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Systematic Structure–Property Relationship Studies in Palladium-Catalyzed Methane Complete Combustion

To limit further rising levels in methane emissions from stationary and mobile sources and to enable promising technologies based on methane, the development of efficient combustion catalysts that completely oxidize CH 4 to CO 2 and H 2 O at low temperatures in the presence of high steam concentrations is required. Palladium is widely considered as one of the most promising materials for this reaction, and a better understanding of the factors affecting its activity and stability is crucial to design even more improved catalysts that efficiently utilize this precious metal. Here we report a study of the effect of three important variables (particle size, support, and reaction conditions including water) on the activity of supported Pd catalysts. We use uniform palladium nanocrystals as catalyst precursors to prepare a library of well-defined catalysts to systematically describe structure–property relationships with help from theory and in situ X-ray absorption spectroscopy. With this approach, we confirm that PdO is the most active phase and that small differences in reaction rates as a function of size are likely due to variations in the surface crystal structure. We further demonstrate that the support exerts a limited influence on the PdO activity, with inert (SiO 2 ), acidic (Al 2 O 3 ), and redox-active (Ce 0.8 Zr 0.2 O 2 ) supports providing similar rates, while basic (MgO) supports show remarkably lower activity. Finally, we show that the introduction of steam leads to a considerable decrease in rates that is due to coverage effects, rather than structural and/or phase changes. Altogether, the data suggest that to further increase the activity and stability of Pd-based catalysts for methane combustion, increasing the surface area of supported PdO phases while avoiding strong adsorption of water on the catalytic surfaces is required. Furthermore, this study clarifies contrasting reports in the literature about the active phase and stability of Pd-based materials for methane combustion.

36 MATERIALS SCIENCE↗

A broadly applicable function for describing luminescence dose response

The basic form of luminescence dose response is investigated, with the aim of developing a single function to account for the appearance of linear, superlinear, sublinear, and supralinear behaviors and variations in saturation signal level and rate. A function is assembled based on the assumption of first order behavior in different major factors contributing to measured luminescence-dosimetric signals. Different versions of the function are developed for standardized and non-dose-normalized responses. Data generated using a two trap two recombination center model and experimental data for natural quartz are analyzed to compare results obtained using different signals, measurement protocols, pretreatment conditions, and radiation qualities. The function well describes a range of dose dependent behavior, including sublinear, superlinear, supralinear, and non-monotonic responses and relative response to α and β radiation, based on change in relative recombination and trapping probability affecting signals sourced from a single electron trap.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Photosynthetic responses to temperature across the tropics: a meta-analytic approach

Background and Aims Tropical forests exchange more carbon dioxide (CO 2 ) with the atmosphere than any other terrestrial biome. Yet, uncertainty in the projected carbon balance over the next century is roughly three times greater for the tropics than other for ecosystems. Our limited knowledge of tropical plant physiological responses, including photosynthetic, to climate change is a substantial source of uncertainty in our ability to forecast the global terrestrial carbon sink. Methods Here, we used a meta-analytic approach, focusing on tropical photosynthetic temperature responses, to address this knowledge gap. Our dataset, gleaned from 18 independent studies, included leaf-level light-saturated photosynthetic (A sat ) temperature responses from 108 woody species, with additional temperature parameters (35 species) and rates (250 species) of both maximum rates of electron transport (J max ) and Rubisco carboxylation (V cmax ). We investigated how these parameters responded to mean annual temperature (MAT), temperature variability, aridity and elevation, as well as also how responses differed among successional strategy, leaf habit and light environment. Key Results Optimum temperatures for A sat (T optA ) and J max (T optJ ) increased with MAT but not for V cmax (T optV ). Although photosynthetic rates were higher for ‘light’ than ‘shaded’ leaves, light conditions did not generate differences in temperature response parameters. T optA did not differ with successional strategy, but early successional species had ~4 °C wider thermal niches than mid/late species. Semi-deciduous species had ~1 °C higher T optA than broadleaf evergreen species. Most global modelling efforts consider all tropical forests as a single ‘broadleaf evergreen’ functional type, but our data show that tropical species with different leaf habits display distinct temperature responses that should be included in modelling efforts. Conclusions This novel research will inform modelling efforts to quantify tropical ecosystem carbon cycling and provide more accurate representations of how these key ecosystems will respond to altered temperature patterns in the face of climate warming.

