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At least 703 records · Page 39

Application of ion-induced nucleation mass spectrometry in the analysis of trace gases evolved from a polyimide film during the thermal curing stages

Trace gases evolved from a polyimide film during its thermal curing stages have been studied using ion-induced nucleation mass spectrometry. The technique involved exposing the test gas sample to a low energy beta source and recording the masses of the ion-induced molecular clusters formed in the reaction chamber. On the basis of the experimentally observed molecular cluster spectra, it has been concluded that the dominant trace component had a molecular weight of 87 atomic mass units. This component has been identified as a molecule of dimethylacetamide (DMAC) which had been used as a solvent in the preparation of the test polyimide specimen. This identification has been further confirmed by comparing the spectra of the test gas sample and the DMAC calibration sample obtained with a conventional mass spectrometer. The advantages of the ion-induced nucleation mass spectrometer versus the conventional mass spectrometer are discussed.

Smith, A. C.↗

Evaluating the energy impact potential of energy efficiency measures for retrofit applications: A case study with U.S. medium office buildings

Quantifying the energy savings of various energy efficiency measures (EEMs) for an energy retrofit project often necessitates an energy audit and detailed whole building energy modeling to evaluate the EEMs; however, this is often cost-prohibitive for small and medium buildings. In order to provide a defined guideline for projects with assumed common baseline characteristics, this paper applies a sensitivity analysis method to evaluate the impact of individual EEMs and groups these into packages to produce deep energy savings for a sample prototype medium office building across 15 climate zones in the United States. We start with one baseline model for each climate zone and nine candidate EEMs with a range of efficiency levels for each EEM. Three energy performance indicators (EPIs) are defined, which are annual electricity use intensity, annual natural gas use intensity, and annual energy cost. Then, a Standard Regression Coefficient (SRC) sensitivity analysis method is applied to determine the sensitivity of each EEM with respect to the three EPIs, and the relative sensitivity of all EEMs are calculated to evaluate their energy impacts. For the selected range of efficiency levels, the results indicate that the EEMs with higher energy impacts (i.e., higher sensitivity) in most climate zones are high-performance windows, reduced interior lighting power, and reduced interior plug and process loads. However, the sensitivity of the EEMs also vary by climate zone and EPI; for example, improved opaque envelope insulation and efficiency of cooling and heating systems are found to have a high energy impact in cold and hot climates.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

The Determination of the Spatial Distribution of Indigenous Lipid Biomarkers in an Immature Jurassic Sediment Using Time-of-Flight–Secondary Ion Mass Spectrometry

The ability to detect and map lipids, including potential lipid biomarkers, within a sedimentary matrix using mass spectrometry (MS) imaging may be critical to determine whether potential lipids detected in samples returned from Mars are indigenous to Mars or are contaminants. Here, we use gas chromatography–mass spectrometry (GC-MS) and time-of-flight–secondary ion mass spectrometry (ToF-SIMS) datasets collected from an organic-rich, thermally immature Jurassic geologic sample to constrain MS imaging analysis of indigenous lipid biomarkers in geologic samples. GC-MS data show that the extractable fractions are dominated by C 27 –C 30 steranes and sterenes as well as isorenieratene derivatives. ToF-SIMS spectra from organic matter-rich laminae contain a strong, spatially restricted signal for ions m/z 370.3, m/z 372.3, and m/z 386.3, which we assign to C 27 sterenes, cholestane (C 27 ), and 4- or 24-methyl steranes (C 28 ), respectively, as well as characteristic fragment ions of isorenieratene derivatives, including m/z 133.1, m/z 171.1, and m/z 237.1. We observed individual steroid spatial heterogeneity at the scale of 10's to 100's of microns. The fine-scale heterogeneity observed implies that indigenous lipid biomarkers concentrated within specific regions may be detectable via ToF-SIMS in samples with even low amounts of organic carbon, including in samples returned from Mars.

