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At least 1,135 records · Page 63

Nonlinear Time Delayed Feedback Control of Aeroelastic Systems: A Functional Approach

In addition to its intrinsic practical importance, nonlinear time delayed feedback control applied to lifting surfaces can result in interesting aeroelastic behaviors. In this paper, nonlinear aeroelastic response to external time-dependent loads and stability boundary for actively controlled lifting surfaces, in an incompressible flow field, are considered. The structural model and the unsteady aerodynamics are considered linear. The implications of the presence of time delays in the linear/nonlinear feedback control and of geometrical parameters on the aeroelasticity of lifting surfaces are analyzed and conclusions on their implications are highlighted.

Marzocca, Piergiovanni↗

The influence of atmospheric stratification on scatterometer winds

Scatterometers measure surface roughness which is empirically related either to surface stress or to the equivalent neutral stability wind. The importance of atmospheric stability effects for the analysis of these data is studied. For low wind speeds and neutral to slightly stable conditions, neutral stability wind is quite sensitive to stability. A variational analysis procedure for the scatterometer data, which adjusts both the near-surface velocity and temperature, is developed. In simulation tests, temperature analysis increments are found to be small. Also, the differences in the wind analyses due to differences in the temperature background field are small. However, if stability effects are not accounted for, there will be small systematic errors in the wind analysis.

Hoffman, Ross N.↗

Operational stability of mixed Sn–Pb perovskite solar cells: Mechanisms, mitigation strategies, and perspectives

Mixed Sn–Pb perovskites provide the 1.2–1.3 eV narrow-bandgap absorber needed for high efficiency of all perovskite tandems, but their deployment is limited by operational instability under light. This review synthesizes mechanistic origins and recent mitigation strategies for mixed Sn–Pb perovskite solar cells. The oxidation of Sn 2+ to Sn 4+ , often driven by iodine formation under light and bias, is the primary failure pathway; it creates Sn vacancies, self-doping, and nonradiative loss. Surface/grain-boundary defects, halide migration, reactive oxygen species, and interfacial redox at charge-transport layers, along with hole accumulation from poor band alignment, further accelerate Sn–Pb perovskite degradation. Here we survey recent stability advances across additive chemistry, surface and grain-boundary passivation, buried-interface redesign with modified or alternative hole transport layers, and solvent systems that preserve Sn 2+ and correct Sn–Pb speciation for scalable coating. Together, these recent advances have enabled devices to retain 80%–90% output for hundreds to over a thousand hours. Lastly, we provide our perspectives on further improving the operational stability of Sn–Pb perovskite and solar cells.

14 SOLAR ENERGY↗

Direct Observation of Solvent–Reaction Intermediate Interactions in Heterogeneously Catalyzed Alcohol Coupling

The relative stability of reactive intermediates and reactants on a surface, which dictates the rate and selectivity of catalytic reactions in both gas and liquid phases, is dependent on numerous factors. One well-established example is secondary interactions, such as van der Waals interactions between the catalyst surface and the pendant group of the intermediate, which can govern reaction selectivity for coupling reactions. In this work, we directly show that interactions between adsorbed reaction intermediates and reactant molecules increase the binding energy and affects the geometrical arrangement of coadsorbed reactant/solvent molecules. Evidence for this effect is demonstrated for the oxidative coupling reaction of methanol on a single crystal gold (Au(110)) surface. The rate-limiting reaction intermediate for methanol selfcoupling, methoxy, stabilizes excess adsorbed methanol, which desorbs as a result of beta-hydride decomposition of the adsorbed methoxy. Direct molecular-scale imaging by scanning tunneling microscopy, supplemented by density functional theory, revealed interactive structures formed by methoxy and coadsorbed methanol. Interactions between the methoxy intermediate and coadsorbed methanol stabilizes a hydrogen-bonded network comprising methoxy and methanol by a minimum of 0.13 eV per methanol molecule. Inclusion of such interactions between reaction intermediates and coadsorbed reactants and solvents in kinetic models is important for microkinetic analysis of the rates and selectivities of catalytic reactions in both the gas and liquid phases whenever appreciable coverages of species from the ambient phase exist.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Version 2 Goddard Satellite-Based Surface Turbulent Fluxes (GSSTF2)