Carter, Kelsey R. [Oak Ridge National Laboratory (↗

Vapor Growth of Alloy-Type Semiconductor Crystals

The present effort is part of a continuing research program directed towards the investigation of basic vapor transport phenomena and of crystal growth properties of electronic materials. The primary purpose of ground-based studies is the development and definition of optimum experimental parameters for flight experiments. The ground-based effort includes the investigation of gravity-driven convection effects on mass transport rates and on crystal morphology for different orientations of the density gradient with respect to the gravity vector, and as a function of pressure and of temperature. In addition to the experimental tasks, theoretical efforts involve the quantitative thermodynamic analysis of the systems under investigation, the computation of fluid dynamic parameters, and the consideration of other possible effects on fluid flow under vertical, stabilizing and microgravity conditions. The specific experiments to be performed in a microgravity environment include the investigation of vapor transport and crystal growth phenomena of the GeSe-Xenon system and of the mass flux and growth of bulk and layer-type crystals of Hg sub (1-x) Cd sub x Te using HgI as a transport agent.

Wiedemeier, H.↗

Orbital Injection of the SEDSAT Satellite: Tethered Systems Dynamics and Flight Data Analysis

This report deals with the following topics which are all related to the orbital injection of the SEDSAT satellite: Dynamics and Stability of Tether Oscillations after the First Cut. The dynamics of the tether after the first cut (i.e., without the Shuttle attached to it) is investigated. The tether oscillations with the free end are analyzed in order to assess the stability of the rectilinear configuration in between the two tether cuts; analysis of Unstable Modes. The unstable modes that appear for high libration angles are further investigated in order to determine their occurrences and the possible transition from bound librations to rotations; Orbital Release Strategies for SEDSAT. A parametric analysis of the orbital decay rate of the SEDSAT satellite after the two tether cuts has been carried out as a function of the following free parameters: libration amplitude at the end of deployment, deviation angle from LV at the first cut, and orbital anomaly at the second cut. The values of these parameters that provide a minimum orbital decay rate of the satellite (after the two cuts) have been computed; and Dynamics and Control of SEDSAT. The deployment control law has been modified to cope with the new ejection velocity of the satellite from the Shuttle cargo bay. New reference profiles have been derived as well as new control parameters. Timing errors at the satellite release as a function of the variations of the initial conditions and the tension model parameters have been estimated for the modified control law.

Lorenzini, Enrico C.↗

J-2X Abort System Development

The J-2X is an expendable liquid hydrogen (LH2)/liquid oxygen (LOX) gas generator cycle rocket engine that is currently being designed as the primary upper stage propulsion element for the new NASA Ares vehicle family. The J-2X engine will contain abort logic that functions as an integral component of the Ares vehicle abort system. This system is responsible for detecting and responding to conditions indicative of impending Loss of Mission (LOM), Loss of Vehicle (LOV), and/or catastrophic Loss of Crew (LOC) failure events. As an earth orbit ascent phase engine, the J-2X is a high power density propulsion element with non-negligible risk of fast propagation rate failures that can quickly lead to LOM, LOV, and/or LOC events. Aggressive reliability requirements for manned Ares missions and the risk of fast propagating J-2X failures dictate the need for on-engine abort condition monitoring and autonomous response capability as well as traditional abort agents such as the vehicle computer, flight crew, and ground control not located on the engine. This paper describes the baseline J-2X abort subsystem concept of operations, as well as the development process for this subsystem. A strategy that leverages heritage system experience and responds to an evolving engine design as well as J-2X specific test data to support abort system development is described. The utilization of performance and failure simulation models to support abort system sensor selection, failure detectability and discrimination studies, decision threshold definition, and abort system performance verification and validation is outlined. The basis for abort false positive and false negative performance constraints is described. Development challenges associated with information shortfalls in the design cycle, abort condition coverage and response assessment, engine-vehicle interface definition, and abort system performance verification and validation are also discussed.