59 BASIC BIOLOGICAL SCIENCES↗

Aluminum Clad Spent Nuclear Fuel Task 4: Performance of Aluminum SNF in Dry Storage Experiment Test Plan

This document presents the activities to be performed in support of understanding the performance of aluminum spent nuclear fuel (ASNF) in dry storage. These activities will visually examine and acquire baseline samples of as-irradiated ATR fuel assembly components to determine fuel condition and the morphology of the aluminum oxyhydroxides present on the fuel external surfaces. Because the boehmite phase of oxyhydroxide is projected to be a significant contributor to radiolytic hydrogen production and general corrosion, being able to quantify its presence is of major importance to long term storage of aluminum spent nuclear fuel. Baseline samples will be taken from irradiated end adapters, removed from ATR SNF elements, stored in the ATR Canal. These will be transferred to Idaho National Laboratory (INL) Materials and Fuels Complex (MFC) to perform non-destructive and destructive testing to determine the degree of hydration of the wet-stored aluminum components prior to drying and air storage. Examination of the dry stored SNF at Idaho Nuclear Technology and Engineering Center (INTEC) in CPP-603 Irradiated Fuel Storage Facility (IFSF) will allow the opportunity to identify gross degradation and as conditions permit, sample the surface oxide on fueled and un-fueled portions of the stored assemblies. The information resulting from analysis of the ATR Canal samples will be used to support validation of surrogate samples prepared under Task 6, sample surrogate preparation, and used in Task 1, oxyhydroxide layer behavior and chemistry, Task 2, oxide layer radiolytic gas generation, and Task 5, oxide layer response to drying. Surface oxide samples collected from SNF in IFSF dry storage will SNF dry storage prediction modeling from Task 3, sealed and vented system episodic breathing and gas generation prediction.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Test results on the Viking gas chromatograph-mass spectrometer experiment

The gas chromatograph-mass spectrometer instrument to be utilized in the Viking 1975 Molecular Analysis experiment has undergone preliminary testing in its flight configured version. A synthetic mixture of 24 components as well as a sample of the Murchison meteorite has been used for this purpose. The resulting data not only allowed the identification of most of the organic compounds known to be present, but also revealed the identity of a few unexpected ones. Thus, the sensitivity and reliability of the instrument and data system are satisfactorily demonstrated.

Biemann, K.↗

The Effect of Glass Chemistry on Caesium Volatility in Iron Phosphate Glass Systems - 19344

The UK currently has a stockpile of 99,000 m{sup 3} of intermediate level waste (ILW), with this figure expected to rise to 191,000 m{sup 3} by 2125. Current immobilisation options include cementation and thermal treatment, with cementation being the preferred candidate due to the simplicity of processing. However, thermal processing such as vitrification could offer significant volume reductions, up to 75 % for some waste-streams. In comparison, cementation is generally associated with a volume increase, with a typical waste package seeing a volume increase of 200 - 400 %. For vitrification to be accepted as the preferred treatment option of ILW in the UK, the issue of volatility during the vitrification process must be addressed. Volatile components of ILW such as Cs-137 and Sr-90 account for almost 50 % of the current total radioactivity produced by the UK's ILW stockpile. Therefore, the efficient retention of these elements into the glass immobilisation medium must be considered. Various approaches can be employed when trying to increase volatile retention, however this project has focussed on the influence of glass chemistry on volatility. A series of iron phosphate glasses containing 5 mol % of B{sub 2}O{sub 3}, MnO and ZnO have been produced, where additives have been substituted in place of Fe{sub 2}O{sub 3} in a standard 40Fe{sub 2}O{sub 3}-60P{sub 2}O{sub 5} system. All glass samples were characterised using Raman spectroscopy, SEM-EDX, thermal analysis, XRD and XRF. The glasses were then doped with caesium carbonate and re-melted in the system described below. A simple off-gas system has been developed and commissioned to capture and characterise volatiles released from the glass during melting. The off-gas system has been refined several times, with the most recent design comprising of a sealed stainless steel system, connected to two gas washing bottles containing 150 ml of 50 % nitric acid. Nitrogen gas is passed through the system for the duration of the experiment at a flow rate of ∼ 0.9 L/min to ensure efficient carryover of the volatiles released from the glass melt into the solutions in the gas washing bottles. The total retention of the volatiles can be measuring by analysing the contents of the gas washing bottles using ICP-MS and XRF of the final glass product. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Thermal and Evolved Gas Analysis of Mars Analog Paleosols

