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At least 541 records · Page 30

Electrolytes for Use in High Energy Lithium-ion Batteries with Wide Operating Temperature Range

Met programmatic milestones for program. Demonstrated improved performance with wide operating temperature electrolytes containing ester co-solvents (i.e., methyl butyrate) containing electrolyte additives in A123 prototype cells: Previously demonstrated excellent low temperature performance, including 11C rates at -30 C and the ability to perform well down to -60 C. Excellent cycle life at room temperature has been displayed, with over 5,000 cycles being demonstrated. Good high temperature cycle life performance has also been achieved. Demonstrated improved performance with methyl propionate-containing electrolytes in large capacity prototype cells: Demonstrated the wide operating temperature range capability in large cells (12 Ah), successfully scaling up technology from 0.25 Ah size cells. Demonstrated improved performance at low temperature and good cycle life at 40 C with methyl propionate-based electrolyte containing increasing FEC content and the use of LiBOB as an additive. Utilized three-electrode cells to investigate the electrochemical characteristics of high voltage systems coupled with wide operating temperature range electrolytes: From Tafel polarization measurements on each electrode, it is evident the NMC-based cathode displays poor lithium kinetics (being the limiting electrode). The MB-based formulations containing LiBOB delivered the best rate capability at low temperature, which is attributed to improved cathode kinetics. Whereas, the use of lithium oxalate as an additive lead to the highest reversible capacity and lower irreversible losses.

low temperature batteries↗

Reverse Micelle Based Synthesis of Microporous Materials in Microgravity

Microporous materials include a large group of solids of varying chemical composition as well as porosity. These materials are characterized by channels and cavities of molecular dimensions. The framework structure is made up of interconnecting T-O-T' bonds, where T and T' can be Si, Al, P, Ga, Fe, Co, Zn, B and a host of other elements. Materials with Si-O-Al bonding in the framework are called zeolites and are extensively used in many applications. Ion-exchange properties of these materials are exploited in the consumer and environmental industries. Chemical and petroleum industries use zeolites as catalysts in hydrocarbon transform ations. Synthesis of new microporous frameworks has led to the development of new technologies, and thus considerable effort worldwide is expended in their discovery. Microporous materials are typically made under hydrothermal conditions. Influence of nature of starting reactants, structure directing agents, pH, temperature, and aging all have profound influence on the synthesis process. This is primarily because the most interesting open frameworks are not necessarily the stable structures in the reaction medium. Thus, the discovery of new frameworks is often tied to finding the right composition and synthesis conditions that allow for kinetic stabilization of the structure. This complexity of the synthesis process and limited understanding of it has made it difficult to develop directed is of microporous materials and most advances in this field have been made by trial and error. The basic issues in crystal growth of these materials include: (1) Nature of the nucleation process; (2) Molecular structure and assembly of nuclei; (3) Growth of nuclei into crystals; (4) Morphology control; and (5) Transformation of frameworks into other structures. The NASA-funded research described in this paper focuses on all the above issues and has been described in several publications. We present the highlights of our program, especially with the focus on possible experiments in microgravity.

Dutta, Prabir K.↗

Distonic radical anion species in cysteine oxidation processes

Oxidation of cysteine residues constitutes an important regulatory mechanism in the function of biological systems. Much of this behavior is controlled by the specific chemical properties of the thiol side-chain group, where reac-tions with reactive oxygen species take place. Herein, we in-vestigated the entire cysteine oxidation cycle Cys-SH ? Cys-SOnH (n = 1, 2, 3) using cryogenic negative ion photoelectron spectroscopy and quantum-chemical calculations. The conven-tional view on the first reversible oxidation step (n = 1) is as-sociated with sulfinate species. Yet our results indicate that an alternative option exists in the form of novel distonic radical anion •OS-CH2CH(NH2)-COO- with an unpaired electron on the thiol group and excess negative charge on the carboxylate. Higher order oxidation states (n = 2, 3) are thought to be asso-ciated with irreversible oxidative damage, and our results show that excess negative charge in those cases migrates to -SOn- group. Furthermore, these species are stable towards 1e oxidation, as opposed to the n = 1 case that undergoes intra-molecular proton transfer. The molecular level insights report-ed in this work provide direct spectroscopic evidences towards unique chemical versatility of Cys-sulfenic acid (Cys-SOH) in post-translational modifications of protein systems. This research was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (X.-B. W. and M. V.) and was performed at the EMSL, a national scientific user facility sponsored by DOE's Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory. Z. B. Q. acknowledges additional support from the National Natural Science Foundation of China (Grant No. 21873003 and 21503003) and the Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) (Grant No. U1501501) and Super Computation of Shenzhen.

