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A modular approach for automated sample preparation and chemical analysis

Changes in international relations, especially within the past several years, have dramatically affected the programmatic thrusts of the U.S. Department of Energy (DOE). The DOE now is addressing the environmental cleanup required as a result of 50 years of nuclear arms research and production. One major obstacle in the remediation of these areas is the chemical determination of potentially contaminated material using currently acceptable practices. Process bottlenecks and exposure to hazardous conditions pose problems for the DOE. One proposed solution is the application of modular automated chemistry using Standard Laboratory Modules (SLM) to perform Standard Analysis Methods (SAM). The Contaminant Analysis Automation (CAA) Program has developed standards and prototype equipment that will accelerate the development of modular chemistry technology and is transferring this technology to private industry.

Clark, Michael L.↗

Propulsion Research at the Propulsion Research Center of the NASA Marshall Space Flight Center

The Propulsion Research Center of the NASA Marshall Space Flight Center is engaged in research activities aimed at providing the bases for fundamental advancement of a range of space propulsion technologies. There are four broad research themes. Advanced chemical propulsion studies focus on the detailed chemistry and transport processes for high-pressure combustion, and on the understanding and control of combustion stability. New high-energy propellant research ranges from theoretical prediction of new propellant properties through experimental characterization propellant performance, material interactions, aging properties, and ignition behavior. Another research area involves advanced nuclear electric propulsion with new robust and lightweight materials and with designs for advanced fuels. Nuclear electric propulsion systems are characterized using simulated nuclear systems, where the non-nuclear power source has the form and power input of a nuclear reactor. This permits detailed testing of nuclear propulsion systems in a non-nuclear environment. In-space propulsion research is focused primarily on high power plasma thruster work. New methods for achieving higher thrust in these devices are being studied theoretically and experimentally. Solar thermal propulsion research is also underway for in-space applications. The fourth of these research areas is advanced energetics. Specific research here includes the containment of ion clouds for extended periods. This is aimed at proving the concept of antimatter trapping and storage for use ultimately in propulsion applications. Another activity in this involves research into lightweight magnetic technology for space propulsion applications.

Blevins, John↗

Hierarchies of Models: Toward Understanding Planetary Nebulae

Stars like our sun (initial masses between 0.8 to 8 solar masses) end their lives as swollen red giants surrounded by cool extended atmospheres. The nuclear reactions in their cores create carbon, nitrogen and oxygen, which are transported by convection to the outer envelope of the stellar atmosphere. As the star finally collapses to become a white dwarf, this envelope is expelled from the star to form a planetary nebula (PN) rich in organic molecules. The physics, dynamics, and chemistry of these nebulae are poorly understood and have implications not only for our understanding of the stellar life cycle but also for organic astrochemistry and the creation of prebiotic molecules in interstellar space. We are working toward generating three-dimensional models of planetary nebulae (PNe), which include the size, orientation, shape, expansion rate and mass distribution of the nebula. Such a reconstruction of a PN is a challenging problem for several reasons. First, the data consist of images obtained over time from the Hubble Space Telescope (HST) and spectra obtained from Kitt Peak National Observatory (KPNO) and Cerro Tololo Inter-American Observatory (CTIO). These images are of course taken from a single viewpoint in space, which amounts to a very challenging tomographic reconstruction. Second, the fact that we have two disparate and orthogonal data types requires that we utilize a method that allows these data to be used together to obtain a solution. To address these first two challenges we employ Bayesian model estimation using a parameterized physical model that incorporates much prior information about the known physics of the PN. In our previous works we have found that the forward problem of the comprehensive model is extremely time consuming. To address this challenge, we explore the use of a set of hierarchical models, which allow us to estimate increasingly more detailed sets of model parameters. These hierarchical models of increasing complexity are akin to scientific theories of increasing sophistication, with each new model/theory being a refinement of a previous one by either incorporating additional prior information or by introducing a new set of parameters to model an entirely new phenomenon. We apply these models to both a simulated and a real ellipsoidal PN to initially estimate the position, angular size, and orientation of the nebula as a two-dimensional object and use these estimates to later examine its three-dimensional properties. The efficiency/accuracy tradeoffs of the techniques are studied to determine the advantages and disadvantages of employing a set of hierarchical models over a single comprehensive model.