Decades of space exploration have shown that three to four billion-year old surface environments on Mars may have been habitable. Ancient surface environments which resemble paleosols (buried sedimentary deposits which formed from subaerial weathering) on Mars have recently been named a high-priority target for biosignature investigation and Mars Sample Return because paleosol mineralogy records valuable information about past climates, and because Archean (~2.6 Ga) paleosols from Earth preserve some of the oldest biosignatures of life on land. However, there has been little effort to characterize terrestrial paleosols with Mars-like mineralogy using instruments analogous to those on current and future missions to Mars, which is imperative for understanding if putative paleosols on Mars should be targeted for future exploration. The objectives of this study were to perform the first comprehensive analysis of Mars-analog paleosols with Mars flight-analog instrumentation and to determine if organic carbon in these paleosols is detectable in the presence of a perchlorate salt.

A. P. Broz↗

Atmosphere Processing Module Automation and Catalyst Durability Analysis for Mars ISRU Pathfinder

The Mars In-Situ Resource Utilization Pathfinder was designed to create fuel using components found in the planet’s atmosphere and regolith for an ascension vehicle to return a potential sample return or crew return vehicle from Mars. The Atmosphere Processing Module (APM), a subunit of the pathfinder, uses cryocoolers to isolate and collect carbon dioxide from Mars simulant gas. The carbon dioxide is fed with hydrogen into a Sabatier reactor where methane is produced. The APM is currently undergoing the final stages of testing at Kennedy Space Center prior to process integration testing with the other subunits of the pathfinder. The automation software for the APM cryocoolers was tested and found to perform nominally. The catalyst used for the Sabatier reactor was investigated to determine the factors contributing to catalyst failure. The results from the catalyst testing require further analysis, but it appears that the rapid change in temperature during reactor start up or the elevated operating temperature is responsible for the changes observed in the catalyst.

Atmosphere Processing Module↗

Kinematics of the H α and H β broad-line region in an SDSS sample of type-1 AGNs

Here, we investigate the kinematics of the part of the broad-line region (BLR) in active galactic nuclei (AGNs) emitting H β and H α emission lines. We explore the widths and asymmetries of the broad H β and H α emission lines in a sample of high-quality (i.e. high signal-to-noise ratio) spectra of type-1 AGN taken from the Data Release 16 of the Sloan Digital Sky Survey in order to explore possible deviation from the gravitationally bound motion. To find only the broad component of H β and H α, we use the FANTASY (Fully Automated pythoN Tool for AGN Spectra analYsis) code for the multicomponent modelling of the AGN spectra and for careful extraction of the broad emission-line parameters. Here, we show that based on the broad-line profiles widths and asymmetries, the BLR gas emitting H β and H α lines follows similar kinematics, and seems to be virialized in our sample of type-1 AGN.

79 ASTRONOMY AND ASTROPHYSICS↗

Swelling and permeability effects during propellant cookoff

Large rocket motors may violently explode when exposed to accidental fires. Even hot metal fragments from a nearby accident may penetrate the propellant and ultimately cause thermal ignition. A mechanistic understanding of heated propellants leading to thermal runaway is a major unsolved problem. Here we show that thermal ignition in propellants can be predicted using a universal cookoff model coupled to a micromechanics pressurization model. Our model predicts the time to thermal ignition in cookoff experiments with variable headspace volumes. Furthermore, we found that experiments with headspace volumes are more prone to deformation which distorts pores and causes increased permeability when the propellant expands into this headspace. Delayed ignition with larger headspace volume correlates with lower headspace pressures during decomposition. We found that our predictions matched experimental measurements best when the initial propellant was impermeable to gas flow rather than being permeable. Similar behavior is expected with other energetic materials with rubbery binders. Our model is validated using data from a separate laboratory. We also present an uncertainty analysis using Latin Hypercube Sampling (LHS) of thermal ignition caused by a steel fragment embedded in the propellant.