Santi, Louis M.↗

Molten salt to supercritical CO2 diffusion-bonded heat exchanger testing to support component certification for advanced nuclear power systems

Commercial utilization of the diffusion-bonded heat exchanger (DBHE) for high-temperature applications has prompted an ASME Boiler and Pressure Vessel Code Case development effort to employ these components in Section III (nuclear plant) applications. As part of this effort, a series of DBHE have been fabricated. These heat exchangers will be among the first printed-circuit geometries to be tested for functionality in a molten salt environment. These 15-25kW test specimens will be evaluated under steady-state conditions to compare pressure drop and terminal temperatures measurements with those predicted by existing flow and heat transfer correlations. The test units will then be subjected to thermal transients similar to those expected in Generation IV reactor systems by varying the hot and cold fluid mass flow rates and by changing inlet temperatures. Data collected from these tests will narrow the technical gaps related to two-fluid PCHE and identify special design requirements of compact heat exchangers containing primary reactor coolant. Descriptions of one of two test units and the testing plan are discussed here.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Development of Kinetics and Mathematical Models for High Pressure Gasification of Lignite-Switchgrass Blends

The overall objective of the current project was to investigate the high pressure gasification characteristics of a feed containing both coal and biomass. The two feed types differ in their ash contents and ash composition, particularly the alkali content. Gasification of a combined feed of coal and biomass has the potential for considerable synergies that might lead to a dramatic improvement in process economics and flexibility. The proposed study aimed to develop a detailed understanding of the chemistry, kinetics, and transport effects during high pressure gasification of coal-biomass blend feed. Specifically, we studied to develop: (a) an understanding of the catalytic effect of alkali and other inorganic species present in the biomass and coal, (b) an understanding of processing conditions under which synergistic effects of the blending of coal and biomass might be observed. This included the role of particle size, residence time, and proximity of the two feed types, (c) kinetics of high pressure gasification of individual feeds as well as the blends, and (d) development of mathematical models that incorporate kinetics and transport models to enable prediction of gasification rate at a given set of operating conditions, and (e) protocols to extend the results to other feed resources. The goal was to provide a fundamental understanding of the gasification process and guide in optimizing the configurations and design of the next generation of gasifiers. The approach undertaken was centered on two basic premises: (1) the gasification for small particles without internal mass transfer limitations can be treated as the sum of two processes in series (pyrolysis and char gasification) , and (2) the reactivity of the char generated during pyrolysis not only depends on the pressure and temperature but is also affected by the heating rates. Thus low heating rates (10-50 °C/min) typical of PTGA fail to produce char that would typically be formed at high heating rates (~10 4 °C/sec), encountered in entrained flow gasifiers. The char morphology, also a function of the heating rate, would influence the transport rates during the char gasification phase. Thus, heating rate plays a critical role through which both, pyrolysis and char gasification, are interconnected. We utilized two complementary gasification experiments: PEFR (pressurized entrained flow gasifier) and PTGA (pressurized thermo-gravimetric analyzer). The PEFR allowed us to study gasification at pressures, temperatures, and heating rates relevant for coal-biomass gasifiers. The PTGA work was useful in understanding the basic chemistry of the evolution of various gaseous species during pyrolysis. These results helped improved our understanding of the chemistry and chemical changes during pyrolysis. The role alkali metals and other inorganics in char gasification using steam and/or CO 2 was investigated. Finally, the mathematical models for char gasification without the transport effects were developed at commercial operating conditions.