The global air-sea fluxes of momentum, latent and sensible heat, radiation, and freshwater (precipitation-evaporation) are required for driving Ocean models and validating coupled ocean- atmosphere global models. Wind stress is the major forcing for driving the oceanic circulation, while evaporation is a key component of hydrological cycle and surface heat budget. We have produced a 13.5-year (July 1987-December 2000) dataset containing daily, monthly, and climatological surface fluxes of momentum, latent and sensible heat over the global Oceans from the Special Sensor Microwave/Imager (SSM/I) radiance easurements. This dataset is called version 2 Goddard Satellite-based Surface Turbulent Fluxes (GSSTF-2). The GSSW-2 has a spatial resolution of 1.0deg x 1.0deg lat-long. In addition, evaporation has been combined with the satellite-retrieved precipitation to produce monthly freshwater fluxes over the global Ocean for the same period. Daily turbulent fluxes are derived from the S S M surface winds and surface air humidity, and 2-m air and sea surface temperatures (SST) of the NCEP/NCAR reanalysis, using an improved stability-dependent bulk flux algorithm based on the surface layer similarity theory. Hourly fluxes computed from the GSSTF-2 bulk flux algorithm using the observed hourly input variables validate well against those of ten experiments observed by the research ships over the tropical and midlatitude oceans. In addition, daily wind stresses, latent heat fluxes, wind speeds, surface air humidity and SSTs of the GSSTF-2 compare reasonably well with those of the collocated in situ measurements of the ten experiments. The global distributions of 1988-2000 annual- and seasonal-mean turbulent fluxes show reasonable patterns related to the atmospheric general circulation and its seasonal variations. The comparison of zonally-averaged wind stress and latent heat fluxes of the GSSTF-2 with those of other satellite products as well as the NCEPNCAR and ECMWF reanalyses for the annual mean and seasonal variations during 1992-93 will be discussed. .

Chou, Shu-Hsien↗

Understanding the Origin of Irreversible Capacity loss in Non-Carbonized Carbonate - based Metal Organic Framework (MOF) Sulfur hosts for Lithium - Sulfur battery

Li-Sulfur (Li-S) batteries are emergent next-generation energy storage devices due to their very high specific energy density (~2567 Wh g -1 ) but are limited by polysulfide dissolution issues. In this paper, chemically synthesized sulfur containing non-carbonized metal organic framework (S-MOF) cathodes show initial specific capacities of 1476 mAh g -1 stabilizing at ~609 mAh g -1 with almost no fade for over 200 cycles. Post-cycled separators of the S – MOF cathodes display complete absence of polysulfides after cycle 1, 20 and 200, respectively. It was identified that the occurrence of carbonate species in the MOF structure resulted in the formation of C-S bonded species causing retention of polysulfide at the electrode surface ensuring long-term stability. However, this observed capacity drop during the first 10 cycles is attributed to the oxidation of some of the infiltrated sulfur by the MOF as determined by electrochemical and X-ray photoelectron spectroscopy (XPS) analyses. Nevertheless, the negligible fade rate (0.0014% cycle -1 ) and complete prevention of polysulfide dissolution renders these cathodes most promising candidates for Li-S batteries. Finally, understanding of this transformation behavior in sulfur-containing MOF is essential to engineer chemically-bonded host-structures capable of efficient polysulfide trapping, a key pathway to establishing novel platforms for achieving high power Li – S batteries.

25 ENERGY STORAGE↗

Investigating the Performance of the Jason-2/OSTM Radar Altimeter Over Lakes and Reservoirs

Many inland water investigations utilize archival and near-real time radar altimetry data to enable observation of the variation in surface water level. A multi-altimeter approach allows a more global outlook with improved spatial resolution, and combined long-term observations improve statistical analyses. Central to all programs is a performance assessment of each instrument. Here, we focus on data quantity and quality pertaining to the Poseidon-3 radar altimeter onboard the Jason-2/OSTM satellite.Utilizing an interim data set (IGDR), studies show that the new on-board DIODE/median and DIODE/DEM tracking modes are performing well, acquiring and maintaining the majority of lake and reservoir surfaces in varying terrains. The 20-Hz along-track resolution of the data, and particularly the availability of the range output from the ice-retracker algorithm, also improves the number of valid height measurements. Based on test-case lakes and reservoirs, output from the ice-retracker algorithm is also seen to have a clear advantage over the ocean-retracker having better height stability across calm and icy surfaces, a greater ability to gain coastline waters, and less sensitivity to loss of water surface when there is island contamination in the radar echo. Such on-board tracking and postprocessing retracking enables the lake waters to be quickly gained after coastline crossing. Values can range from <0.1 s to 2.5 s, but the majority of measurements are obtained in less than 0.4 s or <2.3 km from the coast. Validation exercises reveal that targets of 150 km2 surface area and 0.8 km width are able to be monitored offering greater potential to acquire lakes in the 100 C300 km2 size-category. Time series of height variations are also found to be accurate to 3 to 33 cm rms depending on target size and the presence of winter ice. These findings are an improvement over the IGDR/GDR results from the predecessor Jason-1 and TOPEX/Poseidon missions and can satisfy the accuracy requirements of both the science-related and operational lake study programs.

