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At least 613 records · Page 34

Temperature-Following Thermal Barrier Coatings for High Efficiency Engines (Final Report)

HRL Laboratories and General Motors (GM), pursued this effort to increase the efficiency of internal combustion engines (ICEs) by developing and implementing temperature-following thermal barrier coatings (TBCs) to decrease heat loss from the combustion chamber. HRL developed microsphere TBCs based on hollow high-temperature alloy spheres with average diameter of 50 μm and wall thickness ~1 μm (microspheres) that achieve unprecedented low thermal conductivity and heat capacity (10X lower than the state of the art) while offering exceptional environmental and mechanical resistance.> In current ICEs, approximately 29% of the fuel’s energy is lost to the cooling system and about 22% goes into moving the car. By limiting heat losses from the combustion chamber with insulating coatings, fuel energy can be redirected into additional piston work and into the exhaust stream. The additional energy that goes into the exhaust stream can be turned into useful work through the use of an exhaust energy recovery device, such as turbocompounding and/or through driving a turbocharger to increase the power density of the engine allowing downsizing. Insulating coatings for piston crowns have been pursued in the past, but previous materials—typically ceramics—exhibited low thermal conductivity but retained high heat capacity. Such materials reduce heat losses but stabilize at a high surface temperature. The high surface temperature heats the incoming gases, which lowers volumetric efficiency and increases propensity for knock, resulting in degraded engine performance. This program developed an innovative new material that combines low thermal conductivity with low heat capacity. These unique properties allow it to follow rapid changes in gas temperature during each combustion cycle. A metallic microsphere TBC has been demonstrated that exhibits increased surface temperature during the combustion period, resulting in reduced heat transfer losses, while still returning to a low surface temperature during the gas exchange period. A 10X lower thermal conductivity and heat capacity than state-of-the-art thermal barrier coatings has been demonstrated. These unprecedented thermal properties are achieved through the coating architecture, which consists of closed pores on the microscale and exhibits a total porosity of 90% to 95%. By selecting a high-temperature nickel alloy as the coating material, the ductility and strength of metals can be harnessed to achieve much better durability and damage tolerance than brittle ceramic coatings can achieve.

33 ADVANCED PROPULSION SYSTEMS↗

Strategic Stability in South Asia: An Indian?s Perspective.

The security environment in South Asia has been marked by instability for several decades. The foremost causes of regional instability are the nuclear weapons-cum-missile development program of China, North Korea and Pakistan, the strident march of Islamist fundamentalism, the diabolical nexus between narcotics trafficking and terrorism, the proliferation of small arms and the instability inherent in the rule of despotic regimes. Instability on the Indian sub-continent is manifested, first and foremost, in the continuing conflict in Afghanistan, its tense relations with Iran and the Central Asian Republics (CARs); Pakistan’s struggle against the Taliban, the emerging fissiparous tendencies in Balochistan and Pakhtoonkhwa, the rise of Jihadi Islam and what some fear is Pakistan’s gradual slide towards becoming a ‘failed state’ despite some economic gains in the last five years. Also symptomatic of an unstable and uncertain security environment in the South Asian region are what some see as Sri Lanka’s inability to find a lasting solution to its internal challenges; the potential for Bangladesh’s gradual emergence as the new hub of Islamist fundamentalist terrorism and its struggle for economic upliftment to subsistence levels; the continuing negative impact of Maoist insurgency on Nepal’s fledgling democracy; the simmering discontent in Tibet and Xinjiang and what some see as a low-key uprising against China’s regime; and, the Myanmar peoples’ nascent movement for democracy. In all these countries, socio-economic development has been slow and, consequently, per capita income is alarmingly low. Transborder narcotics trafficking – the golden triangle lies to the east of South Asia and the golden crescent to its west – and the proliferation of small arms, make a potent cocktail. Ethnic tensions and fairly widespread radicalization, worsened by the advent of the vicious ideology of the Islamic state, add further to regional instability.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Channel Gap Probe EMPIrE Report