09 BIOMASS FUELS↗

Reaction analogy based forcing for incompressible scalar turbulence

Here, we present a novel reaction analogy (RA) based forcing method for generating statistically stationary scalar fields in incompressible turbulence. The new method can produce more general scalar probability density functions (PDFs), for example, quasi-double- δ PDF, than current methods, while ensuring that scalar fields remain bounded, unlike existent forcing methodologies that can potentially violate naturally existing bounds. Such features are useful for generating initial fields in nonpremixed combustion, inlet conditions for spatially developing flows, or for studying non-Gaussian scalar turbulence. The RA method mathematically models hypothetical chemical reactions that convert reactants in a mixed state back into its pure unmixed components. Various types of chemical reactions are formulated and the corresponding mathematical expressions derived such that the reaction term is smooth in scalar space and is consistent with mass conservation. For large values of the scalar forcing rate, the method produces statistically stationary quasi-double- δ scalar PDFs. Quasiuniform, Gaussian, and stretched exponential scalar statistics are recovered for smaller values of the scalar forcing rate. The shape of the scalar PDF can be further controlled by changing the stoichiometric coefficients of the reaction. Finally, the ability of the new method to produce fully developed passive scalar fields with quasi-Gaussian PDFs is also investigated, by exploring the convergence of the scalar variance spectrum to the Obukhov-Corrsin scaling and of the third-order mixed structure function to the “four-thirds” Yaglom's law.

42 ENGINEERING↗

The active titration method for measuring local hydroxyl radical concentration

We are developing a method for measuring ambient OH by monitoring its rate of reaction with a chemical species. Our technique involves the local, instantaneous release of a mixture of saturated cyclic hydrocarbons (titrants) and perfluorocarbons (dispersants). These species must not normally be present in ambient air above the part per trillion concentration. We then track the mixture downwind using a real-time portable ECD tracer instrument. We collect air samples in canisters every few minutes for roughly one hour. We then return to the laboratory and analyze our air samples to determine the ratios of the titrant to dispersant concentrations. The trends in these ratios give us the ambient OH concentration from the relation: dlnR/dt = -k(OH). A successful measurement of OH requires that the trends in these ratios be measureable. We must not perturb ambient OH concentrations. The titrant to dispersant ratio must be spatially invariant. Finally, heterogeneous reactions of our titrant and dispersant species must be negligible relative to the titrant reaction with OH. We have conducted laboratory studies of our ability to measure the titrant to dispersant ratios as a function of concentration down to the few part per trillion concentration. We have subsequently used these results in a gaussian puff model to estimate our expected uncertainty in a field measurement of OH. Our results indicate that under a range of atmospheric conditions we expect to be able to measure OH with a sensitivity of 3x10(exp 5) cm(exp -3). In our most optimistic scenarios, we obtain a sensitivity of 1x10(exp 5) cm(exp -3). These sensitivity values reflect our anticipated ability to measure the ratio trends. However, because we are also using a rate constant to obtain our (OH) from this ratio trend, our accuracy cannot be better than that of the rate constant, which we expect to be about 20 percent.

Sprengnether, Michele↗

Recent Advances in Understanding the Structure and Properties of Amorphous Oxide Semiconductors

Here, amorphous oxide semiconductors (AOSs)—ternary or quaternary oxides of post-transition metals such as In-Sn-O, Zn-Sn-O, or In-Ga-Zn-O—have been known for a decade and have attracted a great deal of attention as they pos-sess several technological advantages, including low-temperature large-area deposition, mechanical flexibility, smooth surfaces, and high carrier mobility that is an order of magnitude larger than that of amorphous silicon (a-Si:H). Compared to their crystalline counterparts, the structure of AOSs is extremely sensitive to deposition conditions, stoichiometry, and composition, giving rise to a wide range of tunable optical and electrical properties. The large parameter space and the resulting complex deposition–structure–property relationships in AOSs make the currently available theoretical and experimental research data rather scattered and the design of new materials difficult. In this work, the key properties of several In-based AOSs are studied as a function of cooling rates, oxygen stoichiometry, cation composition, or lattice strain. Based on a thor-ough comparison of the results of ab initio mode ling, comprehensive structural analysis, accurate property calculations, and systematic experimental measure-ments, a four-dimensional parameter space for AOSs is derived, serving as a solid foundation for property optimization in known AOSs and for design of next-generation transparent amorphous semiconductors.