Qin, Zhengbo↗

Understanding Proton Movement in [Fe-Fe] Hydrogenases

Nature uses specialized metalloenzymes to carry out small molecule activation reactions, including CO 2 fixation, O 2 activation, and proton reduction, with unparalleled efficiency, rates, and selectivity. The latter reactions are performed by hydrogenases, protein metallo-complexes that interconverts H 2 to protons and electrons (H 2 oxidation) and the reverse reaction (H 2 production) with incredibly low energy input and amazingly fast kinetics. Reproducing both the activity and efficiency of metalloenzymes in sustainable anthropogenic systems remains one of the “holy grails” of inorganic chemistry. However, identifying the precise molecular components responsible for these desirable properties has been challenging in the natural metalloenzymes, hindering efforts to develop analogous processes in synthetic compounds. Considering the inherent complexity of a metalloenzyme and the many interactions, both strong and weak, that contribute to the function of an enzyme, we have elected to model natural metalloenzymes on a biochemical platform. Towards this end, we have a developed structural, functional, and mechanistic mimic of the [Ni-Fe] hydrogenases within a robust protein scaffold, rubredoxin, to understand the influence of the secondary coordination environment on the metal center. This involved preparing a series of three rubredoxin constructs containing a single point mutation at Val positions and making the NMR chemical shift assignments for the paramagnetic (nickel-substituted) and non-paramagnetic (zinc-substituted) form. These physical studies were complemented with in silico molecular dynamic studies on proteins with [Fe-S] clusters to engineer new proton channels to test in vitro . To assist our search for new natural metalloprotein scaffolds within the vast number of sequenced genomes, we created a neural network-based program to identify proteins with specific metal-binding sites. These computational and physical studies with metalloenzymes provide direct insight into the fundamental chemical principles driving the natural systems and offer design principles for developing catalysts that utilize analogous principles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving Uintah's Scalability Through the Use of Portable Kokkos-Based Data Parallel Tasks

The University of Utah’s Carbon Capture Multidisciplinary Simulation Center (CCMSC) is using the Uintah Computational Framework to predict performance of a 1000 MWe ultra-supercritical clean coal boiler. The center aims to utilize the Intel Xeon Phi-based DOE systems, Theta and Aurora, through the Aurora Early Science Program by using the Kokkos C++ library to enable node-level performance portability. This paper describes infrastructure advancements and portability improvements made possible by the integration of Kokkos within Uintah. This integration marks a step towards consolidating Uintah’s MPI+PThreads and MPI+CUDA hybrid parallelism approaches into a single MPI+Kokkos approach. Scalability results are presented that compare serial and data parallel task execution models for a challenging radiative heat transfer calculation, central to the center’s predictive boiler simulations. Here, these results demonstrate both good strong-scaling characteristics to 256 Knights Landing (KNL) processors on the NSF Stampede system, and show the KNL-based calculation to compete with prior GPU-based results for the same calculation.

97 MATHEMATICS AND COMPUTING↗

Excess chemical potential of small solutes across water--membrane and water--hexane interfaces

The excess chemical potentials of five small, structurally related solutes, CH4, CH3F, CH2F2, CHF3, and CF4, across the water-glycerol 1-monooleate bilayer and water-hexane interfaces were calculated at 300, 310, and 340 K using the particle insertion method. The excess chemical potentials of nonpolar molecules (CH4 and CF4) decrease monotonically or nearly monotonically from water to a nonpolar phase. In contrast, for molecules that possess permanent dipole moments (CH3F, CH2F, and CHF3), the excess chemical potentials exhibit an interfacial minimum that arises from superposition of two monotonically and oppositely changing contributions: electrostatic and nonelectrostatic. The nonelectrostatic term, dominated by the reversible work of creating a cavity that accommodates the solute, decreases, whereas the electrostatic term increases across the interface from water to the membrane interior. In water, the dependence of this term on the dipole moment is accurately described by second order perturbation theory. To achieve the same accuracy at the interface, third order terms must also be included. In the interfacial region, the molecular structure of the solvent influences both the excess chemical potential and solute orientations. The excess chemical potential across the interface increases with temperature, but this effect is rather small. Our analysis indicates that a broad range of small, moderately polar molecules should be surface active at the water-membrane and water-oil interfaces. The biological and medical significance of this result, especially in relation to the mechanism of anesthetic action, is discussed.