EMPIrE aims to provide data for the "comprehension phase" of the European Low Enriched Uranium (LEU ) U-Mo Fuel Development program for the conversion of European civilian research reactors. The majority of the fuel performance data will be obtained during post-irradiation examinations (PIE) of the fuel. The primary EMPIrE fuel specimen design is based on uranium-molybdenum (U-Mo) alloy particles dispersed in an aluminum matrix clad in the European alloy AG3NE and in the form of mini-plate sized specimens (1" x 4" plates). Secondary EMPIrE specimens include U Mo monolithic fuel clad in European alloy AlFeNi. The experiment is designed in such a way that U-Mo samples achieve three distinct end-of-life burnup groupings. Irradiation has taken place at ATR (Advance Treatment Reactor). The fuel plates are contained in fuel capsules holding four plates each, with 2 plates at 2 levels. Once the capsules with the plates are irradiated, they have to be inspected during the outage in-between cycles. The capsules need to have visual inspection performed and channel gap widths measured prior to reinsertion. These inspections are to ensure that the plates have not deformed significantly. Obstruction of the coolant channels and restriction of the coolant flow are less of a concern in EMPIrE testing as the channels were made intentionally wide. The Channel Gap Probe (CGP) has been developed to measure channel gap widths, which serves as indirect measures of the fuel plate performance and deformation in the course of irradiation which enables the evaluation of the risk from continuing irradiation prior to reinsertion of the plates in reactor.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Elucidating the corrosion mechanism of Ni-based superalloys in the presence of uranium-containing chloride molten salt

The United States Department of Energy (DOE) is committed to the advancement of nuclear reactor technology through initiatives such as the Advanced Reactor Development Program (ARDP), in an effort to diversify the United States energy portfolio towards more sustainable energy options. The ARDP includes demonstration by industry partners of molten chloride fast reactors (MCFRs). Construction of MCFRs requires qualified nuclear structural materials. Unfortunately, there are no current materials that are fully qualified by the Nuclear Regulatory Commission for the construction of molten salt reactors, including MCFRs. Adapting current structural material qualifications requires expansion of our current knowledgebase on the property-performance relationships regarding corrosion performance. In this investigation, we assess microstructural changes in a Ni-based superalloy after exposure to a UCl3¬-containing chloride salt eutectic mixture through a correlated multi-modal approach combining several advanced characterization techniques, including scanning electron microscopy/focused ion beam (SEM/FIB) and transmission electron microscopy (TEM). SEM/FIB analysis will illustrate changes in elemental composition, microstructure, and isotopic information acquired from energy x-ray dispersive spectroscopy (EDS), electron backscatter diffraction (EBSD), and secondary ion mass spectroscopy (SIMS), respectively. This information will then aid in identifying localized regions to elucidate the corrosion mechanism with TEM through a combination of electron diffraction, electron energy loss spectroscopy (EELS), and additional EDS. The findings from this investigation will further expand our assessment of the corrosion performance of structural materials in molten salt chloride systems, aiding to developing fully qualified materials for construction of MCFRs.

36 MATERIALS SCIENCE↗

VCTR: A Versatile Coupled Test Reactor Concept

The United States has currently no domestic fast neutron test and irradiation capabilities necessary to pursue a strong research and development program related to fast neutron reactors. This lack prevents the testing of fast reactor fuels in a prototypic environment, the testing of new safety features and of new coolants. A new irradiation test reactor is a costly investment that will operate for several decades and the initial specifications are crucial to ensure the relevance of such a facility in the long run. This new test reactor should be highly reconfigurable and allow operation as a fast test reactor or a thermal test reactor or a cou-pled fast-thermal test reactor. This report presents the on-going effort at Idaho National Laboratory (INL) to design a versatile coupled test reactor (VCTR—pronounced Victor) that could fulfill the R&D needs requiring high fast neutron fluxes but also high thermal neutron fluxes in configurations that could not be met in current thermal neutron test reactors such as ATR. The objective of this report is to summarize the efforts undertaken at INL from May 2015 to March 2016 aimed at understanding the main options for designing and building a versatile test reactor, with a primary mission to provide thermal and fast neutrons for irradiation of fuels and materials in a manner complementary to the ATR and HFIR reactors. Other missions can also be considered, including the validation of computer codes and the development of specific reactor technologies.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Idaho National Laboratory Integrated Multisite SSHAC Level 3: Probabilistic Volcanic Hazards Assessment