Knuth, Kevin H.↗

Hierarchies of Models: Toward Understanding Planetary Nebulae

Stars like our sun (initial masses between 0.8 to 8 solar masses) end their lives as swollen red giants surrounded by cool extended atmospheres. The nuclear reactions in their cores create carbon, nitrogen and oxygen, which are transported by convection to the outer envelope of the stellar atmosphere. As the star finally collapses to become a white dwarf, this envelope is expelled from the star to form a planetary nebula (PN) rich in organic molecules. The physics, dynamics, and chemistry of these nebulae are poorly understood and have implications not only for our understanding of the stellar life cycle but also for organic astrochemistry and the creation of prebiotic molecules in interstellar space. We are working toward generating three-dimensional models of planetary nebulae (PNe), which include the size, orientation, shape, expansion rate and mass distribution of the nebula. Such a reconstruction of a PN is a challenging problem for several reasons. First, the data consist of images obtained over time from the Hubble Space Telescope (HST) and spectra obtained from Kitt Peak National Observatory (KPNO) and Cerro Tololo Inter-American Observatory (CTIO). These images are of course taken from a single viewpoint in space, which amounts to a very challenging tomographic reconstruction. Second, the fact that we have two disparate and orthogonal data types requires that we utilize a method that allows these data to be used together to obtain a solution. To address these first two challenges we employ Bayesian model estimation using a parameterized physical model that incorporates much prior information about the known physics of the PN. In our previous works we have found that the forward problem of the comprehensive model is extremely time consuming. To address this challenge, we explore the use of a set of hierarchical models, which allow us to estimate increasingly more detailed sets of model parameters. These hierarchical models of increasing complexity are akin to scientific theories of increasing sophistication, with each new model/theory being a refinement of a previous one by either incorporating additional prior information or by introducing a new set of parameters to model an entirely new phenomenon. We apply these models to both a simulated and a real ellipsoidal PN to initially estimate the position, angular size, and orientation of the nebula as a two-dimensional object and use these estimates to later examine its three-dimensional properties. The efficiency/accuracy tradeoffs of the techniques are studied to determine the advantages and disadvantages of employing a set of hierarchical models over a single comprehensive model.

Knuth, Kevin H.↗

The Science Goals of NASA's Exploration Initiative

The recently released policy directive, "A Renewed Spirit of Discovery: The President's Vision for U. S. Space Exploration," seeks to advance the U. S. scientific, security and economic interest through a program of space exploration which will robotically explore the solar system and extend human presence to the Moon, Mars and beyond. NASA's implementation of this vision will be guided by compelling questions of scientific and societal importance, including the origin of our Solar System and the search for life beyond Earth. The Exploration Roadmap identifies four key targets: the Moon, Mars, the outer Solar System, and extra-solar planets. First, a lunar investigation will set up exploration test beds, search for resources, and study the geological record of the early Solar System. Human missions to the Moon will serve as precursors for human missions to Mars and other destinations, but will also be driven by their support for furthering science. The second key target is the search for past and present water and life on Mars. Following on from discoveries by Spirit and Opportunity, by the end of the decade there will have been an additional rover, a lander and two orbiters studying Mars. These will set the stage for a sample return mission in 2013, increasingly complex robotic investigations, and an eventual human landing. The third key target is the study of underground oceans, biological chemistry, and their potential for life in the outer Solar System. Beginning with the arrival of Cassini at Saturn in July 2004 and a landing on Titan in 2006, the next decade will see an extended investigation of the Jupiter icy moons by a mission making use of Project Prometheus, a program to develop space nuclear power and nuclear-electric propulsion. Finally, the search for Earth-like planets and life includes a series of telescopic missions designed to find and characterize extra-solar planets and search them for evidence of life. These missions include HST and Spitzer, operating now; Kepler, SIM, JWST, and TPF, currently under development; and the vision missions, Life Finder and Planet Imager, which will possibly be constructed in space by astronauts.