36 MATERIALS SCIENCE↗

Versatile Liquid Crystal Elastomer Formulations Using Amine-Acrylate Chemistry and Processing for Advanced Manufacturing

This study aims to tune rheological properties of liquid crystal elastomers (LCEs) through a strategic approach, leveraging the differing reaction rates of thiols and primary and secondary amines with acrylate monomers or the inclusion of processing additives to enable amenability to advanced manufacturing. We found that varying the time of oligomerization at elevated temperatures of amine-functional monomers with acrylate-functional monomers enabled simple control of rheological properties. Additionally, we could also control rheological properties by introducing reinforcing fillers or organic solvents. By varying the oligomerization conditions, we achieved a broad range of viscosities, from 1.1 Pa s to 560 Pa s as measured at 60 °C. When the rheological properties were varied through the incorporation of various solid and liquid inclusions, viscosities could range from less than 1 Pa s to nearly 1000 Pa s when measured at 60 °C. The shape morphing capabilities that are intrinsic to LCEs and the mechanical properties were also characterized. Here, we find that the oligomerization conditions and the addition of fillers influence shape morphing and energy absorption, as characterized by the stress–strain characteristics, further suggesting their potential to be used in energy dissipation applications where performance can be turned. Last, we demonstrate how the range of accessible rheological properties grants formulations amenable to various advanced manufacturing techniques.

Liquid chromatography↗

Enhancing nanoscale charged colloid crystallization near a metastable liquid binodal

Achieving predictive control over crystallization using non-classical nucleation while avoiding kinetic traps would be a step towards designing materials with new functionalities. We address these challenges by inducing the bottom-up assembly of nanocrystals into ordered arrays, or superlattices. Using electrostatics—rather than density—to tune the interactions between particles, we watch self-assembly proceed through a metastable liquid phase. Here, we systematically investigate the phase behaviour as a function of quench conditions in situ and in real time using small-angle X-ray scattering. By fitting to colloid, liquid and superlattice models, we extract the time evolution of each phase and the system phase diagram, which we find to be consistent with short-range attractive interactions. Using the predictive power of the phase diagram, we establish control of the self-assembly rate over three orders of magnitude, and we identify one- and two-step self-assembly regimes, with only the latter implicating the metastable liquid as an intermediate. The presence of the metastable liquid increases the superlattice formation rate relative to the equivalent one-step pathway, and the superlattice order increases with the rate, revealing a generalizable kinetic strategy for promoting and enhancing ordered assembly.

Tanner, Christian P. N. [University of California,↗

A highly active, CO 2 -tolerant electrode for the oxygen reduction reaction

One challenge facing the development of high-performance cathodes for solid oxide fuel cells (SOFC) is the fast degradation rate of cathodes due to poisoning by contaminants commonly encountered in ambient air such as CO 2 . In this paper we report a double perovskite PrBa 0.8 Ca 0.2 Co 2 O 5+δ (PBCC) cathode with excellent ORR activity and remarkable CO 2 tolerance under realistic operation conditions. When tested in a symmetrical cell in air with ~1 vol% CO 2 at 750 °C, the PBCC electrode shows an area specific resistance of ~0.024 Ω cm 2 , which increases to 0.028 Ω cm 2 after 1000 h operation. The degradation rate is ~1/24 of that of the state-of-the-art La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF) cathode under the same conditions. Impedance spectroscopy and in situ surface enhanced Raman spectroscopy analyses indicate that the surface of the PBCC electrode is much more active for oxygen exchange and more robust against CO 2 than that of LSCF, as confirmed by density functional theory calculations. The fast ORR kinetics and excellent durability of PBCC in air with CO 2 highlight the potential of PBCC as a highly promising material for devices involving oxygen electrochemistry such as solid oxide fuel cells, electrolysis cells, or gas separation membranes.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Establishing structure-sensitivity of ceria reducibility: real-time observations of surface-hydrogen interactions

The first layer of atoms on an oxide catalyst provides the first sites for adsorption of reactants and the last sites before products or oxygen are desorbed. We employ a unique combination of morphological, structural, and chemical analyses of a model ceria catalyst with different surface terminations under an H 2 environment to unequivocally establish the effect of the last layer of atoms on surface reduction. (111) and (100) terminated epitaxial islands of ceria are simultaneously studied in situ allowing for a direct investigation of the structure–reducibility relationship under identical conditions. Kinetic rate constants of Ce 4+ to Ce 3+ transformation and equilibrium concentrations are extracted for both surface terminations. Unlike the kinetic rate constants, which are practically the same for both types of islands, more pronounced oxygen release, and overall higher reducibility were observed for (100) islands compared to (111) ones. The findings are in agreement with coordination-limited oxygen vacancy formation energies calculated by density functional theory. The results point out the important aspect of surface terminations in redox processes, with particular impact on the catalytic reactions of a variety of catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimal Run Strategies in Monte Carlo Iterated Fission Source Simulations