NASA Center ARC↗

Color Changing Hydrogen Sensors

During the Space Shuttle Program, one of the most hazardous operation that occurred was the loading of liquid hydrogen (LH2) during fueling operations of the spacecraft. Due to hydrogen's low explosive limit, any amount leaked could lead to catastrophic event. Hydrogen's chemical properties make it ideal as a rocket fuel; however, the fuel is deemed unsafe for most commercial use because of the inability to easily detect the gas leaking. The increased use of hydrogen over traditional fossil fuels would reduce greenhouse gases and America's dependency on foreign oil. Therefore a technology that would improve safety at NASA and in the commercial sector while creating a new economic sector would have a huge impact to NASA's mission. The Chemochromic Detector for sensing hydrogen gas leakage is a color-changing detector that is useful in any application where it is important to know not only the presence but also the location of the hydrogen gas leak. This technology utilizes a chemochromicpigment and polymer matrix that can be molded or spun into rigid or pliable shapes useable in variable temperature environments including atmospheres of inert gas, hydrogen gas, or mixtures of gases. A change in color of the detector material indicates where gaseous hydrogen leaks are occurring. The irreversible sensor has a dramatic color change from beige to dark grey and remains dark grey after exposure. A reversible pigment changes from white to blue in the presence of hydrogen and reverts back to white in the presence of oxygen. Both versions of the sensor's pigments were comprised of a mixture of a metal oxide substrate and a hydro-chromic compound (i.e., the compound that changed color in the presence of hydrogen) and immediately notified the operator of the presence of low levels of hydrogen. The detector can be used in a variety of formats including paint, tape, caulking, injection molded parts, textiles and fabrics, composites, and films. This technology brings numerous benefits over the traditional hydrogen sensors: The technology has excellent temperature stability (4K to 373 K), it can be used in cryogenic fluid applications, it is easy to apply and remove; it requires no power to operate; it has a quick response time; the leak points can be detected visually or electronically; it is nonhazardous, thus environmentally friendly; it can be reversible or irreversible; it does not require on-site monitoring; has a long shelf life; the detector is very durable; and the technology is inexpensive to manufacture.

Chemochromic sensor↗

MISR Level 1A CCD Science data, all cameras (MIL1A_V1)

The Level 1A data are raw MISR data that are decommutated, reformatted 12-bit Level 0 data shifted to byte boundaries, i.e., reversal of square-root encoding applied and converted to 16 bit, and annotated (e.g., with time information). These data are used by the Level 1B1 processing algorithm to generate calibrated radiances. The science data output preserves the spatial sampling rate of the Level 0 raw MISR CCD science data. CCD data are collected during routine science observations of the sunlit portion of the Earth. Each product represents one 'granule' of data. A 'granule' is defined to be the smallest unit of data required for MISR processing. Also, included in the Level 1A product are pointers to calibration coefficient files provided for Level 1B processing. [Location=GLOBAL] [Temporal_Coverage: Start_Date=2000-02-24; Stop_Date=] [Spatial_Coverage: Southernmost_Latitude=-90; Northernmost_Latitude=90; Westernmost_Longitude=-180; Easternmost_Longitude=180].

CCD↗

Four large-scale field-aligned current systmes in the dayside high-latitude region

A system of four current sheets of large-scale field-aligned currents (FACs) was discovered in the data set of simultaneous Viking and Defense Meteorological Satellire Program-F7 (DMSP-F7) crossing of the dayside high-latitude region. This paper reports four examples of this system that were observed in the prenoon sector. The flow polarities of FACs are upward, downward, upward, and downward, from equatorward to poleward. The lowest-latitude upward current is flowing mostly in the central plasma sheet (CPS) precipitation region, often overlapping with the boundary plasma sheet (BPS) at its poleward edge, andis interpreted as a region 2 current. The pair of downward and upward FACs in the middle of te structure are collocated with structured electron precipitation. The precipitation of high-energy (greater than 1 keV) electrons is more intense in the lower-latitude downward current sheet. The highest-latitude downward flowing current sheet is located in a weak, low-energy particle precipitation region, suggesting that this current is flowing on open field lines. Simulaneous observations in the postnoon local time sector reveal the standard three-sheet structure of FACs, sometimes described as region 2, region 1, and mantle (referred to the midday region O) currents. A high correlation was found between the occurrence of the four FAC sheet structure and negative interplanetary magnetic field (IMF) B(sub Y). We discuss the FAC structurein terms of three types of convection cells: the merging, viscous, andlobe cells. During strongly negative IMF B(sub Y), two convection reversals exist in the prenoon sector; one is inside the viscous cell, and the other is between the viscous cell and the lobe cell. This structure of convection flow is supported by the Viking electric field and auroral UV image data. Based on the convection pattern, the four FAC sheet structure is interpreted as the latitude overlap of midday and morning FAC systems. We suggest that the for-current sheet structure is common in a certain prenoon localtime sector during strongly negative IMF B(sub Y).