Birkett, C. M.↗

Thermal Stability of the Dot-in-Well Gain Medium for Photonic Crystal Surface Emitting Lasers

Self-assembled quantum dots (QDs) embedded in InGaAs quantum wells (QWs) are used as active regions for photonic-crystal surface-emitting lasers (PCSELs). An epitaxial regrowth method is developed to fabricate the dot-in-well (DWELL) PCSELs. Here, the epitaxial regrowth starts with the growth of a partial laser structure containing bottom cladding, waveguide, active region, and the photonic crystal (PC) layer. The PC layer is patterned to realize the cavity. Subsequently a top cladding layer is regrown to complete the laser structure. During the regrowth of the top cladding layer, the partial laser structure is subjected to high growth temperatures in excess of 600 °C resulting in an unintentional annealing of the active region. This annealing of the active region can alter the QDs by changing their size resulting in a blue shift in photoluminescence (PL) and narrowing PL emission. This effect results in the misaligning of the gain peak and the cavity resonance, resulting in sub-optimal lasing performance. DWELL active regions are known to have better thermal stability compared to both QDs and QWs and could be an ideal candidate for regrown PCSELs. We successfully demonstrate an optically-pumped epitaxially-regrown DWELL PCSEL with an emission wavelength of 1230 nm operating at room temperature. Furthermore, the DWELL active region shows excellent emission wavelength stability and intensity despite the high temperature regrowth process.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Interaction of Zinc Oxide Nanoparticles with Water: Implications for Catalytic Activity

Novel technological applications in catalysis and bactericidal formulation have emerged for zinc oxide (ZnO) nanoparticles owing to their ability to generate reactive oxygen species by fostering H 2 O dissociation. Rational improvement of those properties requires a mechanistic understanding of ZnO nanoparticle reactivity, which is currently lacking. In this work, we determine the structural and electronic properties of nanometer-sized ZnO, determine the binding energetics of H 2 O adsorption, and compare to an extended macroscopic surface. We show that the electronic density of states of ZnO nanoparticles is size-dependent, exhibiting a decreasing bandgap with the increase of nanoparticle diameter. The electronic states near the Fermi energy dominantly arise from O 2p states, which are spatially localized on “reactive” surface O atoms on the nanoparticle edges that are doubly coordinated. The frontier electronic states localized at the low coordinated atoms induce a spontaneous dissociation of H 2 O at the nanoparticle edges. The surface Zn and O atoms have inhomogeneous electronic and geometrical/topological properties, thus providing nonequivalent sites for dissociative and molecular H 2 O adsorption. The free energy of H 2 O binding is dominated by the electronic DFT interaction energy, which is site-dependent and correlated with the Bader charge of surface Zn atom. Entropy is found to stabilize the bound form, because the increase in the vibrational contribution is greater than the decrease in the translational and rotational contribution, whereas solvation stabilizes the unbound state. The absence of rough edges on an extended, macroscopic ZnO surface prevents spontaneous dissociation of a single H 2 O. This study underlies the importance of coupling geometrical and electronic degrees of freedom in determining the reactivity of nanoparticles and provides a simple elucidation of the superior catalytic activity of ZnO nanoparticles compared to ZnO in macroscopic forms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Active and stable Ir@Pt core–shell catalysts for electrochemical oxygen reduction