The Idaho National Laboratory (INL) resides on the eastern Snake River Plain (ESRP), part of the Snake River Plain (SRP) with a complex origin and geologic history of volcanism. Much of the Quaternary (last 2.58 million years) volcanism within 400 km of INL is genetically associated with a major thermal anomaly referred to as the Yellowstone hotspot, which is currently located more than 180 km northeast of INL. Near INL, local volcanic sources include silicic domes near its southern border, and numerous dike-fed basaltic vents of the ESRP, some of which are near or within the INL boundaries. Quantitative probabilistic assessments of screened-in volcanic hazardous phenomena for nine different facility complexes at the INL are presented for a Senior Seismic Hazard Analysis Committee (SSHAC) Level 3 (SL3) study. The comprehensive, integrated multisite SSHAC study consists of a single regional Probabilistic Volcanic Hazards Assessment (PVHA) that pertains to all nine INL facility complexes, with site-specific information developed at each respective area of interest (AOI), referred to as the "INL facility AOI" (Figure ES-1). Hazard products are generated for specified INL facility AOIs for use by multiple stakeholders from different agencies in risk-informed decision-making regarding site selection, operations, and design of nuclear facilities at INL, consistent with U.S. Department of Energy (DOE) and U.S. Nuclear Regulatory Commission (NRC) regulatory guidance. The study also serves as the basis for future periodic safety assessments required for existing DOE facilities, such as 10-year evaluations of natural-phenomena hazards. Elements of the INL PVHA including initial characterization, screening, quantitative assessments of eruption and hazard potential, and consideration of facility needs are conducted using the three phases of the SSHAC process: evaluation, integration, and documentation. As per regulatory guidance, the SSHAC framework provided the necessary processes and procedures for the PVHA Technical Integration (TI) team, at three workshops, five formal working meetings and many TI team remote meetings, to conduct initial characterization, screen the volcanic hazards, create PVHA model inputs, exercise those models in the PVHA, consider facility-specific volcanic hazard needs, and perform final hazard calculations. The Participatory Peer Review Panel (PPRP) provided independent oversight and performed process and technical reviews of the PVHA throughout its duration. The study included an extensive New Data Collection and Analyses (NDCA) program developed by the PVHA TI team to reduce uncertainties in hazard-significant elements in the PVHA model. NDCA activities generated 20 reports providing important contributory datasets and results to the project database for characterizing the ESRP. For example, a report compiling the dimensions of ESRP shield volcanoes and lava fields was used to construct volcanic footprints (areas of impact), was compared with data from INL subsurface cores, and was used to validate the results of lava-flow inundation modeling on the contemporary terrain. Another example is the acquisition of aeromagnetic data over INL and its surrounding area, with maps of buried magmatic features (e.g., subsurface volcanoes and swarms of feeder dikes) that informed the PVHA conceptual model of volcanism. The SSHAC evaluation process was used to conduct all elements of the PVHA including initial characterization and screening. Existing data and NDCA activities provided the foundation to develop the tectonomagmatic conceptual model of volcanism for the region of geographical interest in the SRP and Yellowstone hotspot volcanic system, and for considering volcanoes in the western US. Considering Quaternary volcanic sources active during this period, the screening approach identified and evaluated magma compositions, types of eruptive and intrusive phenomena, types of hazardous phenomena, and proximity of sources to INL. The PVHA TI team evaluated 18 types of magmatic sources in terms of 20 potentially hazardous phenomena, resulting in 360 screening decisions. The screening process resulted in 140 screened-in hazardous volcanic phenomena for Quaternary volcanic sources 1) proximal to INL facility complexes in the ESRP (64 basaltic and 54 silicic), 2) regional sources associated with the Yellowstone caldera system and Blackfoot Reservoir volcanic field (7), and 3) more distal sources from thirteen Cascade volcanoes and two volcanoes at Long Valley caldera (CA).