Ohtani, S.↗

Retrieval of High Level Waste for the Cigeo Project - A Practical Retrieval Test Story - 16085

Since the passing of the June 28, 2006 Act, Andra has incorporated in its step-wise design development of the French high level waste (HLW) and intermediate level long lived waste (IL-LLW) deep geological repository (DGR, aka Cigeo) various requirements linked to 'reversibility' at different stages of the repository life cycle (from its construction phase to its final closure). Reversibility is based on a number of practical dispositions including the progressivity of the development and deployment of the facility, the flexibility of the nature of operations being carried out, the adaptability of the facility to future modifications and the possible retrieval of waste. The capacity to retrieve waste from Cigeo, also called 'retrievability', bears specific requirements. On a shorter term, one must demonstrate that the waste container retrieval operations are technically safe and feasible over at least 100 years. The current paper starts with two acceptations: retrievability and reversibility. It details how those two notions are defined and inter-linked. The 'Retrievability Scale' as proposed by OECD/NEA (and adopted by Andra) is also reminded. The needs for demonstration of retrieval operations are also exposed for the two categories of waste containers disposed of in Cigeo (IL-LLW and HLW) within the context of their respective emplacement configurations (in disposal horizontal vaults and micro-tunnels) at different stages of the repository life cycle. The technical part of the paper is then focused on a practical case story: a technological test campaign (still running) of HLW container retrieval out of a steel cased disposal micro-tunnel. On a test bench built on surface to simulate (create) the environmental conditions that may prevail inside a HLW micro-tunnel at time of retrieval, it was possible to check whether the mechanical means developed for the purpose were adequate and sufficient. The test case story is exposed, c/w the problems and challenges encountered (high temperature impairing the retrieval robot's proper functioning, presence of corrosion products...). The trouble-shooting solutions implemented and the results are commented. This article concludes with a critical analysis of the methods and equipment used, the results obtained and provides some perspectives of improvement. The positive outcomes of this technical test campaign pave the way for planning the in situ retrieval tests to be programmed in the 'industrial pilot phase' of Cigeo (to be implemented over the ten first years of operations, including the active and inactive test period and the first years of disposal activities): the industrial pilot phase is presently scheduled around 2026-2036 (provided the Cigeo construction is authorized in 2021, following the licensing request filing scheduled in 2018). The issues of IL-LLW containers retrieval (for which specific solutions are also studied and technical demonstrations engaged or planned) are also briefly presented. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Efficient Discovery of Novel Multicomponent Mixtures for Hydrogen Storage: A Combined Computational/Experimental Approach

The objective of the proposed program is to discover novel mixed hydrides for hydrogen storage, which enable the DOE 2010 system-level goals. Our goal is to find a material that desorbs 8.5 wt.% H 2 or more at temperatures below 85°C. The research program will combine first-principles calculations of reaction thermodynamics and kinetics with material and catalyst synthesis, testing, and characterization. We will combine materials from distinct categories (e.g., chemical and complex hydrides) to form novel multicomponent reactions. Systems to be studied include mixtures of complex hydrides and chemical hydrides [e.g. LiNH 2+ NH 3 BH 3 ] and nitrogen-hydrogen based borohydrides [e.g. Al(BH 4 ) 3 (NH 3 ) 3 ]. The 2010 and 2015 FreedomCAR/DOE targets for hydrogen storage systems are very challenging, and cannot be met with existing materials. The vast majority of the work to date has delineated materials into various classes, e.g., complex and metal hydrides, chemical hydrides, and sorbents. However, very recent studies indicate that mixtures of storage materials, particularly mixtures between various classes, hold promise to achieve technological attributes that materials within an individual class cannot reach. Our project involves a systematic, rational approach to designing novel multicomponent mixtures of materials with fast hydrogenation/dehydrogenation kinetics and favorable thermodynamics using a combination of state-of-the-art scientific computing and experimentation. We will use the accurate predictive power of first-principles modeling to understand the thermodynamic and microscopic kinetic processes involved in hydrogen release and uptake and to design new material/catalyst systems with improved properties. Detailed characterization and atomic-scale catalysis experiments will elucidate the effect of dopants and nanoscale catalysts in achieving fast kinetics and reversibility. And, state-of-the-art storage experiments will give key storage attributes of the investigated reactions, validate computational predictions, and help guide and improve computational methods. In sum, our approach involves a powerful blend of: 1) H2 Storage measurements and characterization, 2) State-of-the-art computational modeling, 3) Detailed catalysis experiments, 4) In-depth automotive perspective.