Electrochemical oxygen reduction is an important reaction for many sustainable energy technologies, such as fuel cells and metal–air batteries. Kinetic limitations of this reaction, expensive electrocatalysts, and catalyst instability, however, limit the commercial viability of such devices. Herein, we report an active Ir@Pt core–shell catalyst that combines platinum overlayers with nanostructure effects to tune the oxygen binding to the Pt surface, thereby achieving enhanced activity and stability for the oxygen reduction reaction. Ir@Pt nanoparticles with several shell thicknesses were synthesized in a scalable, inexpensive, one-pot polyol method. Electrochemical analysis demonstrates the activity and stability of the Ir@Pt catalyst, with specific and mass activities increasing to 2.6 and 1.8 times that of commercial Pt/C (TKK), respectively, after 10 000 stability cycles. Furthermore, activity enhancement of the Ir@Pt catalyst is attributed to weakening of the oxygen binding to the Pt surface induced by the Ir core.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

SiC Composite for Fuel Structure Applications

Extensive evaluation was performed to determine the suitability of using SiC composite as a boiling water reactor (BWR) fuel channel material. A thin walled SiC composite box, 10 cm in dimension by approximately 1.5 mm wall thickness was fabricated using chemical vapor deposition (CVD) for testing. Mechanical test results and performance evaluations indicate the material could meet BWR channel mechanical design requirement. However, large mass loss of up to 21% was measured in in-pile corrosion test under BWR-like conditions in under 3 months of irradiation. A fresh sister sample irradiated in a follow-up cycle under PWR conditions showed no measureable weight loss and thus supports the hypothesis that the oxidizing condition of the BWR-like coolant chemistry was responsible for the high corrosion rate. A thermodynamic evaluation showed SiC is not stable and the material may oxidize to form SiO 2 and CO 2 . Silica has demonstrated stability in high temperature steam environment and form a protective oxide layer under severe accident conditions. However, it does not form a protective layer in water under normal BWR operational conditions due to its high solubility. Corrosion product stabilization by modifying the SiC CVD surface is an approach evaluated in this study to mitigate the high corrosion rate. Titanium and zirconium have been selected as stabilizing elements since both TiSiO 4 and ZrSiO 4 are insoluble in water. Corrosion test results in oxygenated water autoclave indicate TiSiO4 does not form a protective layer. However, zirconium doped test samples appear to form a stable continuous layer of ZrSiO 4 during the corrosion process. Additional process development is needed to produce a good ZrSiC coating to verify functionality of the mitigation concept.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Studies of clusters in the gas phase and application to an understanding of transitions from gaseous to the surface and condensed state

Studies of the structure, stability, electronic properties, and formation kinetics of small clusters were reviewed which provide information useful in furthering understanding of nucleation processes, liquid state properties, and the nature of surfaces. Using mass spectrometric coupled with various high pressure ion clustering and Stark effect-molecular beam techniques, the details of the primary clustering steps leading to the nucleation of bulk liquid from the vapor were and obtained by direct observation results are presented.

Castleman, A. W., Jr.↗

Photo-Crosslinkable Naphthalene Diimide Polymer for Solution-Processed n – i – p Perovskite Solar Cells

We copolymerize a norbornene monomer bearing a pendant naphthalene diimide with a norbornene bearing a cinnamate pendant moiety to synthesize a crosslinkable electron-transporting polymer and study its use in solution-processed n–i–p perovskite solar cells. The crosslinked material exhibits over 90% transparency in the visible region and higher thermal stability (>300 °C) and lower surface energy than the corresponding homopolymer of the naphthalene diimide functionalized norbornene. Coating an ITO surface with the photo-crosslinked copolymer yields a slightly lower work function than homopolymer-coated ITO. We show that the morphologies of the perovskite films deposited on both polymers are similar (~300 nm features) based upon scanning electron microscopy. Our solar-cell device results show that the crosslinked naphthalene diimide polymer gives a higher open-circuit voltage (1.08 vs 1.05 V), fill factor (average 64.43 vs 58.77%), and stabilized power conversion efficiency (12.28 vs 10.33%) compared to its non-crosslinked homopolymer counterpart, as well as reduced hysteresis. As a result, we attribute the improved performance to decreased work function, reduced nonradiative recombination, and higher shunt resistance.

14 SOLAR ENERGY↗

Ion Beam Textured and Coated Surfaces Experiment (IBEX)

Ion beam textured and commercial materials suitable for use in space power systems were flown in low Earth orbit on the Long Duration Exposure Facility (LDEF) for 5.8 years. Because of their location on LDEF (98 deg from the ram direction), the 36 materials were primarily exposed to vacuum ultraviolet radiation, thermal cycling, the vacuum of space, the micrometeoroid environment, and grazing incidence atomic oxygen. Measurements of solar absorptance and thermal emittance (pre- and post-flight) showed no changes for almost all of the materials, except for the S-13G and Kapton and coated Kapton samples. The optical property stability of ion beam textured surfaces and most other surfaces indicates that they are functionally durable to the synergistic rigors of the space environment.