Gardner, Jonathan P.↗

Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗

Tribological evaluation and analysis of coating materials

A physical characterization of coating materials by analytical techniques such as XPS, AES, ellipsometry, and nuclear reaction analysis can contribute to the understanding of adhesion and friction of the coatings and can partially predict the tribological properties of the coatings. This two-part paper describes the tribological properties and physical characteristics of (1) diamondlike carbon (DLC) films and (2) silicon nitride (SiN(x)) films. Emphasis is to relate plasma deposition conditions to the film chemistry and composition and to the adhesion and friction of the films. With the DLC films, the higher the plasma deposition power, the less the hydrogen concentration and the greater the film density and the hardness. The friction behavior of DLC films deposited at higher deposition powers (200 to 300 W) is similar to that of bulk diamond. Even in a vacuum, the DLC films effectively lubricate ceramic surfaces (Si3N4) at temperatures to 500 C. With SiN(x) films, the silicon to nitrogen ratios and the amount of amorphous silicon depend on deposition frequency. The presence of rich amorphous silicon in the high-frequency plasma-deposited SiN(x) films increases their adhesion and friction above 500 C in vacuum.

Miyoshi, Kazuhisa↗

Messengers from the Early Solar System - Comets as Carriers of Cosmic Information

Viewed from a cosmic perspective, Earth is a dry planet yet its oceans are enriched in deuterium by a large factor relative to nebular hydrogen. Can comets have delivered Earth s water? The question of exogenous delivery of water and organics to Earth and other young planets is of critical importance for understanding the origin of Earth s water, and for assessing the possible existence of exo-planets similar to Earth. Strong gradients in temperature and chemistry in the proto-planetary disk, coupled with dynamical models, imply that comets from the Oort Cloud and Kuiper Disk reservoirs should have diverse composition. The primary volatiles in comets (ices native to the nucleus) provide the preferred metric, and taxonomies based on them are now beginning to emerge [1, 2, 3]. The measurement of cosmic parameters such as the nuclear spin temperatures for H2O, NH3, and CH4, and of enrichment factors for isotopologues (D/H in water and hydrogen cyanide, N-14/N-15 in CN and hydrogen cyanide) provide additional important tests for the origin of cometary material.

Mumma, Michael J.↗

Messengers from the Early Solar System - The Similarity and Diversity of Comets

Viewed from a cosmic perspective, Earth is a dry planet yet its oceans are enriched in deuterium by a large factor relative to nebular hydrogen. Can comets have delivered Earth's water? The question of exogenous delivery of water and organics to Earth and other young planets is of critical importance for understanding the origin of Earth's water, and for assessing the possible existence of exo-planets similar to Earth. Strong gradients in temperature and chemistry in the proto-planetary disk, coupled with dynamical models, imply that comets from the Oort Cloud and Kuiper Disk reservoirs should have diverse composition. The primary volatiles in comets (ices native to the nucleus) provide the preferred metric, and taxonomies based on them are now beginning to emerge [1,2,3]. The measurement of cosmic parameters such as the nuclear spin temperatures for H2O, NH3, and CH4, and of enrichment factors for isotopologues (D/H in water and hydrogen cyanide, N-14/N-15 in CN and hydrogen cyanide provide additional important tests for the origin of cometary material. I will provide an overview of these aspects, and their implications for the origin of Earth's water and prebiotic organics.