58 GEOSCIENCES↗

Building a Community Infrastructure for Scalable On-Line Performance Analysis Tools around Open|SpeedShop

In this project we created a community tool infrastructure for program development tools targeting Petascale class machines and beyond. This includes tools for performance analysis, debugging, and correctness tools, as well as tuning and optimization frameworks. The developed infrastructure provides a comprehensive and extensible set of individual tool building components. We started with the basic elements necessary across all tools in such an infrastructure followed by a set of generic core modules that allow a comprehensive performance analysis at scale. Further, we developed a methodology and workflow that allows others to add or replace modules, to integrate parts into their own tools, or to customize existing solutions. In order to form the core modules, we built on the existing Open|SpeedShop infrastructure and decomposed it into individual modules that match the necessary tool components. At the same time, we addressed the challenges found in performance tools for petascale systems in each module. When assembled, this instantiation of community tool infrastructure provides an enhanced version of Open|SpeedShop, which, while completely different in its architecture, provides scalable performance analysis for petascale applications through a familiar interface. This project also built upon and enhances capabilities and reusability of project partner components as specified in the original project proposal. The overall project team’s work over the project funding cycle was focused on several areas of research, which are described in the following sections. The reminder of this report also highlights related work as well as preliminary work that supported the project. In addition to the project partners funded by the Office of Science under this grant, the project team included several collaborators who contribute to the overall design of the envisioned tool infrastructure. In particular, the project team worked closely with the other two DOE NNSA laboratories Los Alamos and Sandia leveraging co-funding for Krell by ASC’s Common Computing Environment (CCE) program as laid out in the original proposal. The ASC CCE co-funding, coordinated through LLNL, was for 50% of the total project funding, with the ASC CCE portion of the funding going entirely to Krell, while the ASCR funding itself was split between Krell and the funded partners. This report covers the entire project from both funding sources. Additionally, the team leveraged the expertise of software engineering researchers from Carnegie Mellon University, who specialize in software framework design, in order to achieve a broadly acceptable component framework. The Component Based Tool Framework (CBTF) software has been released to the community. Information related to the project and the released software can be found on the CBTF wiki page at: http://sourceforge.net/p/cbtf/wiki/Home.

97 MATHEMATICS AND COMPUTING↗

Solar Living House Final Technical Report

The Solar Living House is a high-performance solar-powered dwelling designed by a team of faculty and students from the University of Florida, in collaboration with Santa Fe College, the National University of Singapore, and Alachua Habitat for Humanity. The project was designed in accordance with the Solar Decathlon 2015, a research, design, education, and outreach program developed by the U.S. Department of Energy (DOE). The Solar Living House is fundamentally a house for living, centered on people and the activities of daily life while quietly introducing advanced design, construction, and engineering technologies. The 993 square-foot two-bedroom one-bath home was designed to embrace and frame an exterior courtyard space. This courtyard acts as an extension of the interior living spaces, maximizing the spatial potentials of a modest building footprint and introducing natural light into the primary living spaces of the house. Research Outcomes: The Solar Living House advances work on high-performance buildings through three principal technological innovations: wet/dry modular construction, a building automation system, and solar dehumidification systems. Wet / Dry Modular Construction: The house is designed as a series of five modules, including one that is designated as the “wet core.” The wet core consolidates the mechanical systems and bathroom into a single module to reduce plumbing runs, efficiency losses, and on-site construction time. The other four modules are designed to eliminate interior load bearing walls to allow for maximum flexibility in the reconfiguring of the space over time. The modules are designed to meet the structural challenges of both Florida’s hurricanes and California’s earthquakes. Building Automation System: The house is equipped with an integrated building automation system, allowing the houses environmental systems, lights, security systems, and smoke detectors to be programmed, monitored, and controlled through any mobile or computing device. These systems allow for more precise calibrations of temperature/humidity/lighting to correspond with user needs and preferences, minimizing energy losses with economical night- or day-time setbacks. Solar Dehumidification System: The most significant technological innovation in the Solar Living House is the solar thermal dehumidification system. This system generates hot water through two rooftop-mounted evacuated tube solar thermal collectors. The hot water is used to continually dry a regenerative solid desiccant material, typically white silica gel. The solid desiccant is used to adsorb moisture and humidity from the air without additional mechanical cooling. This strategy allows humidity to be modulated independently of air temperature, providing greater thermal comfort and reducing the opportunity for the growth of mold spores within the house while also reducing the overall energy consumption of the HVAC system. Economic Feasibility: The team set aggressive goals for affordability, targeting a construction cost of $138,710. An independent professional cost estimator determined the overall project costs, as designed, would be $333,799, or $336.15 per square foot of finished floor area. This is more than 2.4 times the target construction cost. By comparison, the average construction cost for a home in the United States in 2015 was $289,415, or $103.29 per square foot of finished floor area. Following work on the Solar Living House, team leaders incorporated many of its objectives into a net-zero energy home on a site in Gainesville, Florida. This site-built home avoided many of the constraints and complications of modular construction necessitated by the Solar Decathlon, allowing it to be built for a much more modest budget. This two-bedroom two bath 1,800 square foot home was constructed for $135.39 per square foot, including active photovoltaic solar systems, careful attention to continuous air barriers, increased insulation levels, and permanent site constructions. This project suggest that high-performance buildings can be realized for more modest budgets. Public Benefits: Work on the Solar Living House and Solar Decathlon 2015 offered our student team unparalleled learning opportunities. Because of the duration of the project, a number of students participated at different points in their education, from first year undergraduates all the way through to advanced graduate students. The opportunity for collaboration with students and faculty from the National University of Singapore was also extraordinary, allowing for a sharing of technical knowledge and cultural exchange. The wider public has benefited from this work as its findings have been shared through public presentations and publications. It serves as a useful stepping stone along the path towards affordable, high-performance buildings.

