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NDT System for Metal Components in Concrete Structures (Final Report)

Steel reinforcements embedded within concrete can corrode and crack, leading to weakening of the structures, and existing NDT (non-destructive testing) techniques do not provide the full picture. Condition assessment is critical in evaluating these structures in order to ensure safe, long-term operation of the nuclear power plants. Improved NDT techniques are needed as the nation’s generating stations age and require action based on increasingly critical inspection data. The power industry uses eddy current test (ECT) during in-service inspections to detect and monitor defects such as cracks and corrosion in metals, particularly metal pipes. However, the detection of defects in the reinforcing steel embedded in concrete is far more challenging for numerous reasons. Primary among them is the concrete layer’s thickness, which prevents the ability to have a close proximity between sensor and metallic sample. One solution to this problem is to create a higher sensitivity technique which can inspect at depth, with good spatial resolution and excellent directional sensitivity, to isolate the metal buried deep in the concrete and characterize defects in the metal. The goal of the phase II research program was to study and develop a new reinforced concrete NDT technology based on anisotropic magnetoresistive (AMR) sensors designed specifically for ECT of steel reinforcements in concrete. The first technical objective was to demonstrate the capability of inspecting steel reinforcement structures, including metal rebar and tensioning cable at or below 6” of depth embedded in concrete. Another objective was to be able to confidently identify multiple layers of reinforcements at varying depths. In addition, the technique needed to be able to provide condition assessment of the metal, providing data on the structure and positioning of the steel members, material loss, and detection of the presence of breaks. An important part of the research and development was aimed at achieving superior performance compared to existing technology. The ability to detect corrosion breaks in unbonded multi-wire and multi-strand tendons was another important objective. The final objective that led to a successful program was to build a complete prototype portable scanning system capable of demonstrating the probe performance in the field. All of these objectives were met, which provided data for the system development work going forward. RMD worked with the engineering firm Simpson Gumpertz & Heger to develop a detailed problem definition for concrete structures and the necessary sensor specifications. In addition, we developed finite element simulation models for the eddy current based NDT system through the analysis of the electromagnetic (EM) properties of sample materials and the orientation of the transmitter, sensor array (receivers), metal, and intervening materials like concrete and air. Based on the modeling and specifications, we designed and fabricated prototype sensor modules. We then acquired and fabricated test samples to characterize and optimize the sensors. Finally, we built a complete prototype for testing on actual concrete structures. This new NDT technology has high promise for greatly improving capabilities in the inspection of steel reinforcements within concrete structures, such as rebar, liners, anchors, and prestressing cables. This method could be valuable in the maintenance of nuclear power plants, and many other structures critical to our nation’s infrastructure.

42 ENGINEERING↗

Metall: A persistent memory allocator for data-centric analytics

Data analytics applications transform raw input data into analytics-specific data structures before performing analytics. Unfortunately, such data ingestion steps are often more expensive than analytics. In addition, various types of NVRAM devices are already used in many HPC systems today. Such devices will be useful for storing and reusing data structures beyond a single process life cycle. We developed Metall, a persistent memory allocator built on top of the memory-mapped file mechanism. Metall enables applications to transparently allocate custom C++ data structures into various types of persistent memories. Metall incorporates a concise and high-performance memory management algorithm inspired by Supermalloc and the rich C++ interface developed by Boost.Interprocess library. On a dynamic graph construction workload, Metall achieved up to 11.7x and 48.3x performance improvements over Boost.Interprocess and memkind (PMEM kind), respectively. We also demonstrate Metall’s high adaptability by integrating Metall into a graph processing framework, GraphBLAS Template Library. Here this study’s outcomes indicate that Metall will be a strong tool for accelerating future large-scale data analytics by allowing applications to leverage persistent memory efficiently.