Mumma, Michael J.↗

Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite

We have demonstrated a route to reversibly intercalate fluoride-anion receptor complexes in graphite via a nonaqueous electrochemical process. This approach may find application for a rechargeable lithium-fluoride dual-ion intercalating battery with high specific energy. The cell chemistry presented here uses graphite cathodes with LiF dissolved in a nonaqueous solvent through the aid of anion receptors. Cells have been demonstrated with reversible cathode specific capacity of approximately 80 mAh/g at discharge plateaus of upward of 4.8 V, with graphite staging of the intercalant observed via in situ synchrotron X-ray diffraction during charging. Electrochemical impedance spectroscopy and B-11 nuclear magnetic resonance studies suggest that cointercalation of the anion receptor with the fluoride occurs during charging, which likely limits the cathode specific capacity. The anion receptor type dictates the extent of graphite fluorination, and must be further optimized to realize high theoretical fluorination levels. To find these optimal anion receptors, we have designed an ab initio calculations-based scheme aimed at identifying receptors with favorable fluoride binding and release properties.

electrolytes↗

Evaluation of tantalum-alloy-clad uranium mononitride fuel specimens from 7500-hour, 1040 C pumped-lithium-loop test

Simulated nuclear fuel element specimens, consisting of uranium mononitride (UN) fuel cylinders clad with tungsten-lined T-111, were exposed for up to 7500 hr at 1040 C (1900 F) in a pumped-lithium loop. The lithium flow velocity was 1.5 m/sec (5 ft/sec) in the specimen test section. No evidence of any compatibility problems between the specimens and the flowing lithium was found based on appearance, weight change, chemistry, and metallography. Direct exposure of the UN to the lithium through a simulated cladding crack resulted in some erosion of the UN in the area of the defect. The T-111 cladding was ductile after lithium exposure, but it was sensitive to hydrogen embrittlement during post-test handling.

Watson, G. K.↗

Environmental Stress Testing of the Single Sample Cylinder: A Proven Consensus Standard for Internal Gas Analysis (IGA) or Residual Gas Analysis (RGA)

In August 2008, Schuessler Consulting was contracted by NASA GSFC in support of the NASA Electronic Parts and Packaging (NEPP) program to perform two separate studies on moisture laden air in a stainless steel cylinder that had been designed to become a consensus standard for Test Method 1018. This Test Method was originally released for hybrids under Mil. Std. 883 but was quickly utilized on other microelectronic devices under the auspice of Mil. Std. 750. The cylinder had subsequently been fabricated for the 750 community. It was back-filled with moist air and subsequently analyzed over a period of time under a previous NASA contract. It had been shown that moisture in the 4000 - 5000 ppm range could be analyzed rather precisely with a mass spectrometer, commonly referred to as a Residual Gas Analyzer (RGA). The scope of this study was to ascertain if the composition and precision varied as a function of thermal shock at sub-zero temperatures and whether there was consensus when the standard was submitted to other RGA units. It was demonstrated and published that the consensus standard would yield precise RGA data for moisture within +/- 1% when optimized for a given RGA unit. It has been subsequently shown in this study at Oneida Research Services, that sub-zero storage did not affect that precision when a well-defined protocol for the analysis was followed. The consensus standard was taken to a second facility for analysis where it was found that moisture adsorption on the transfer lines caused precision to drop to +/- 12%. The Single Sample Cylinder (SSC) is a one liter stainless steel cylinder with associated sampling valves and has considerable weight and volume. But this considerable size allows for approximately 300 gas samples of the same composition to be delivered to any RGA unit. Lastly, a smaller cylinder, approximately 75 cc, of a second consensus standard was fabricated and tested with a different mix of fixed gases where moisture was kept in the 100 ppm range. This second standard has the potential of providing 30 gaseous samples and can be readily shipped to any analytical facility that desires to generate comparison RGA data. A series of comparison residual gas analyses was performed at the Honeywell Federal Manufacturing & Technologies facility in the National Nuclear Facility Administration s plant in Kansas City to complete this project. It was shown that improvements in the precision of a given RGA unit can be done by controlling the cycle time for each analysis and increasing analysis temperatures to minimize moisture adsorption. It was also found that a "one time event" in the subzero storage of the large SSC did not effect the units ability to continuously supply precise samples of the same chemistry, however the "event" caused a permanent +8% shift in the reported value of the moisture content. Lastly, a set of SSC RGA results was plotted on a common graph with DSCC "correlation study" RGA data. The result demonstrates the ability of the SSC to remove many of the individual variances that single, individual samples introduce. The consensus standards are now in storage at Oneida Research Services, one of the DSCC certified houses that does RGA to Military Standards, where they await future studies. The analytical data and the operational parameters of the instruments used are provided in the following discussion. Limitations and suggested means for improvement of both precision and accuracy are provided.