14 SOLAR ENERGY↗

Acoustic sensors for fission gas characterization: R and D skills devoted to innovative instrumentation in MTR, non-destructive devices in hot lab facilities and specific transducers for measurements of LWR rods in nuclear plants

First of all, we will present the main principle of the method. A piezoelectric transducer, driven by a pulse generator, generates the acoustic waves in a cavity that may be the fuel rod or a chamber connected to an instrumented rod. The composition determination consists in measuring the time of flight of the acoustic signal emitted. The pressure can be estimated by a calibration process, above the measurement of the amplitude of the signal. Two projects will then be detailed. The first project consists in the development of advanced instrumentation for in-pile experiments in Material Testing Reactor. It constitutes a main goal for the improvement of the nuclear fuel behavior knowledge. This acoustic method was tested with success during a first experiment called REMORA 3, and the results were used to differentiate helium and fission gas release kinetics under transient operating conditions. This experiment was lead at OSIRIS reactor (CEA Saclay, France). As a first step of the development program, we performed in-pile tests on the most sensitive component, i.e., the piezoelectric transducer. For this purpose, the active part of this sensor has been qualified on gamma and neutron radiations and at high temperature. Various industrial piezo-ceramics were exposed to a high activity Cobalt source for few days. The cumulated dose was ranged from 50 kGy up to 2 MGy. Next, these devices were placed inside a Material Test Reactor to investigate their reliability towards neutron fluence. The final fluence after 150 days of irradiation was up to 1.6.10{sup 21}n/cm{sup 2} (for thermal neutron). Irreversible variations have been measured. Next, a specific sensor has been implemented on an instrumented fuel rod and tested in the frame of a REMORA 3 Irradiation test. It was the first experiment under high mixed, temperature neutron and gamma flux. A first irradiation phase took place in March 2010 in the OSIRIS reactor and in November 2010 for the second step of the irradiation. The instrumented fuel rod incorporating the ultrasonic gas composition sensor was finally irradiated during 2 weeks in nominal conditions. Neutronics calculation will be performed in order to calculate the thermal and fast neutron fluence and the gamma dose absorbed by acoustic sensor. A first evaluation gives a thermal fluence about 4,5.10{sup 19} n/cm{sup 2}, a fast neutrons fluence about 4,5.1018 n/cm{sup 2} and a total gamma dose up to 0,25 MGy The maximal temperature during the irradiation test was about 150 C. Although the ultrasonic sensor appears to be damaged, the optimization of the electrical attack parameters and the development of a new signal processing maintain the measurement feasibility up the end of the irradiation campaign. It was the first time that the composition of fission gas has been monitored all along an irradiation experiment in a MTR, giving access to the gas release kinetics. New researches involve thick film transducers produced by screen-printing process in order to propose piezoelectric structures for harsh temperature and irradiation measurements. The second project consists in the development of a non-destructive device that can be directly applied on a LWR fuel rod. The problem to be solved relates to the measurement of the fission gas pressure and composition in a fuel rod using a non-destructive method. Fuel rod internal pressure is one of the safety criteria applied in nuclear power analyses. This criterion must be verified in order to avoid any fuel-cladding gap reopening risk and therefore any local clad ballooning. Apart from the safety implications, this parameter is also a fuel behaviour indicator and reflects the overall fuel performance in operation, but also during shipping and long-term storage. Rod internal pressure is one criterion amongst others, like cladding corrosion, against which the acceptable fuel burn-up limit is set. A sensor has been achieved in 2007. A full-scale hot cell test of the internal gas pressure and composition measurement by an acoustic sensor was conducted successfully between 2008 and 2010 on 5 high burn-up MOX fuel rods and 2 very high burn-up UO{sub 2} fuel rods in LECA Facility at Cadarache Centre. An improvement of this sensor has been proposed, allowing us to divide by two the uncertainty on the pressure measurement. In the case of hot-cell measurements, viscous liquid can be used to couple the sensor with the rod. For gas content with a pressure exceeding 15 bars and a 10% Xe/Kr ratio, such coupling may reduce relative acoustic method accuracy by ±7% for pressure measurement result and ±0.25 % for the assessment of gas composition. These results make it possible to demonstrate the feasibility of the technique on LWR fuel rods. The transducer and the associated methodology are now operational for non-destructive measurements in hot lab facilities and allow characterising the fission gas without puncturing the fuel rods. Up to now, any other non-destructive method can be proposed. A next step will be the development of an industrial application in a fuel storage pool in order to perform a large number of measurements on a fuel assembly in nuclear plants.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Slag Management of Carbon Feedstock Used in Gasification FY17 TCF between Eastman Chemical and NETL (Final Report)