97 MATHEMATICS AND COMPUTING↗

B-Trees and Cache-Oblivious B-Trees with Different-Sized Atomic Keys

Most B-tree articles assume that all $\textit{N}$ keys have the same size $\textit{K}$, that $\textit{f = B/K}$ keys fit in a disk block, and therefore that the search cost is $O(\text{log}_{f+1}N) $ block transfers. When keys have variable size, B-tree operations have no nontrivial performance guarantees, however. This article provides B-tree-like performance guarantees on dictionaries that contain keys of different sizes in a model in which keys must be stored and compared as opaque objects. The resulting atomic-key dictionaries exhibit performance bounds in terms of the average key size and match the bounds when all keys are the same size. Atomic-key dictionaries can be built with minimal modification to the B-tree structure, simply by choosing the pivot keys properly. Further, this article describes both static and dynamic atomic-key dictionaries. In the static case, if there are $\textit{N}$ keys with average size $\textit{K}$, the search cost is $O(\lceil K/B\rceil \text{log}_{1 + \lceil K/B\rceil} N)$ expected transfers. It is not possible to transform these expected bounds into worst-case bounds. The cost to build the tree is $\textit{O(NK)}$ operations and $\textit{O(NK/B)}$ transfers if all keys are presented in sorted order. If not, the cost is the sorting cost. For the dynamic dictionaries, the amortized cost to insert a key $\textit{κ}$ of arbitrary length at an arbitrary rank is dominated by the cost to search for $\textit{κ}$. Specifically, the amortized cost to insert a key $\textit{κ}$ of arbitrary length and random rank is $O(\lceil K/B\rceil log_{1+ \lceil B/K\rceil } N + |κ|/B)$ transfers. A dynamic-programming algorithm is shown for constructing a search tree with minimal expected cost. This article also gives a cache-oblivious static atomic-key B-tree, which achieves the same asymptotic performance as the static B-tree dictionary, mentioned previously. A cache-oblivious data structure or algorithm is not parameterized by the block size $\textit{B}$ or memory size $\textit{M}$ in the memory hierarchy; rather, it is universal, working simultaneously for all possible values of $\textit{B}$ or $\textit{M}$. On a machine with block size $\textit{B}$, if there are $\textit{N}$ keys with average size $\textit{K}$, search operations costs $O(\lceil K/B \rceil log_{1+ \lceil B/K \rceil} N)$ block transfers in expectation. This cache-oblivious layout can be built in $\textit{O(N}\text{log}\textit{(NK))}$ processor operations.

97 MATHEMATICS AND COMPUTING↗

Magnetic Structures and Magnetic Phase Transitions in Rare-Earth RMn{sub 2}Si{sub 2} Intermetallic Compounds (R = Sm, Tb)

The magnetic structures that form in La{sub 1–x}R{sub x}Mn{sub 2}Si{sub 2} (R = Sm, Tb) layered compounds with various concentrations x have been determined by magnetic neutron diffraction and magnetic measurements, and the magnetic phase diagrams have been built. It is shown that the formation of the magnetic structures is dependent not only on exchange interactions, but also on the type of the magnetic anisotropy of a rare-earth atom. It is found that, in La{sub 1–x}Tb{sub x}Mn{sub 2}Si{sub 2} compounds with 0.2 < x < 0.5, the competition of the Tb–Mn and Mn–Mn interlayer exchange interactions and the existence of a strong uniaxial magnetic anisotropy in the Mn and Tb sublattices leads to the frustrated magnetic state and prevents the formation of the long-range magnetic order in the Tb sublattice.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The CompTox Chemistry Dashboard: a community data resource for environmental chemistry