Mirtich, Michael J.↗

The Venus SAGE Atmospheric Structure Investigation

Experiment goals and objectives are: a) To accurately define the state properties as a function of altitude from below the 10(exp -4) mb level (approx.150 km) to 92 bars (surface); b) To measure the stability of the atmosphere, and identify convective layers and stable layers, where they exist; c) To detect cloud levels from changes in the lapse rate at their boundaries; d) To provide state properties within the cloud levels, and thus provide supplementary information on cloud composition; e) To search for and characterize wave structure within the atmosphere; f) To search for and measure the intensity and scale of turbulence; g) To measure descent and surface wind speed and direction; h) To provide Lander altitude and attitude during decent for descent imaging analysis; and i) To provide a back-up landing sensor.

Colaprete, Anthony↗

High-Temperature Solid Lubricant Coating

NASA PS400 is a solid lubricant coating invented for high-temperature tribological applications. This plasma-sprayed coating is a variant of the previously patented PS304 coating, and has been formulated to provide higher density, smoother surface finish, and better dimensional stability. This innovation is a new composite material that provides a means to reduce friction and wear in mechanical components. PS400 is a blend of a nickel-molybdenum binder, chrome oxide hardener, silver lubricant, and barium fluoride/calcium fluoride eutectic lubricant that can either be sprayed or deposited by other means, such as powder metallurgy. The resulting composite material is then finished by grinding and polishing to produce a smooth, self-lubricating surface.

DellaCorte, Christopher↗

Surface Chemistry, Passivation, and Electrode Performance in Core–Shell Architectures of LiCoO 2 Nanoplates

Core–shell structures offer opportunities to overcome challenges to the durability of Li-ion batteries with high energy density due to instability at the cathode/electrolyte interface. Achieving complete stability requires fundamental understanding of the role of the shell in providing passivation without compromising carrier transport, by tuning surface chemistry and structural features in a highly conformal barrier layer. Here, individual LiCoO 2 nanoplates were employed as the core, and passivating shells were grown at a tailored thickness and composition, through different Al loadings and annealing temperatures. Depending on the annealing conditions, the sub-5 nm shells were shown to vary from amorphous aluminum oxide layers to LiAl x Co 1–x O 2 gradients, resulting in an Al-rich outer layer on a Co-rich core. This control revealed the differing balance between effective minimization of redox-active Co 3+ at the surface and transport properties of the two types of shell. Based on correlations with electrode performance, the requirements in thickness of the layers were proposed to critically depend on their chemical composition, with epitaxial shells based on surface substitution being favored. As a result, the outcomes of the study simultaneously advance the ability to assemble complex oxides into heterostructures and refine the rules of design for tunable passivation through a barrier layer, so as to maximize electrode properties in practical batteries.

25 ENERGY STORAGE↗

Atomic Layer Deposition Overcoating Improves Catalyst Selectivity and Longevity in Propane Dehydrogenation

Propylene, a precursor for commodity chemicals and plastics, is produced by propane dehydrogenation (PDH). An increase in PDH yield via added catalyst activity, lifetime, or selectivity represents significant energy and economic savings. Using Pt dispersed on Al2O3 extrudate supports as a commercially relevant model system, we demonstrate that atomic layer deposition (ALD) metal oxide overcoats, used to tailor metal-active sites, can increase PDH yield and selectivity. We investigate the interplay of Pt loading, ALD overcoat thickness, and Al 2 O 3 support surface area on PDH activity, selectivity, and catalyst stability to show that applying a 6-8 A thick layer of Al 2 O 3 on low-surface area Al 2 O 3 supports of similar to 90 m 2 /g surface area yields the optimal combination of stability and activity, while increasing propylene selectivity from 91 to 96%. Increased stability upon steaming deactivation occurs because the Al 2 O 3 overcoat prevents the Pt nanoparticles from sintering. We speculate that the ALD overcoat selectively binds to the undercoordinated sites on the Pt nanoparticles, while leaving the more selective terrace sites available for dehydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