08 HYDROGEN↗

Miniature Time-of-Flight Mass Spectrometer

Major advances must occur to protect astronauts from prolonged periods in near-zero gravity and high radiation associated with extended space travel. The dangers of living in space must be thoroughly understood and methods developed to reverse those effects that cannot be avoided. Six of the seven research teams established by the National Space Biomedical Research Institute (NSBRI) are studying biomedical factors for prolonged space travel to deliver effective countermeasures. To develop effective countermeasures, each of these teams require identification of and quantitation of complex pharmacological, hormonal, and growth factor compounds (biomarkers) in humans and in experimental animals to develop an in-depth knowledge of the physiological changes associated with space travel. At present, identification of each biomarker requires a separate protocol. Many of these procedures are complicated and the identification of each biomarker requires a separate protocol and associated laboratory equipment. To carry all of this equipment and chemicals on a spacecraft would require a complex clinical laboratory; and it would occupy much of the astronauts time. What is needed is a small, efficient, broadband medical diagnostic instrument to rapidly identify important biomarkers for human space exploration. The Miniature Time-Of- Flight Mass Spectrometer Project in the Technology Development Team is developing a small, high resolution, time-of-flight mass spectrometer (TOFMS) to quantitatively measure biomarkers for human space exploration. Virtues of the JHU/APL TOFMS technologies reside in the promise for a small (less than one cubic ft), lightweight (less than 5 kg), low-power (less than 50 watts), rugged device that can be used continuously with advanced signal processing diagnostics. To date, the JHU/APL program has demonstrated mass capability from under 100 to beyond 10,000 atomic mass units (amu) in a very small, low power prototype for biological analysis. Further, the electronic nature of the TOFMS output makes it ideal for rapid telemetry to earth for in-depth analysis by ground support teams.

Potember, Richard S.↗

Microstructural development and mechanical properties of a near-eutectic directionally solidified Sn–Bi solder alloy

Sn–Bi solders may be applied for electronic applications where low-temperature soldering is required, i.e., sensitive components, step soldering and soldering LEDs. In spite of their potential to cover such applications, the mechanical response of soldered joints of Sn–Bi alloys in some cases does not meet the strength requirements due to inappropriate resulting microstructures. Hence, careful examination and control of as-soldered microstructures become necessary with a view to pre-programming reliable final properties. The present study aims to investigate the effects of solidification thermal parameters (growth rate — V{sub L} and cooling rate — T-dot{sub L}) on the microstructure of the Sn–52 wt.%Bi solder solidified under unsteady-state conditions. Samples were obtained by upward directional solidification (DS), followed by characterization through metallography and scanning electron microscopy (SEM). The microstructures are shown to be formed by Sn-rich dendrites decorated with Bi precipitates surrounded by a complex regular eutectic mixture, with alternated Bi-rich and Sn-rich phases. Experimental correlations of primary (λ{sub 1}), secondary (λ{sub 2}), tertiary (λ{sub 3}) dendritic and eutectic spacings (λ{sub coarse} and λ{sub fine}) with cooling rate and growth rate are established. Two ranges of lamellar eutectic sizes were determined, described by two experimental equations λ = 1.1 V{sub L}{sup −1/2} and λ = 0.67 V{sub L}{sup −1/2}. The onset of tertiary branches within the dendritic array along the Sn–52 wt.%Bi alloy DS casting is shown to occur for cooling rates lower than 1.5 °C/s. - Highlights: • The Sn–52 wt.%Bi solder was shown to have two eutectic sizes. • The fishbone eutectic is preferably located adjacent to the Bi-rich lamellar phases. • The onset of tertiary dendritic branches in Sn–Bi is associated with T-dot{sub L} < 1.5 °C/s. • Higher eutectic fraction and λ{sub 3} provoked a reverse increase in σ{sub u} and σ{sub y}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Evaluation of Mars CO2 Capture and Gas Separation Technologies