Despite an abundance of online databases providing access to chemical data, there is increasing demand for highquality, structure-curated, open data to meet the various needs of the environmental sciences and computational toxicology communities. The U.S. Environmental Protection Agency’s (EPA) web-based CompTox Chemistry Dashboard is addressing these needs by integrating diverse types of relevant domain data through a cheminformatics layer, built upon a database of curated substances linked to chemical structures. These data include physicochemical, environmental fate and transport, exposure, usage, in vivo toxicity, and in vitro bioassay data, surfaced through an integration hub with link-outs to additional EPA data and public domain online resources. Batch searching allows for direct chemical identifer (ID) mapping and downloading of multiple data streams in several diferent formats. This facilitates fast access to available structure, property, toxicity, and bioassay data for collections of chemicals (hundreds to thousands at a time). Advanced search capabilities are available to support, for example, non-targeted analysis and identifcation of chemicals using mass spectrometry. The contents of the chemistry database, presently containing ~ 760,000 substances, are available as public domain data for download. The chemistry content underpinning the Dashboard has been aggregated over the past 15 years by both manual and auto-curation techniques within EPA’s DSSTox project. DSSTox chemical content is subject to strict quality controls to enforce consistency among chemical substance-structure identifers, as well as list curation review to ensure accurate linkages of DSSTox substances to chemical lists and associated data. The Dashboard, publicly launched in April 2016, has expanded considerably in content and user trafc over the past year. It is continuously evolving with the growth of DSSTox into high-interest or data-rich domains of interest to EPA, such as chemicals on the Toxic Substances Control Act listing, while providing the user community with a fexible and dynamic web-based platform for integration, processing, visualization and delivery of data and resources. The Dashboard provides support for a broad array of research and regulatory programs across the worldwide community of toxicologists and environmental scientists.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interface engineering of phase separation in SrRuO 3 /SrTiO 3 hybrid superlattices

Most observed phase separation phenomena in complex oxides occur in systems with chemical dopants or structural defects, and theories have established the strong connection between phase separation and the random distribution of chemical dopants. Recent experiments on fabricated high-quality oxide superlattices also confirmed that the phase separation is suppressed in the clean systems without chemical disorders. Thus far, phase separation in strongly correlated oxides without the need of chemical dopants or structural defects has not been fully demonstrated. Here, we have built chemically ordered hybrid superlattices using prototypical SrRuO 3 and SrTiO 3 perovskite oxides. Contrary to previous understandings, we observe phase separation of two magnetic phases with different spin easy axes. We elucidate this phenomenon through first-principles calculations that the hybrid superlattices have a spontaneous structural instability, leading to a coexistence of ferromagnetic and antiferromagnetic phases. In this work, our findings provide an alternative pathway other than chemical doping to introduce phase separation in correlated oxides and imply that phase separation can exist in clean systems without the need of chemical disorders.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electronic and structural properties of RbCe X 2 ( X 2 : O 2 , S 2 , SeS, Se 2 , TeSe, Te 2 )

We report triangular lattice delafossite compounds built from magnetic lanthanide ions are a topic of recent interest due to their frustrated magnetism and realization of quantum disordered magnetic ground states. Here we report the evolution of the structure and electronic ground states of RbCeX 2 compounds, built from a triangular lattice of Ce 3+ ions, upon varying their anion character (X 2 =O 2 , S 2 , SeS, Se 2 , TeSe, Te 2 ). This includes the discovery of a new member of this series, RbCeO 2 , that potentially realizes a quantum disordered ground state analogous to NaYbO 2 . Magnetization and susceptibility measurements reveal that all compounds manifest mean-field antiferromagnetic interactions and, with the exception of the oxide, possess signatures of magnetic correlations onset below 1 K. The crystalline electric field level scheme is explored via neutron scattering and ab initio calculations in order to model the intramultiplet splitting of the J=5/2 multiplet. In addition to the two excited doublets expected within the J=5/2 manifold, we observe one extra local mode present across the sample series. This added mode shifts downward in energy with increasing anion mass and decreasing crystal field strength, suggesting a long-lived anomalous mode endemic to anion motion about the Ce3 + sites.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}

A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, and its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity . Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A national facility for biological cryo-electron microscopy