NETL, in collaboration with Eastman Chemical Corp (Kingsport, TN), targeted the joint evaluation and refinement of a slag management program developed by NETL (NETL IP, patent applied for) to control gasifier slag properties formed from ash in individual or combinations of different coal-based carbon feedstock materials and specific slag modifiers used in gasification. Slag forms from mineral or organic-metallic impurities in the carbon feedstock that melt at the high temperatures of gasification, coalescing to form a liquid (slag) that must flow from the gasifier. Slag additives, also known as slag modifiers, are often added to the carbon feedstock to modify the ash chemistry and achieve desired slag flow properties at target temperatures used in gasification. If slag does not flow from a gasifier, its buildup within the gasification chamber will cause either gasifier shutdown to physically remove the slag (consuming time and damaging the protective refractory lining), or the gasification temperature must be increased to lower slag viscosity so it can flow from the gasifier, leading to greater refractory wear/corrosion, along with increased fouling and downstream component wear. Because of these issues, gasification is typically targeted at the lowest temperature possible where slag will flow in a controlled manner (a temperature range called T100 for the lowest temperature, with T250 being the highest temperature where the slag has achieved the desired fluidity). That temperature range also needs to yield a desired syngas composition, highlighting the importance of knowing and being able to control carbon feedstock slag viscosity and the temperature of thermal breakdown of the carbon feedstock. Slag viscosity varies with changes in the gasification chamber temperature, oxygen partial pressure, and slag chemistry. The slag model work with Eastman Chemical targeted predicting and controlling molten coal ash slag behavior at specific gasification conditions. The final goal of the refined model was to develop/refine the NETL slag model so a gasifier operator would be able to predict slag behavior prior to purchasing or using a carbon feedstock and control slag properties once a carbon feedstock is being gasified, allowing a gasifier user to determine what mineral additives or blends of different carbon materials would be needed to achieve desired slag properties at targeted gasification conditions. For a given carbon feedstock and desired gasification condition, the actual gasification cost and slag behavior would be able to be predicted using the slag management program in advance of purchasing or using the carbon feedstock – allowing accurate control of slag ash behavior in real time. As part of the TCF project work with Eastman Chemical, the viscosity of several ash compositions of interest to them would be measured and used to populate the slag model, along with a large database of historical slag temperature, chemistry, and viscosity information they possess – information that would in-crease the predictive accuracy of the slag management model with slag ash chemistry of interest to them. As part of the model evaluation and refinement, the predictive model and its database will be installed on computers at Eastman Chemical and used to manage slag properties in a gasifier during real-time operation of their gasifier. In summary, success of the slag management program at Eastman Chemical would support its use by other gasifier operators to manage slag chemistry and properties over other desired gasification temperature ranges, allowing greater process control and efficiency of their carbon feedstock conversion during gasification.