33 ADVANCED PROPULSION SYSTEMS↗

Energetics of oxidation and formation of uranium monocarbide

To enable better implementation of uranium monocarbide (UC) as an advanced nuclear fuel for future high-temperature reactors, it is essential to have a thorough knowledge of its thermal and thermodynamic properties under reactor operational conditions. In this work, we studied thermal bulk oxidation of UC by simultaneous thermal analysis consisting of thermogravimetric analysis – differential scanning calorimetry coupled with evolved gas mass spectrometry (TGA-DSC-MS), and we examined the thermodynamic stability of UC using high temperature oxide melt drop solution calorimetry. Further, in air, our studied UC sample (which contains ~5 mol% UO 2 ) was found to undergo a step-wise thermal oxidation process consisting of consecutive oxidations and thermal decomposition reactions: 0.95UC·0.05UO 2 → UO 3 ·0.29(C x O y ) + 0.66CO 2 → UO 3 ·0.20(C x O y ) + 0.09CO 2 → UO 3 ·0.03(C x O y ) + 0.17CO 2 → U 3 O 8 + 0.03CO 2 + 0.166O 2 . DSC was further used to determine the enthalpies of reactions associated with this series of oxidation reactions. Synchrotron X-ray diffraction (XRD) and extended X-ray absorption spectroscopy (EXAFS) were performed to characterize both the long- and short-range structures of UC. The standard enthalpy of formation (ΔH° f ) of UC was determined to be –50.7 ± 10.8 kJ/mol·atom, in good agreement with previous values measured by bomb calorimetry. Lastly, the enthalpic landscape of U-C compounds, including UC, U 2 C 3 , and α-UC 1.94 , were established based on the enthalpy normalized per mole atom, which suggests that U-C phases are thermodynamically stable at lower C/U ratios.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Сrystallinity and size control of silicon nanoparticles synthesized from monosilane in glow-discharge plasma

Decomposition reaction of monosilane in glow discharge plasma of both direct (DC) and alternating current (AC) have been performed. The possibility of nanosilicon synthesis using the glow discharge plasma has been shown. The Raman spectroscopy is applied to study the phase composition and granulometric analysis of the obtained nanosilicon samples. The possibility of the structure and size control of amorphous silicon films with nano crystalline inclusions (a-Si:H/c-Si + nc-Si) by varying pressure and composition of a gas mixture in the process of synthesis has been demonstrated.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Mars Geochemical Instrument (MarGI): An instrument for the analysis of the Martian surface and the search for evidence of life

The Mars Geochemical Instrument, MarGI, was developed to provide a comprehensive analysis of the rocks and surface material on Mars. The instrument combines Differential Thermal Analysis (DTA) with miniature Gas Chromatography-Ion Mobility Spectrometry (GC-IMS) to identify minerals, the presence and state of water, and organic compounds. Miniature pyrolysis ovens are used to both, conduct DTA analysis of soil or crushed rocks samples, and pyrolyze the samples at temperatures up to 1000 degrees C for GC-IMS analysis of the released gases. This combination of analytical processes and techniques, which can characterize the mineralogy of the rocks and soil, and identify and quantify volatiles released during pyrolysis, has applications across a wide range of target sites including comets, planets, asteroids, and moons such as Titan and Europa. The MarGI analytical approach evolved from the Cometary Ice and Dust Experiment (CIDEX) selected to fly on the Comet Rendezvous Asteroid Flyby Mission (CRAF).