This review provides a brief update on the use of cryo-electron microscopy for integrated structural biology, along with an overview of the plans for the UK national facility for electron microscopy being built at the Diamond synchrotron. Three-dimensional electron microscopy is an enormously powerful tool for structural biologists. It is now able to provide an understanding of the molecular machinery of cells, disease processes and the actions of pathogenic organisms from atomic detail through to the cellular context. However, cutting-edge research in this field requires very substantial resources for equipment, infrastructure and expertise. Here, a brief overview is provided of the plans for a UK national three-dimensional electron-microscopy facility for integrated structural biology to enable internationally leading research on the machinery of life. State-of-the-art equipment operated with expert support will be provided, optimized for both atomic-level single-particle analysis of purified macromolecules and complexes and for tomography of cell sections. The access to and organization of the facility will be modelled on the highly successful macromolecular crystallography (MX) synchrotron beamlines, and will be embedded at the Diamond Light Source, facilitating the development of user-friendly workflows providing near-real-time experimental feedback.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Morphology and Current Transport in a Thin-Film Polycrystalline Au–Zn{sub x}Cd{sub 1–x}S–Mo Structure with Wide Photosensitivity Range in the Ultraviolet and Visible Radiation Spectral Region

Studies are carried out on the morphology of the surface and photovoltaic characteristics of a thinfilm Au–Zn{sub x}Cd{sub 1–x}S–Mo structural injection photodetector with a wide photosensitivity range in the ultraviolet and visible radiation spectral regions. The composition of Zn{sub x}Cd{sub 1–x}S film in the Au–Zn{sub x}Cd{sub 1–x}S–Mo structure with a wide photosensitivity spectrum in the ultraviolet and visible spectrum, where x on the surface varies from 0.22 to 0.24, is studied. The mechanism of current transport is investigated, and the main electrophysical parameters of the semiconducting materials are determined. The use of Zn{sub x}Cd{sub 1–x}S film with a variable band gap in the thin-film heterojunction solar cells, where they are used as the buffer layer, will provide an opportunity to increase the photosensitivity of the structure in the short-wave region of the radiation spectrum, increase the value of the built-in potential, short-circuit current and value of the open-circuit voltage of the structure.

14 SOLAR ENERGY↗

Tunable surface acoustic wave device using semiconducting MgZnO and piezoelectric NiZnO dual-layer structure on glass

Tunable surface acoustic wave (SAW) devices have attracted considerable interests due to its applications in emerging fields, such as secured wireless communication, adaptive signal processing, and smart sensing systems. We report a dual-input-voltage-controlled tunable SAW built on glass, which uses a ZnO-based dual-layer structure consisting of a piezoelectric Ni- doped ZnO (NZO) and semiconducting Mg-doped ZnO (MZO). The interdigital (IDT) electrodes are buried in the piezoelectric NZO layer to form the delay line for SAW propagation, while the semiconductor MZO layer serves as the channel of a thin film transistor (TFT) to modulate the conductivity. Results show the interface between MZO channel and SiO 2 gate dielectric layer of the TFTT significantly impacts on SAW tuning performances due to Zn diffusion from MZO into SiO 2 . The TFT-SAW device using an ultra-thin MgO layer as interface modification enables SAW frequency tuning of 0.53% under solely V gs control with 0–12 V. The required voltage range is significantly reduced compared regular MZO-NZO TFT-SAW counterpart (Δf/f c ~ 0.25%; V gs –30 to –14 V) without interface modification. With additional control of V ds , the SAW frequency tunability is further expanded from 0.46% to 0.63%. As a result, this dual-input voltage-controlled frequency tuning device on glass is promising for low-voltage, low-cost portable smart sensors and voltage-controlled reconfigurable radio-frequency identification tags.

36 MATERIALS SCIENCE↗

Evaluation of changes in the microbial community structure in the sediments of a constructed wetland over the years