Recent national policy statements have established that the ultimate destination of NASA's human exploration program is Mars. In Situ Resource Utilization (ISRU) is a key technology required to ,enable such missions and it is appropriate to review progress in this area and continue to advance the systems required to produce rocket propellant, oxygen, and other consumables on Mars using the carbon dioxide atmosphere and other potential resources. The Mars Atmospheric Capture and Gas separation project is selecting, developing, and demonstrating techniques to capture and purify Martian atmospheric gases for their utilization for the production of hydrocarbons, oxygen, and water in ISRU systems. Trace gases will be required to be separated from Martian atmospheric gases to provide pure CO2 to processing elements. In addition, other Martian gases, such as nitrogen and argon, occur in concentrations high enough to be useful as buffer gas and should be captured as well. To achieve these goals, highly efficient gas separation processes will be required. These gas separation techniques are also required across various areas within the ISRU project to support various consumable production processes. The development of innovative gas separation techniques will evaluate the current state-of-the-art for the gas separation required, with the objective to demonstrate and develop light-weight, low-power methods for gas separation. Gas separation requirements include, but are not limited to the selective separation of: (1) methane and water from unreacted carbon oxides (C02-CO) and hydrogen typical of a Sabatier-type process, (2) carbon oxides and water from unreacted hydrogen from a Reverse Water-Gas Shift process, (3)/carbon oxides from oxygen from a trash/waste processing reaction, and (4) helium from hydrogen or oxygen from a propellant scavenging process. Potential technologies for the separations include' freezers, selective membranes, selective solvents, polymeric sorbents, zeolites, and new technologies. This paper summarizes the results of an extensive literature review of candidate technologies for the capture and separation of CO2 and other relevant gases. This information will be used to prioritize the technologies to be developed further during this and other ISRU projects.

Muscatello, Anthony C.↗

Advanced diesel engine component development program, tasks 4-14

This report summarizes the Advanced Diesel Engine Component Development (ADECD) Program to develop and demonstrate critical technology needed to advance the heavy-duty low heat rejection engine concept. Major development activities reported are the design, analysis, and fabrication of monolithic ceramic components; vapor phase and solid film lubrication; electrohydraulic valve actuation; and high pressure common rail injection. An advanced single cylinder test bed was fabricated as a laboratory tool in studying these advanced technologies. This test bed simulates the reciprocator for a system having no cooling system, turbo compounding, Rankine bottoming cycle, common rail injection, and variable valve actuation to achieve fuel consumption of 160 g/kW-hr (.26 lb/hp-hr). The advanced concepts were successfully integrated into the test engine. All ceramic components met their functional and reliability requirements. The firedeck, cast-in-place ports, valves, valve guides, piston cap, and piston ring were made from silicon nitride. Breakthroughs required to implement a 'ceramic' engine included the fabrication of air-gap cylinder heads, elimination of compression gaskets, machining of ceramic valve seats within the ceramic firedeck, fabrication of cast-in-place ceramic port liners, implementation of vapor phase lubrication, and elimination of the engine coolant system. Silicon nitride valves were successfully developed to meet several production abuse test requirements and incorporated into the test bed with a ceramic valve guide and solid film lubrication. The ADECD cylinder head features ceramic port shields to increase insulation and exhaust energy recovery. The combustion chamber includes a ceramic firedeck and piston cap. The tribological challenge posed by top ring reversal temperatures of 550 C was met through the development of vapor phase lubrication using tricresyl phosphate at the ring-liner interface. A solenoid-controlled, variable valve actuation system that eliminated the conventional camshaft was demonstrated on the test bed. High pressure fuel injection via a common rail system was also developed to reduce particulate emissions.

Kaushal, Tony S.↗

Effect of Minerals on the Removal of Uranium (VI) in the Presence of Humic Acid and Colloidal Silica - 19406