Schuessler, Philipp WH↗

Annual Conference on Nuclear and Space Radiation Effects, 14th, College of William and Mary, Williamsburg, Va., July 12-15, 1977, Proceedings

Topics related to processing and hardness assurance are considered, taking into account the radiation hardening of CMOS technologies, technological advances in the manufacture of radiation-hardened CMOS integrated circuits, CMOS hardness assurance through process controls and optimized design procedures, the application of operational amplifiers to hardened systems, a hard off-the-shelf SG1524 pulse width modulator, and the gamma-induced voltage breakdown anomaly in a Schottky diode. Basic mechanisms are examined, giving attention to chemical and structural aspects of the irradiation behavior of SiO2 films on silicon, experimental observations of the chemistry of the SiO2/Si interface, leakage current phenomena in irradiated SOS devices, the avalanche injection of holes into SiO2, the low-temperature radiation response of Al2O3 gate insulators, and neutron damage mechanisms in silicon at 10 K. Other subjects discussed are related to radiation effects in devices and circuits, space radiation effects, and aspects of simulation, energy deposition, and dosimetry.

Stahl, R. H.↗

Joint Conference on Sensing of Environmental Pollutants, 4th, New Orleans, La., November 6-11, 1977, Proceedings

Papers are presented on such topics as environmental chemistry, the effects of sulfur compounds on air quality, the prediction and monitoring of biological effects caused by environmental pollutants, environmental indicators, the satellite remote sensing of air pollution, weather and climate modification by pollution, and the monitoring and assessment of radioactive pollutants. Consideration is also given to empirical and quantitative modeling of air quality, disposal of hazardous and nontoxic materials, sensing and assessment of water quality, pollution source monitoring, and assessment of some environmental impacts of fossil and nuclear fuels.

Source record↗

The Role of Comets as Possible Contributors of Water and Prebiotic Organics to Terrestrial Planets

The question of exogenous delivery of organics and water to Earth and other young planets is of critical importance for understanding the origin of Earth's water, and for assessing the prospects for existence of Earth-like exo-planets. Viewed from a cosmic perspective, Earth is a dry planet yet its oceans are enriched in deuterium by a large factor relative to nebular hydrogen. Can comets have delivered Earth's water? The deuterium content of comets is key to ,assessing their role as contributors of water to Earth. Icy bodies today reside in two distinct reservoirs, the Oort Cloud and the Kuiper Disk (divided into the classical disk, the scattered disk, and the detached or extended disk populations). Orbital parameters can indicate the cosmic storage reservoir for a given comet. Knowledge of the diversity of comets within a reservoir assists in assessing their possible contribution to early Earth, but requires quantitative knowledge of their components - dust and ice. Strong gradients in temperature and chemistry in the proto-planetary disk, coupled with dynamical dispersion of an outer disk of icy planetesimals, imply that comets from KD and OC reservoirs should have diverse composition. The primary volatiles (native to the nucleus) provide the preferred metric for building a taxonomy for comets, and the number of comets so quantified is growing rapidly. Taxonomies based on native species (primary volatiles) are now beginning to emerge [1, 2, 3]. The measurement of cosmic parameters such as the nuclear spin temperatures for H2O, NH3 and CH4, and of enrichment factors for isotopologues (D/H in water and hydrogen cyanide, N-14/N-15 in CN and hydrogen cyanide) provide additional tests of the origin of cometary material. I will provide an overview of these aspects, and implications for the origin of Earth's water and prebiotic organics.