This study presents the results of the long term (2007–2014) monitoring of the microbial community structure in the surface sediments of the H-02 constructed wetland system, which was built on the Savannah River Site in Aiken, SC, USA, to treat the waste water generated at the Tritium facility. Microbial community structure provides valuable information about the functioning of constructed wetlands and helps understand the biogeochemical cycling of nutrients and contaminants. Phospholipids fatty acid (PLFA) analysis and qPCR were used to identify major bacterial phyla in the sediments. The physiochemical properties of the sediments were also used to deduce potential effects on the microbial community structure over the years. Sulfate-reducing bacteria (SRB) were the most dominant bacterial groups, and their prevalence was progressively increasing throughout the years most likely on the account of methane producers. Concentrations of trace metals (copper and zinc) were negatively associated with methane producers and oxidizer while positively correlated with SRB. Overall, the H-02 wetland system was efficient in immobilizing copper and zinc through the anaerobic respiration of sulfate by SRB and minimizing methane emission through the progressive elimination of methane producers by SRB and Geobacter. Furthermore, the aim of this study was to monitor the changes in the microbial community structure in the surface sediments of a constructed wetland during the first 7 years of operation.

59 BASIC BIOLOGICAL SCIENCES↗

Syntheses, crystal structures, and properties of new metal-5-bromonicotinate coordination polymers

Four metal–5-bromonicotinate (Brnic) coordination polymers [Fe(Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (1), [Ni(Brnic){sub 2}]{sub n} (2), [Ni(Brnic)(bpy)(H{sub 2}O){sub 2}]{sub n}·n(Brnic)·4.5nH{sub 2}O (3), and [Co{sub 2}(Brnic){sub 3}(bpy){sub 2}(OH)]{sub n}·nH{sub 2}O (4) have been synthesized and structurally characterized (bpy=4,4′-bipyridine). Complex 1 has corrugated (4,4) sheets formed by μ-Brnic ligands and planar nodes Fe(II). As for 2–4, they all built up from Brnic-bridged dinuclear subunits, but have very different structure features. Complex 2 is a twin-like polymer with (4,4) layers formed by twin paddle-wheel [Ni{sub 2}(Brnic){sub 4}] subunits. Through the bridge coordination of bpy ligands with dinuclear rings [Ni{sub 2}(Brnic){sub 2}] and trigons [Co{sub 2}(Brnic){sub 3}(OH)], 6{sup 3}-topological cationic layers with nanosized grids of 3 and chiral ladder-type double chains of 4 formed, respectively. Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules 1–4. The thermostabilities of all compounds have been discussed in detail. Moreover, the magnetic investigations of 2 and 4 indicate that there exist antiferromagnetic interactions in the paddle-wheel [Ni{sub 2}(Brnic){sub 4}] and trigon [Co{sub 2}(Brnic){sub 3}(OH)] cores, respectively. - Highlights: • Four novel metal–5-bromonicotinate coordination polymers have been synthesized. • Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules. • Antiferromagnetic interactions in nickel(II) paddle-wheel and cobalt(II) trigon cores were observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing Chromophore Energetics and Couplings for Singlet Fission in Solar Cell Applications: Final technical report

The overall goal of this project is to provide a molecular-level understanding of the mechanisms and requirements for efficient exciton multiplication through singlet fission processes. Such understanding would open the paths for improving alternative sources of energy including an improved efficiency of dye-sensitized solar cells. Using high-resolution anion photoelectron spectroscopy, electronic structures of chromophores are explored by probing directly the singlet and triplet states involved in singlet fission, determining precisely their energetics, vibrational structures and couplings. To carry out these experiments, we built a flexible-source instrument that allows for cryogenic cooling of precursor anions, providing improved spectral resolutions. Moreover, our velocity map imaging spectrometer includes novel design considerations that provide better focus with less stringent parameters. Using this instrument, we studied the three-ring polycyclic aromatic hydrocarbon molecules, anthracene and fluoranthene, the latter can be considered as a covalently-bonded benzyl and naphthyl system. Starting from the radical anion ground state, we accessed the singlet and triplet states at the same time, and the results revealed intriguing vibronic coupling signatures in both electronic states, which may possibly be related to singlet fission mechanisms. We further studied aromatic oxide molecules, phenoxy, 1-naphthoxy, and 2-naphthoxy, whose large molecular dipole moments supported highly delocalized dipole bound states. An intrinsic property of singlet fission is the delocalization of excitation to nearby chromophore molecules. In an effort to extend our studies to solvated chromophore clusters, we development new instrumental capabilities that allowed for formation of weakly bound clusters around any ion by utilizing liquid-nitrogen cooled octupole ion traps. In characterizing this new approach for gas phase cluster formation, we studied the structures of a variety of solvated clusters, from solvated ionic liquid cation, where intermolecular interactions are dominated by electrostatic interactions, to solvated peptides, where hydrogen-bonding with solvent molecules can directly alter the peptide structure. Overall, we found that the formation of weakly-bound clusters in a cryogenic ion trap can be a viable approach for accessing structures that better represent those found in condensed phase. In the process, we also implemented a straightforward double-resonance setup and established a protocol for isotopic substitution using cryogenic ion traps, both of which aided in decongesting crowded experimental spectra that often accompany these larger solvated systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural geology investigation on Massif Central and Parisian Basin (France)