Uranium is one of the key contaminants of concern in groundwater as a result of past nuclear processing activities at the Department of Energy (DOE) facilities such as the Savannah River Site (SRS) in Aiken, South Carolina. SRS was one of the major nuclear processing facilities during the Cold War where plutonium was produced. Beginning with the implementation of the environmental cleanup program in 1981, SRS has become a hazardous waste management facility responsible for the storage and remediation of contaminated soil and groundwater from radionuclides. Approximately 1.8 billion gallons of acidic waste containing radionuclides and dissolved heavy metals was disposed in the F/H Area seepage basins. This led to the unintentional creation of highly contaminated groundwater plumes, consisting of radionuclides with an acidic pH between 3 and 5.5. The acidity of the plumes contributed to the mobility of several constituents of concern (COC) such as tritium ({sup 3}H), uranium-238 ({sup 238}U), iodine-129 ({sup 129}I), and strontium-90 ({sup 90}Sr) for the F-Area plume and {sup 3}H, {sup 90}Sr and mercury for the H-Area plume. This investigation will focus on uranium in the oxidation state +6 (U(VI)), which is a key contaminant of concern in the groundwater plume of the FArea. Initially, the pump-treat-reinject system was implemented from 1997 to 2003 to remove contaminants from polluted groundwater. Downgrade groundwater within the system would be pumped to the water treatment facility and re-injected upgrade within the aquifer. The effectiveness and sustainability of this process diminished over time. Therefore, it was discontinued and replaced with a funnel-and-gate process in 2004. This new process injects sodium hydroxide directly into the gates of the F-Area groundwater to effectively raise pH levels. By raising the pH of the groundwater, a treatment zone is created by reversing the acidic nature of the contaminated sediments and producing a negative net charge on the surface of sediment particles. As a result, the adsorption of cationic contaminants is expected to be enhanced. So far, this process has resulted in a decrease of {sup 90}Sr and {sup 238}U concentrations, though the concentration of iodine has been unaffected by this treatment. The solution used for the injections contains a high carbonate alkalinity in order to overcome the surface acidic conditions and natural partitions in the groundwater system. To maintain the neutral pH in the treatment zone, systematic injections are required. The continuous use of high concentrations of a carbonate solution to raise pH could re-mobilize uranium previously adsorbed within the treatment zone, though this has not been observed in the monitoring data. Humic substances (HS) are major components of soil organic matter. HS are polyfunctional organic macromolecules formed by the chemo-microbiological decomposition of biomass or dead organic matter. These substances are usually divided into three main fractions: humin (insoluble at all pH values), humic acid (soluble at pH greater than 3.5), and fulvic acid (soluble at all pH values). Humic acid carries a large number of functional groups such as aromatic rings, carboxyl groups, phenols, aliphatic chains, etc. Humic acid is an important ion exchange and metal complexing ligand with a high complexation capacity. The ability of humic acid to chemically bind to metals influences in their migration behavior and fate in natural systems. Various studies have suggested that the retention of U(VI) via sorption in the presence of humic acid is a complex process. For instance, humic acid can form an organic coating at the surface of minerals, which can enhance the sequestration of metals. Ivanov et al. (2012) studied the sorption of U(VI) sorption onto bentonite in the presence and absence of humic acid. The study found that uranium sorption in the presence of humic acid was enhanced at low pH (below 3.8) while at moderate pH (3.8 and 6.5) uranium sorption was reduced compared to the absence of humic acid. At high pH (7 and 9), uranium sorption was reduced for both the presence and absence of humic acid. Also, Krepelova et al. (2007) not only found that U(VI) sorption onto kaolinite was influenced by pH, U(VI) concentration, the presence of inorganic carbon species, and humic acid but also that U(VI) preferred to be adsorbed onto kaolinite as a uranyl-humate complex. This investigation analyzed the mechanisms of the synergetic interactions of humic acid and colloidal silica on the removal of uranium in the presence of pure minerals such as quartz, kaolinite and goethite which are characteristic of the F/H area. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Electron Temperature Fluctuation Measurements and Transport Model Validation at Alcator C-Mod

The tokamak is a type of toroidal device used to confine a fusion plasma using large magnetic fields. Tokamaks and stellarators the leading devices for confining plasmas for fusion, and the capability to predict performance in these magnetically confined plasmas is essential for developing a sustainable fusion energy source. The magnetic configuration of tokamaks and stellarators does not exist in Nature, yet, the fundamental processes governing transport in fusion plasmas are universal – turbulence and instabilities, driven by inhomogeneity and asymmetry in the plasma, conspire to transport heat and particles across magnetic field lines and can play critical roles in impurity confinement and generation of intrinsic rotation. Turbulence exists in all plasmas, and in neutral fluids as well. The study of turbulence is essential to developing a fundamental understanding of the nature of the fourth state of matter, plasmas. Experimental studies of turbulence in tokamaks date back to early scattering observations from the late 1970s. Since that time, great advances in turbulence diagnostics have been made, all of which have significantly enhanced our knowledge and understanding of turbulence in tokamaks. Through comparisons with advanced gyrokinetic theory and turbulent-transport models a great deal of evidence exists to implicate turbulent-driven transport as an important mechanism determining transport in all channels: heat, particle and momentum However, prediction and control of turbulent-driven transport remains elusive. Key to development of predictive transport models for magnetically confined fusion plasmas is validation of the nonlinear gyrokinetic transport model, which describes transport due to turbulence. Validation of gyrokinetic codes must include detailed and quantitative comparisons with measured turbulence characteristics, in addition to comparisons with inferred transport levels and equilibrium profiles. For this reason, advanced plasma diagnostics for studying core turbulence are needed in order to assess the accuracy of gyrokinetic models for turbulent-driven particle, heat and momentum transport. New core turbulence diagnostics at the world-class tokamaks Alcator C-Mod at MIT and ASDEX Upgrade at the Max Planck Institute for Plasma Physics have been designed, developed, and operated over the course of this project. These new instruments are capable of measuring electron temperature fluctuations and the phase angle between density and temperature fluctuations locally and quantitatively. These new data sets from Alcator C-Mod and ASDEX Upgrade are being used to fill key gaps in our understanding of turbulent transport in tokamaks. In particular, this project has results in new results on the topics of the Transport Shortfall, the role of ETG turbulence in tokamak plasmas, profile stiffness, the LOC/SOC transition, and intrinsic rotation reversals. These data are used in a rigorous process of “Transport model validation”, and this group is a world-leader on using turbulence models to design new hardware and new experiments at tokamaks. A correlation electron cyclotron emission (CECE) diagnostic is an instrument used to measure micro-scale fluctuations (mm-scale, compared to the machine size of meters) of electron temperature in magnetically confined fusion plasmas, such as those in tokamaks and stellarators. These micro-scale fluctuations are associated with drift-wave type turbulence, which leads to enhanced cooling and mixing of particles in fusion plasmas and limits achieving the required temperatures and densities for self-sustained fusion reactions. A CECE system can also be coupled with a reflectometer system that measured micro-scale density fluctuations, and from these simultaneous measurements, one can extract the phase between the density (n) and temperature (T) fluctuations, creating an nT phase diagnostic. Measurements of the fluctuations and the phase angle between them are extremely useful for testing and validating predictive models for the transport of heat and particles in fusion plasmas due to turbulence. Once validated, the models are used to predict performance in ITER and other burning plasmas, such as the MIT ARC design. Most recently, data from the newly developed, so-called “CECE diagnostic” [Cima 1995, White 2008] and “nT phase angle measurements” [Haese 1999, White 2010] ]will be combined with data from density fluctuation diagnostics at ASDEX Upgrade to support a long-term program of physics research in turbulence and transport that will allow for more stringent testing and validation of gyrokinetic turbulent-transport codes. This work directly impacts the development of predictive transport models in the U.S. FES program, such as TGLF, developed by General Atomics, which are used to predict performance in ITER and other burning plasma devices as part of advancing the development of fusion energy sciences.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