Kojiro, Daniel R.↗

Determination of transition metal ions in fossil fuel associated wastewaters using chelation ion chromatography

Here, this study outlines the development and subsequent validation of a method using chelation ion chromatography (CIC) pretreatment followed by traditional ion chromatography (IC) and post column UV/vis detection to measure transition metals in fossil fuel wastewaters, such as oil & gas (O&G) brines and coal mine drainage (CMD) waters. Measurement of transition metals is often an important characterization step in the research of environmental and energy systems. IC represents one way to measure these metals with the advantages of being versatile, simple and relatively low cost compared to other analytical methods. However, high concentrations of alkali and alkaline earth metals present in fossil fuel wastewaters will decrease IC detectability of transition metals in these waters. In this study, a CIC method was developed for the analysis of transition metal ions (Fe 3+ , Cu 2+ , Ni 2+ , Zn 2+ , Co 2+ , Mn 2+ , and Fe 2+ ) in fossil fuel associated wastewaters such as Appalachian CMD and O&G wastewaters from the Permian and Bakken shale basins in the United States. CIC system incorporated an on-line chelator column (e.g., the MetPac CC-1) with high selectivity for transition metals over alkali and alkaline earth metals for salt matrix removal prior to transition metal separation and detection. Additional method developments also included acidifying all samples to 2% v/v HCl and using gradient elution rather than isocratic. The recoverability of transition metals in simple salt solutions commonly found in CMD and brine samples (e.g. NaCl, Na 2 SO 4 , CaCl 2 ) using CIC was evaluated and compared to that using traditional IC. Our results found that the CIC system significantly improved transition metal recoveries for samples in 10,000 mg/L CaCl 2 matrix, reaching 87%-108% recovery for all analytes, as opposed to 2-323% recovery in traditional IC. The limits of detection in this study achieved 10.09 – 161.2 μg/L, comparable to reported values in similar IC studies. The developed method was also verified with certified water samples, resulting in 89% - 111% recoveries in samples with higher analyte concentrations (i.e. >4x the LoDs). The developed method achieved 87% -112% recoveries for most analytes in CMD samples and 72%-138% recoveries for Bakken shale samples, relative to ICP-MS values. Overall, the current IC method can be a very good screening tool for fast and cheap analysis for transition metals at mg/L level, to facilitate selection of samples for more detailed ICP-MS analysis.

01 COAL, LIGNITE, AND PEAT↗

Europan Molecular Indicators of Life Investigation (EMILI) for a Future Europa Lander Mission

The Europan Molecular Indicators of Life Investigation (EMILI) is an instrument concept being developed for the Europa Lander mission currently under study. EMILI will meet and exceed the scientific and technical/resource requirements of the organic composition analyzer identified as a core instrument on the Lander. EMILI tightly couples two complementary analytical techniques, based on 1) liquid extraction and processing with capillary electrophoresis and 2) thermal and chemical extraction with gas chromatography, to robustly detect, structurally characterize, and quantify the broadest range of organics and other Europan chemicals over widely-varying concentrations. Dual processing and analysis paths enable EMILI to perform a thorough characterization of potential molecular biosignatures and contextual compounds in collected surface samples. Here we present a summary of the requirements, design, and development status of EMILI with projected scientific opportunities on the Europa Lander as well as on other potential life detection missions seeking potential molecular biosignatures in situ.

Europa↗

FIB-ToF-SIMS characterization of irradiated U-10Zr

Post-irradiation examination (PIE) is critical for the performance assessment and qualification of nuclear fuels. Secondary ion mass spectrometry (SIMS) is a powerful materials characterization technique that allows for elemental and isotopic mapping with a depth resolution greater than EDS and EPMA. However, it has not yet been applied to PIE of metallic nuclear fuel. Here, in this work, we characterize an fast neutron spectrum irradiated U-10Zr fuel sample using a time-of-flight SIMS (ToF-SIMS) system connected to a FIB/SEM system, which allows for flexible sample analysis compared to a dedicated ToF-SIMS instrument. Analysis of the resulting hyperspectral micrograph data was aided by the development of an unsupervised machine learning (ML) algorithm that iterates on existing methods to segment the 3D micrographic datasets based on the similarity of mass spectra. The results showed that the FIB-ToF-SIMS instrument was potentially capable of spatially resolving closed fission gas bubbles in 3D by continued ion sputtering of the analyzed volume. Additionally, the ML algorithm proved useful in revealing the chemical segregation of light fission products (those with an atomic mass between approximately 85–105 amu, such as ruthenium and rhodium) plus matrix zirconium, heavy fission products (those with an atomic mass between approximately 135–150 amu, such as the lanthanides) and uranium. Future studies are planned to conduct FIB-ToF-SIMS analysis on more irradiated U-Zr samples to study the constituent redistribution.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Precision cleaning verification of fluid components by air/water impingement and total carbon analysis