Mumma, Michael J.↗

Plasma chemistry for inorganic materials

Practical application of plasma chemistry to the development of inorganic materials using both low temperature and warm plasmas are summarized. Topics cover: the surface nitrification and oxidation of metals; chemical vapor deposition; formation of minute oxide particles; the composition of oxides from chloride vapor; the composition of carbides and nitrides; freezing high temperature phases by plasma arc welding and plasma jet; use of plasma in the development of a substitute for petroleum; the production of silicon for use in solar cell batteries; and insulating the inner surface of nuclear fusion reactor walls.

Matsumoto, O.↗

Uncertainty Analysis of Decomposing Polyurethane Foam

Sensitivity/uncertainty analyses are necessary to determine where to allocate resources for improved predictions in support of our nation's nuclear safety mission. Yet, sensitivity/uncertainty analyses are not commonly performed on complex combustion models because the calculations are time consuming, CPU intensive, nontrivial exercises that can lead to deceptive results. To illustrate these ideas, a variety of sensitivity/uncertainty analyses were used to determine the uncertainty associated with thermal decomposition of polyurethane foam exposed to high radiative flux boundary conditions. The polyurethane used in this study is a rigid closed-cell foam used as an encapsulant. Related polyurethane binders such as Estane are used in many energetic materials of interest to the JANNAF community. The complex, finite element foam decomposition model used in this study has 25 input parameters that include chemistry, polymer structure, and thermophysical properties. The response variable was selected as the steady-state decomposition front velocity calculated as the derivative of the decomposition front location versus time. An analytical mean value sensitivity/uncertainty (MV) analysis was used to determine the standard deviation by taking numerical derivatives of the response variable with respect to each of the 25 input parameters. Since the response variable is also a derivative, the standard deviation was essentially determined from a second derivative that was extremely sensitive to numerical noise. To minimize the numerical noise, 50-micrometer element dimensions and approximately 1-msec time steps were required to obtain stable uncertainty results. As an alternative method to determine the uncertainty and sensitivity in the decomposition front velocity, surrogate response surfaces were generated for use with a constrained Latin Hypercube Sampling (LHS) technique. Two surrogate response surfaces were investigated: 1) a linear surrogate response surface (LIN) and 2) a quadratic response surface (QUAD). The LHS techniques do not require derivatives of the response variable and are subsequently relatively insensitive to numerical noise. To compare the LIN and QUAD methods to the MV method, a direct LHS analysis (DLHS) was performed using the full grid and timestep resolved finite element model. The surrogate response models (LIN and QUAD) are shown to give acceptable values of the mean and standard deviation when compared to the fully converged DLHS model.

Hobbs, Michael L.↗

Possible effects of volcanic eruptions on stratospheric minor constituent chemistry

Although stratosphere penetrating volcanic eruptions have been infrequent during the last half century, periods have existed in the last several hundred years when such eruptions were significantly more frequent. Several mechanisms exist for these injections to affect stratospheric minor constituent chemistry, both on the long-term average and for short-term perturbations. These mechanisms are reviewed and, because of the sensitivity of current models of stratospheric ozone to chlorine perturbations, quantitative estimates are made of chlorine injection rates. It is found that, if chlorine makes up as much as 0.5 to 1% of the gases released and if the total gases released are about the same magnitude as the fine ash, then a major stratosphere penetrating eruption could deplete the ozone column by several percent. The estimate for the Agung eruption of 1963 is just under 1% an amount not excluded by the ozone record but complicated by the peak in atmospheric nuclear explosions at about the same time.

Stolarski, R. S.↗