2015 Sensorimotor Risk Standing Review Panel Evidence and Status Review For: the Risk of Impaired Control of Spacecraft/Associated Systems and Decreased Mobility Due to Vestibular/Sensorimotor Alterations Associated with Spaceflight

The 2015 Sensorimotor Risk Standing Review Panel (from here on referred to as the SRP) participated in a WebEx/teleconference with members of the Human Health Countermeasures (HHC) Element, representatives from the Human Research Program (HRP), NASA Headquarters, and NASA Research and Education Support Services (NRESS) on December 17, 2015 (list of participants is in Section VI of this report). The SRP reviewed the new Evidence Report for the Risk of Impaired Control of Spacecraft/Associated Systems and Decreased Mobility Due to Vestibular/Sensorimotor Alterations Associated with Spaceflight (from here on referred to as the 2015 Sensorimotor Evidence Report), and also received a status review of the Risk. The opening section of the 2015 Sensorimotor Evidence Report provides written descriptions of various incidents that have occurred during space missions. In most of these incidents, the main underlying contributing factors are not easy to identify unambiguously. For example, in section 1.9, a number of falls occurred while astronauts were walking on the moon. It is not clear to the SRP, however, why they fell. It is only possible to extrapolate from likely specific psychophysical or physiological abnormalities, but how these abnormalities were determined, and how they were directly responsible for the falls is unclear to the SRP. Section 2.1.2 on proprioception is very interesting, but the functional significance of the abnormalities detected is not clear. The SRP sees this as a problem throughout the report: a mapping between the component abnormalities identified and the holistic behaviors that are most relevant, for example, controlling the vehicle, and locomotion during egress, is generally lacking. The SRP thinks the cognitive section is too strongly focused on vestibular functioning. The SRP questions the notion that the main cognitive effects are mainly attributable to reversible vestibular changes induced by spaceflight. The SRP thinks that there can also be independent cognitive effects. The Functional Task Test (FTT) protocols and the Field Test are particularly valuable. The conclusion is that the unloading of major postural muscles experienced during spaceflight plays a central role in the alteration of functional task performance and balance control. This conclusion stands in contrast with the statements in other parts of the document that emphasize the role of vestibular changes on these functions. It would help to more fully integrate these two views on the predominant effects of spaceflight. Although the SRP thinks the countermeasures section is interesting, the proposed countermeasures are not well integrated with the abnormalities described in previous sections. The SRP thinks it would help enormously to have explicit links among each abnormality, its 2015 Sensorimotor Risk SRP Evidence Review Final Report 2 overall importance/impact on function, and the appropriate countermeasure that can be implemented to maintain adequate functioning.

Steinberg, Susan↗