NASA personnel at Kennedy Space Center's Material Science Laboratory have developed new environmentally sound precision cleaning and verification techniques for systems and components found at the center. This technology is required to replace existing methods traditionally employing CFC-113. The new patent-pending technique of precision cleaning verification is for large components of cryogenic fluid systems. These are stainless steel, sand cast valve bodies with internal surface areas ranging from 0.2 to 0.9 sq m. Extrapolation of this technique to components of even larger sizes (by orders of magnitude) is planned. Currently, the verification process is completely manual. In the new technique, a high velocity, low volume water stream impacts the part to be verified. This process is referred to as Breathing Air/Water Impingement and forms the basis for the Impingement Verification System (IVS). The system is unique in that a gas stream is used to accelerate the water droplets to high speeds. Water is injected into the gas stream in a small, continuous amount. The air/water mixture is then passed through a converging/diverging nozzle where the gas is accelerated to supersonic velocities. These droplets impart sufficient energy to the precision cleaned surface to place non-volatile residue (NVR) contaminants into suspension in the water. The sample water is collected and its NVR level is determined by total organic carbon (TOC) analysis at 880 C. The TOC, in ppm carbon, is used to establish the NVR level. A correlation between the present gravimetric CFC113 NVR and the IVS NVR is found from experimental sensitivity factors measured for various contaminants. The sensitivity has the units of ppm of carbon per mg/sq ft of contaminant. In this paper, the equipment is described and data are presented showing the development of the sensitivity factors from a test set including four NVRs impinged from witness plates of 0.05 to 0.75 sq m.

Barile, Ronald G.↗

Precision Cleaning Verification of Fluid Components by Air/Water Impingement and Total Carbon Analysis

NASA personnel at Kennedy Space Center's Material Science Laboratory have developed new environmentally sound precision cleaning and verification techniques for systems and components found at the center. This technology is required to replace existing methods traditionally employing CFC-113. The new patent-pending technique of precision cleaning verification is for large components of cryogenic fluid systems. These are stainless steel, sand cast valve bodies with internal surface areas ranging from 0.2 to 0.9 m(exp 2). Extrapolation of this technique to components of even larger sizes (by orders of magnitude) is planned. Currently, the verification process is completely manual. In the new technique, a high velocity, low volume water stream impacts the part to be verified. This process is referred to as Breathing Air/Water Impingement and forms the basis for the Impingement Verification System (IVS). The system is unique in that a gas stream is used to accelerate the water droplets to high speeds. Water is injected into the gas stream in a small, continuous amount. The air/water mixture is then passed through a converging-diverging nozzle where the gas is accelerated to supersonic velocities. These droplets impart sufficient energy to the precision cleaned surface to place non-volatile residue (NVR) contaminants into suspension in the water. The sample water is collected and its NVR level is determined by total organic carbon (TOC) analysis at 880 C. The TOC, in ppm carbon, is used to establish the NVR level. A correlation between the present gravimetric CFC-113 NVR and the IVS NVR is found from experimental sensitivity factors measured for various contaminants. The sensitivity has the units of ppm of carbon per mg-ft(exp 2) of contaminant. In this paper, the equipment is described and data are presented showing the development of the sensitivity factors from a test set including four NVR's impinged from witness plates of 0.05 to 0.75 m(exp 2).

Barile, Ronald G.↗