The method of successive generations used in Monte Carlo simulations of nuclear reactor models is known to suffer from intergenerational correlation between the spatial locations of fission sites. One consequence of the spatial correlation is that the convergence rate of the variance of the mean for a tally becomes worse than O(N–1). In this work, we consider how the true variance can be minimized given a total amount of work available as a function of the number of source particles per generation, the number of active/discarded generations, and the number of independent simulations. We demonstrate through both analysis and simulation that under certain conditions the solution time for highly correlated reactor problems may be significantly reduced either by running an ensemble of multiple independent simulations or simply by increasing the generation size to the extent that it is practical. However, if too many simulations or too large a generation size is used, the large fraction of source particles discarded can result in an increase in variance. We also show that there is a strong incentive to reduce the number of generations discarded through some source convergence acceleration technique. Furthermore, we discuss the efficient execution of large simulations on a parallel computer; we argue that several practical considerations favor using an ensemble of independent simulations over a single simulation with very large generation size.

correlation↗

Electron kinetics in a positive column of AC discharges in a dynamic regime

Abstract We have performed hybrid kinetic-fluid simulations of a positive column in alternating current (AC) argon discharges over a range of driving frequencies f and gas pressure p for the conditions when the spatial nonlocality of the electron energy distribution function (EEDF) is substantial. Our simulations confirmed that the most efficient conditions of plasma maintenance are observed in the dynamic regime when time modulations of mean electron energy (temperature) are substantial. The minimal values of the root mean square electric field and the electron temperature have been observed at f/p values of about 3 kHz Torr −1 in a tube of radius R = 1 cm. The ionization rate and plasma density reached maximal values under these conditions. The numerical solution of a kinetic equation allowed accounting for the kinetic effects associated with spatial and temporal nonlocality of the EEDF. Using the kinetic energy of electrons as an independent variable, we solved an anisotropic tensor diffusion equation in phase space. We clarified the role of different flux components during electron diffusion in phase space over surfaces of constant total energy. We have shown that the kinetic theory uncovers a more exciting and rich physics than the classical ambipolar diffusion (Schottky) model. Non-monotonic radial distributions of excitation rates, metastable densities, and plasma density have been observed in our simulations at pR > 6 Torr cm. The predicted off-axis plasma density peak in the dynamic regime has never been observed in experiments so far. We hope our results stimulate further experimental studies of the AC positive column. The kinetic analysis could help uncover new physics even for such a well-known plasma object as a positive column in noble gases.

Physics↗

Selection biases in empirical p(z) methods for weak lensing

To measure the mass of foreground objects with weak gravitational lensing, one needs to estimate the redshift distribution of lensed background sources. This is commonly done in an empirical fashion, i.e. with a reference sample of galaxies of known spectroscopic redshift, matched to the source population. In this paper, we develop a simple decision tree framework that, under the ideal conditions of a large, purely magnitude-limited reference sample, allows an unbiased recovery of the source redshift probability density function p(z), as a function of magnitude and colour. We use this framework to quantify biases in empirically estimated p(z) caused by selection effects present in realistic reference and weak lensing source catalogues, namely (1) complex selection of reference objects by the targeting strategy and success rate of existing spectroscopic surveys and (2) selection of background sources by the success of object detection and shape measurement at low signal to noise. For intermediate-to-high redshift clusters, and for depths and filter combinations appropriate for ongoing lensing surveys, we find that (1) spectroscopic selection can cause biases above the 10 per cent level, which can be reduced to ≈5 per cent by optimal lensing weighting, while (2) selection effects in the shape catalogue bias mass estimates at or below the 2 per cent level. Finally, this illustrates the importance of completeness of the reference catalogues for empirical redshift estimation.

79 ASTRONOMY AND ASTROPHYSICS↗