01 COAL, LIGNITE, AND PEAT↗

Three-dimensional concentration mapping of organic blends

We quantitatively measure the three-dimensional morphology of mixed organic layers using high-angle annular darkfield scanning transmission electron microscopy (HAADF-STEM) with electron tomography for the first time. The mixed organic layers used for organic photovoltaic applications have not been previously imaged using STEM tomography as there is insufficient contrast between donor and acceptor components. We generate contrast by substituting fullerenes with endohedral fullerenes that contain a Lu3N cluster within the fullerene cage. The high contrast and signal-to-noise ratio, in combination with use of the discrete algebraic reconstruction technique (DART), allowed us to generate the most detailed and accurate three-dimensional map of BHJ morphology to date. From the STEM tomography reconstructions we determined that three distinct material phases are present within the BHJs. By observation of the changes to morphology and mixing ratio that occur during thermal and solvent annealing, we are able to determine how mutual solubility and fullerene crystallization affect the formation of morphology and long term stability of the material mixture. This material/technique combination shows itself as a powerful tool for examining morphology in detail and allows for observation of nanoscopic changes in local concentration. This research was supported in part by Laboratory Directed Research & Development program at PNNL. The Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy under contract DE-AC05-76RL01830.

Roehling, John D.↗

The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase

H2 adsorption properties on Pt in aqueous phase was determined by a reaction kinetic measurement of gas H2 reacting with liquid D2O into liquid HDO, gas HD and D2, and a DFT based ab inito molecular dynamic simulation of H2 adsorption on Pt (111) in the presence and absence of water. Both approaches show that the H2 adsorption on Pt in water is much weaker than that in the gas phase. The presence of interfacial water destabilizes the adsorbed H on Pt via decreasing the adsorption heat (hydrogen binding energy) by 19 - 22 kJ·molH2-1 and inducing an extra entropy loss of 50 - 70 J·mol H2-1·K-1. Upon H adsorption on Pt, the closest water layer near Pt surface shifts to a larger distance from the surface and re-orientates to a more ordered structure; in turn, the water layer limits the translation mobility of adsorbed H on Pt. The influence of interfacial water property on H2 adsorption is also reflected by the decrease of adsorption heat with the decrease of local pH provided by the support. Research was funded by the Laboratory Directed Research and Development program at Pacific Northwest National Laboratory.

Yang, Guoju↗

State of Supported Nanoparticle Ni during Catalysis in Aqueous Media

The state of Ni supported on HZSM-5 zeolite, silica, and sulfonated carbon was studied during aqueous-phase catalysis of phenol hydrodeoxygenation using in situ extended X-ray absorption fine structure spectroscopy. On sulfonated carbon and HZSM-5 supports, NiO and Ni(OH)(2) were readily reduced to Ni-0 under reaction conditions (approximate to 35bar H-2 in aqueous phenol solutions containing up to 0.5wt.% phosphoric acid at 473K). In contrast, Ni supported on SiO2 was not stable in a fully reduced Ni-0 state. Water enables the formation of Ni-II phyllosilicate, which is more stable, that is, difficult to reduce, than either -Ni(OH)(2) or NiO. Leaching of Ni from the supports was not observed over a broad range of reaction conditions. Ni-0 particles on HZSM-5 were stable even in presence of 15wt.% acetic acid at 473K and 35bar H-2.