The author has identified the following significant results. Band 5 gives the most information concerning the fracturing in the Massif Central and Parisian Basins. Band 6 and 7 show the fractures emphasized by forest boundaries and by the linear trace of water courses. The most remarkable information drawn from the preliminary investigation of two ERTS-1 images covering two different landscapes, a regular relief of shelving plateau bounded by cuestas having a sedimentary origin and a mountainous region built in crystalline and volcanic rocks, is that the deep structural elements under a thick sedimentary cover can be translated on the surface by indirect criteria. MSS imagery has permitted the Metz fault to be extended towards the west and shows clearly, through land use on the Rhone Valley fluvial deposit, the continuation towards the east of the carboniferous basin of St. Etienne.

Weecksteen, G.↗

First principles free energy model with dynamic magnetism for δ -plutonium

We present an ab initio free energy model derived from a fully relativistic density functional theory (DFT) electronic structure with dynamic magnetism for δ -plutonium (face-centered cubic, fcc). The DFT model is extended with orbital-orbital interaction in a parameter free orbital polarization (OP) mechanism consistent with previous modeling of plutonium. Gibbs free energy is built from components associated with the temperature dependence of the electronic structure and the corresponding electronic entropy, lattice vibrations within an anharmonic lattice dynamics model, and dynamical fluctuations of the magnetization density, i.e. magnetic fluctuations. The fluctuation model consists of transverse and longitudinal modes driven by temperature induced excitations of the DFT + OP electronic structure. The ab initio model thus incorporates fluctuating states beyond the electronic ground state. Thanks to the dynamic magnetism, the theory predicts excellent thermodynamic properties and a Gibbs free energy in accord with CALPHAD and semi-empirical modeling developed from the thermodynamic observables. The magnetic fluctuations further explain anomalous behaviors of the thermal expansion in plutonium. Specifically, a thermal expansion for the δ -plutonium system turning from positive to negative at temperatures above room temperature, a tendency for gallium to reduce and remove the negative thermal expansion depending on composition, and a positive thermal expansion for the high temperature ϵ phase.

dynamic↗

Understanding of the Dynamics of the Stirling Convertor Advanced by Structural Testing

