpected larger shift of the gas-phase peak, we performed electrostatic simulations using COMSOL, to map the potential field in the relevant volume between the sample and the first aperture of the XPS spectrometer. A number of geometric models were considered. We find that when the potential on the sample surface is inhomogeneous, e.g., with ionically isolated electrolyte patches, the gas-phase peak of the spectrum can shift more than the peak due to the electrolyte film. This suggests that at the measured sample position, the local potential was not as set by the potentiostat. Despite this, we find reversible consumption and replenishment of hydroxide in the spectra, which, due to OH– being the reactant of the OER in alkaline electrolyte, makes sense chemically. We propose that this is linked to OH– diffusion across the measured sample position, driven by the potential dependent consumption and replenishment of OH– at the nearby well-connected surface regions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

A priori precision estimation for neutron triples counting

The nondestructive assay of Plutonium bearing items for criticality, safety, security, safeguards, inventory balance, process control, waste management and compliance is often undertaken using correlated neutron counting. In particular Multiplicity Shift Register analysis allows one to extract autocorrelation parameters from the pulse train which can, within the framework of a simple interpretational model, be related to the effective {sup 240}Pu spontaneous fission mass present. The effective {sup 240}Pu mass is a weighted sum of the {sup 238}Pu, {sup 240}Pu and {sup 242}Pu masses so if the relative isotopic composition of the Pu can be established from the measured {sup 240}Pu effective mass one can estimate the total Pu mass and also the masses of the individual isotopes, example the fissile species {sup 239}Pu and {sup 241}Pu. In multiplicity counting three counting rates are obtained. These are the Singles, Doubles and Triples rates. The Singles rate is just the gross, totals or trigger rate. The Doubles and Triples rates are calculated from factorial moments of the observed signal triggered neutron multiplicity distributions following spontaneous fission in the item and can be thought of as the rate of observed coincident pairs and coincident triplets on the pulse train. Coincident events come about because the spontaneous fission and induced fission chains taking place in the item result in bursts of neutrons. These remain time correlated during the detection process and so retain information, through the burst size distribution, about the Pu content. In designing and assessing the performance of a detector system to meet a given goal it is necessary to make a priori estimates of the counting precision for all three kinds of rates. This is non-trivial because the counting does not obey the familiar rules of a Poissonian counting experiment because the pulse train has time correlated events on it and the train is sampled by event triggered gates that may overlap. For Singles and Doubles simple approximate analytical empirical rules for how to estimate the variance have been developed guided by theory and refined by experiment. However, for Triples no equivalent rules have been put forward and tested until now. In this work we propose an analytical expression, the CSH relation, for the variance on the Triples count and exercise it against experimental data gathered for Pu items measured in the Los Alamos National Laboratory's Epithermal Neutron Multiplicity Counter (ENMC). Preliminary results are encouraging and reasonable agreement with observation, considered fit for scoping studies, is obtained. We have also looked at the behavior using Monte Carlo simulations. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

THE COSMOLOGICAL IMPACT OF LUMINOUS TeV BLAZARS. I. IMPLICATIONS OF PLASMA INSTABILITIES FOR THE INTERGALACTIC MAGNETIC FIELD AND EXTRAGALACTIC GAMMA-RAY BACKGROUND

Inverse Compton cascades (ICCs) initiated by energetic gamma rays (E {approx}> 100 GeV) enhance the GeV emission from bright, extragalactic TeV sources. The absence of this emission from bright TeV blazars has been used to constrain the intergalactic magnetic field (IGMF), and the stringent limits placed on the unresolved extragalactic gamma-ray background (EGRB) by Fermi have been used to argue against a large number of such objects at high redshifts. However, these are predicated on the assumption that inverse Compton scattering is the primary energy-loss mechanism for the ultrarelativistic pairs produced by the annihilation of the energetic gamma rays on extragalactic background light photons. Here, we show that for sufficiently bright TeV sources (isotropic-equivalent luminosities {approx}> 10{sup 42} erg s{sup -1}) plasma beam instabilities, specifically the 'oblique' instability, present a plausible mechanism by which the energy of these pairs can be dissipated locally, heating the intergalactic medium. Since these instabilities typically grow on timescales short in comparison to the inverse Compton cooling rate, they necessarily suppress the ICCs. As a consequence, this places a severe constraint on efforts to limit the IGMF from the lack of a discernible GeV bump in TeV sources. Similarly, it considerably weakens the Fermi limits on the evolution of blazar populations. Specifically, we construct a TeV-blazar luminosity function from those objects currently observed and find that it is very well described by the quasar luminosity function at z {approx} 0.1, shifted to lower luminosities and number densities, suggesting that both classes of sources are regulated by similar processes. Extending this relationship to higher redshifts, we show that the magnitude and shape of the EGRB above {approx}10 GeV are naturally reproduced with this particular example of a rapidly evolving TeV-blazar luminosity function.

79 ASTRONOMY AND ASTROPHYSICS↗