catalysis↗

Performance Analysis of OpenSHMEM Applications with TAU Commander

The TAU Performance System® (TAU) is a powerful and highly versatile profiling and tracing tool ecosystem for performance engineering of parallel programs. Developed over the last twenty years, TAU has evolved with each new generation of HPC systems and scales efficiently to hundreds of thousands of cores. TAU’s organic growth has resulted in a loosely coupled software toolbox such that novice users first encountering TAU’s complexity and vast array of features are often intimidated and easily frustrated. To lower the barrier to entry for novice TAU users, ParaTools and the US Department of Energy have developed “TAU Commander,” a performance engineering workflow manager that facilitates a systematic approach to performance engineering, guides users through common profiling and tracing workflows, and offers constructive feedback in case of error. This work compares TAU and TAU Commander workflows for common performance engineering tasks in OpenSHMEM applications and demonstrates workflows targeting two different SHMEM implementations, Intel Xeon “Haswell” and “Knights Landing” processors, direct and indirect measurement methods, callsite, profiles, and traces.

97 MATHEMATICS AND COMPUTING↗

Optimizing I/O Forwarding Techniques for Extreme-Scale Event Tracing

Programming development tools are a vital com- ponent for understanding the behavior of parallel applica- tions. Event tracing is a principal ingredient to these tools, but new and serious challenges place event tracing at risk on extreme-scale machines. As the quantity of captured events increases with concurrency, the additional data can over- load the parallel file system and perturb the application be- ing observed. In this work we present a solution for event tracing on extreme-scale machines. We enhance an I/O for- warding software layer to aggregate and reorganize log data prior to writing to the storage system, significantly reduc- ing the burden on the underlying file system. Furthermore, we introduce a sophisticated write buffering capability to limit the impact. To validate the approach, we employ the Vampir tracing toolset using these new capabilities. Our re- sults demonstrate that the approach increases the maximum traced application size by a factor of 5x to more than 200,000 processes.

atomic append↗

A joint probability approach for coincidental flood frequency analysis at ungauged basin confluences

A reliable and accurate flood frequency analysis at the confluence of streams is of importance. Given that long-term peak flow observations are often unavailable at tributary confluences, at a practical level, this paper presents a joint probability approach (JPA) to address the coincidental flood frequency analysis at the ungauged confluence of two streams based on the flow rate data from the upstream tributaries. One case study is performed for comparison against several traditional approaches, including the position-plotting formula, the univariate flood frequency analysis, and the National Flood Frequency Program developed by US Geological Survey. It shows that the results generated by the JPA approach agree well with the floods estimated by the plotting position and univariate flood frequency analysis based on the observation data.

confluence point↗

Use of Solvatochromism to Assay Preferential Solvation of a Prototypic Catalytic Site

The composition of the reaction medium near photoactive catalytic sites can be inferred from the solvatochromism of the absorption and emission spectra of the wetted sites, which depend on the polarizability of the fluid. In brief, solvatochromism measures the interaction of the dipole moments of the ground and excited states with the electric field imposed by the solvent shell: a field, which does not relax on the time scale of the absorption or emission events. As a first step in establishing the utility of the technique for inorganic catalysts that operate in complex reaction media, such as encountered in the upgrading of biogenic fuels, we have measured the solvatochromism of a common, structural feature of metal oxide catalysts. In toluene, cyclohexene, chloroform and tetrahydrofuran, POSS-ligated oxometalates exhibit strong ligand-to-metal charge-transfer bands in their UV-visible absorption and emission spectra. The magnitudes of the solvatochromic effects agreed well with the calculated changes in dipole moments that accompany the electronic transitions. From the solvatochromism of the chromophores dissolved in toluene-chloroform mixtures we inferred an unexpectedly strong, preferential solvation of the chromophore even when all three components (oxometalate and the two solvents) were highly miscible. This research was supported in part by the Laboratory Directed Research & Development program at Pacific Northwest National Laboratory. PNNL is operated by Battelle for the US Department of Energy under contract DE-AC05-76RL01830. A portion of the research was performed at EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at PNNL.

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