The NASA Glenn Research Center, the U.S. Department of Energy, and the Stirling Technology Company (STC) are developing a highly efficient, long-life, free-piston Stirling convertor for use as an advanced spacecraft power system for future NASA missions, including deep-space and Mars surface applications. As part of this development, four structural dynamic test programs were recently performed on Stirling Technology Demonstration Convertors (TDC's) that were designed and built by STC under contract to the Department of Energy. This testing was performed in Glenn's Structural Dynamics Laboratory and Microgravity Emissions Laboratory. The first test program, in November and December 1999, demonstrated that the Stirling TDC could withstand the harsh random vibration experienced during a typical spacecraft launch and survive with no structural damage or functional power performance degradation. This was a critical step in enabling the use of Stirling convertors for future spacecraft power systems. The most severe test was a 12.3grms random vibration test, with test durations of 3 min per axis. The random vibration test levels were chosen to simulate, with margin, the maximum anticipated launch vibration conditions. The Microgravity Emissions Laboratory is typically used to measure the dynamics produced by operating space experiments and the resulting impact to the International Space Station's microgravity environment. For the second Stirling dynamic test program, performed in January 2001, the Microgravity Emissions Laboratory was used to characterize the structure-borne disturbances produced by the normal operation of a pair of Stirling convertors. The forces and moments produced by the normal operation of a Stirling system must be recognized and controlled, if necessary, so that other nearby spacecraft components, such as cameras, are not adversely affected. The Stirling convertor pair emitted relatively benign tonal forces at its operational frequency and associated harmonics. Therefore, Stirling power systems will not disturb spacecraft science experiments if minimal appropriate mounting efforts are made. The third test program, performed in February and May 2001, resulted in a modal characterization of a Stirling convertor. Since the deflection of the TDC piston rod, under vibration excitation, was of particular interest, the outer pressure shell was removed to allow access to the rod. Through this testing, the Stirling TDC's natural frequencies and modes were identified. This knowledge advanced our understanding of the successful 1999 vibration test and may be utilized to optimize the output power of future Stirling designs. The fourth test program, in April 2001, was conducted to characterize the structural response of a pair of Stirling convertors, as a function of their mounting interface stiffness. The test results provide guidance for the Stirling power package interface design. Properly designed, the interface may lead to increased structural capability and power performance beyond what was demonstrated in the successful 1999 vibration test. Dynamic testing performed to date at Glenn has shown that the Stirling convertors can withstand liftoff random vibration environments and meet "good neighbor" vibratory emission requirements. Furthermore, the future utilization of the information obtained during the tests will allow the corporation selected to be the Stirling system integrator to optimize their convertor and system interfaces designs. Glenn's Thermo-Mechanical Systems Branch provides Stirling technology expertise under a Space Act Agreement with the Department of Energy. Additional vibration testing by Glenn's Structural Systems Dynamics Branch is planned to continue to demonstrate the Stirling power system's vibration capability as its technology and flight system designs progress.

Hughes, William O.↗

Lithium Intercalation in Anatase Titanium Vacancies and the Role of Local Anionic Environment

The structure of bulk and nondefective compounds is generally described with crystal models built from well mastered techniques such the analysis of an X-ray diffractogram. The presence of defects, such as cationic vacancies, locally disrupt the long-range order, with the appearance of local structures with order extending only a few nanometers. To probe and describe the electrochemical properties of cation-deficient anatase, we investigated a series of materials having different concentrations of vacancies, i.e., Ti 1–x–y $\square$ x+y O 2–4(x+y) F 4x (OH) 4y , and compared their properties with respect to defect-free stoichiometric anatase TiO2. At first, we characterized the series of materials Ti 1–x–y $\square$ x+y O 2–4(x+y) F 4x (OH) 4y by means of pair distribution function (PDF), 19 F nuclear magnetic resonance (NMR), Raman and X-ray photoelectron spectroscopies, to probe the compositional and structural features. Second, we characterized the insertion electrochemical properties vs metallic lithium where we emphasized the beneficial role of the vacancies on the cyclability of the electrode under high C-rate, with performances scaling with the concentration of vacancies. The improved properties were explained by the change of the lithium insertion mechanism due to the presence of the vacancies, which act as host sites and suppress the phase transition typically observed in pure TiO 2 , and further favor diffusive transport of lithium within the structure. NMR spectroscopy performed on lithiated samples provides evidence for the insertion of lithium in vacancies. By combining electrochemistry and DFT-calculations, we characterized the electrochemical signatures of the lithium insertion in the vacancies. Importantly, we found that the insertion voltage largely depends on the local anionic environment of the vacancy with a fluoride and hydroxide-rich environments, yielding high and low insertion voltages, respectively. Lastly, this work further supports the beneficial use of defects engineering in electrodes for batteries and provides new fundamental knowledge in the insertion chemistry of cationic vacancies as host sites.

36 MATERIALS SCIENCE↗