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At least 847 records · Page 47

High-indexed Pt 3 Ni alloy tetrahexahedral nanoframes evolved through preferential CO etching

Here, chemically controlling crystal structures in nanoscale is challenging, yet provides an effective way to improve catalytic performances. Pt-based nanoframes are a new class of nanomaterials that have great potential as high-performance catalysts. To date, these nanoframes are formed through acid etching in aqueous solutions, which demands long reaction time and often yields ill-defined surface structures. Herein we demonstrate a robust and unprecedented protocol for facile development of high-performance nanoframe catalysts using size and crystallographic facet-controlled PtNi 4 tetrahexahedral nanocrystals prepared through a colloidal synthesis approach as precursors. This new protocol employs the Mond process to preferentially dealloy nickel component in the <100> direction through carbon monoxide etching of carbon-supported PtNi 4 tetrahexahedral nanocrystals at an elevated temperature. The resultant Pt 3 Ni alloy tetrahexahedral nanoframes possess an open, stable, and high-indexed microstructure, containing a segregated Pt thin layer strained to the Pt–Ni alloy surfaces and featuring a down-shift d-band center as revealed by the density functional theory calculations. These nanoframes exhibit much improved catalytic performance, such as high stability under prolonged electrochemical potential cycles, promoting direct electro-oxidation of formic acid to carbon dioxide and enhancing oxygen reduction reaction activities. Because carbon monoxide can be generated from the carbon support through thermal annealing in air, a common process for pretreating supported catalysts, the developed approach can be easily adopted for preparing industrial scale catalysts that are made of Pt–Ni and other alloy nanoframes.

36 MATERIALS SCIENCE↗

Scanning Tunneling Microscopy methods for spectroscopic imaging of subsurface interfaces

A new method for spatially-resolved, spectroscopic investigation of subsurface interface structure has been developed. The method, Ballistic Electron Emission Microscopy (BEEM), is based on Scanning Tunneling Microscopy (STM) techniques. BEEM combines STM vacuum tunneling with unique ballistic electron spectroscopy capabilities. BEEM enables, for the first time, direct imaging of subsurface interface electronic properties with nanometer spatial resolution. STM topographic images of surface structure and BEEM images of subsurface properties are obtained simultaneously. BEEM capabilities are demonstrated by investigation of important metal-semiconductor interfaces.

Bell, L. D.↗

Solar Array Arcing in LEO How Much Charge is Discharged?

It is often said that only the solar array or spacecraft surface that can be reached by an arc plume are discharged in a solar array arc in LEO (Low Earth Orbit). We present definitive results from ground test experiments done in the National Plasma Interactions (N-PI) facility at the NASA Glenn Research Center that this idea is mistaken. All structure surfaces in contact with the surrounding plasma and connected to spacecraft ground are discharged, whether the arc plasma can reach them or not. Implications from the strength and damaging effects of areas on LEO spacecraft are discussed, and mitigation techniques are proposed.

Ferguson, D. C.↗

Elastic wave analyzer for icy sub-surfaces (EWAIS) in the solar system

The sub-surface structures of water-bearing icy worlds (e.g., Europa, Enceladus, and Titan) and the structures of icy regions on Mars contain critical information about their origin and evolution. These bodies have been identified as high-priority targets in the NRC Planetary Science Decadal Survey, which noted a lack of technology readiness as one impediment to related missions. An Elastic Wave Analyzer for Icy Sub-surfaces (EWAIS) instrument is being developed to acquire data that can provide answers to fundamental science questions related to these bodies. The EWAIS instrument generates and receives elastic waves using an array of piezoelectric transducers capable of operating at temperatures as low as 30K. A developed breadboard acquires reflected signals from discontinuities in the traveled materials’ impedance (the product of wave velocity and density) along the wave path. Analysis of the acquired data can be used to determine the elastic properties, presence of cracks, locations of cavities and other discontinuities, as well as the thicknesses of ice and liquid layers. The EWAIS instrument is being developed with a novel dual-frequency transmitter array that will enable reaching distances of kilometers through ice, as well as resolving smaller acoustic reflectors nearer the EWAIS instrument. The selected dual frequencies correspond to two depth ranges that can be analyzed, with resolutions of tens of centimeters in the region of tens to hundreds of meters and tens of meters on the kilometers scale, respectively. The EWAIS will be applicable for operation from any in-situ platform, including surface assets (e.g., lander and rover) and sub-surface assets (e.g., melting probes).

Bar-Cohen, Y.↗

Growth temperature effect on the structural and magnetic properties of Fe{sub 3}O{sub 4} films grown by the self-template method

We have investigated the effect of growth temperature on the structure, surface morphology, and magnetic properties of Fe{sub 3}O{sub 4} thin films grown on SrTiO{sub 3}(001) substrates by a self-template method. To eliminate the intermixing of (001) and (111) orientations that usually occurs in spinel films grown on perovskite substrates, a thin self-template layer of (001)-oriented Fe{sub 3}O{sub 4} was deposited on a SrTiO{sub 3}(001) substrate at 400 °C prior to the main film growth at temperatures of up to 1100 °C. Increasing the growth temperature from 400 °C to 1100 °C resulted in greatly improved crystallinity of the Fe{sub 3}O{sub 4} thin films, with the rocking curve width dropping from 1.41° to 0.28°. Surface analysis by atomic force microscopy showed that raising the growth temperature increased the grain size and the surface roughness, ultimately leading to the formation of regular nanopyramid arrays at 1100 °C. The surface roughening and pyramid formation are caused by the dominance of the lowest surface energy spinel (111) crystal facet. The nanopyramids were fully relaxed but still perfectly (001)-oriented in the out-of-plane direction. The largest pyramids had the lowest coercivity due to a reduction of the demagnetization effect.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Asteroid (90) Antiope: Another Icy Member of the Themis Family?

Many members of the Themis family show evidence of hydration in the form of oxidized iron in phyllosilicates (Florczak, M. et al. [1999]. Astron. Astrophys. Suppl. Ser. 134, 463–471), and OH-bearing minerals (Takir, D., Emery, J.P. [2012]. Icarus 219, 641–654). The largest member, (24) Themis, has H2O ice covering its surface (Campins, H. et al. [2010]. Nature 464, 1320–1321; Rivkin, A.S., Emery, J.P. [2010]. Nature 464, 1322–1323). We have investigated the second largest Themis-family asteroid, (90) Antiope, which Castillo-Rogez and Schmidt (Castillo-Rogez, J.C., Schmidt, B.E. [2010]. Geophys. Res. Lett. 37, L10202) predict to have a composition that includes water ice and organics. We obtained 2–4-lm spectroscopy of (90) Antiope in 2006 and 2008, and we find an absorption in the 3-lm region clearly present in our 2008 spectrum and likely in our 2006 spectrum. Both spectra have rounded, bowl-shaped absorptions consistent with those ascribed to water ice as in the spectrum of Asteroid (24) Themis. We also present and compare Spitzer 8–12-lm mid-infrared spectra of (24) Themis and (90) Antiope. We find that (90) Antiope is lacking a ‘‘fairy castle’’ dusty surface, which is in contrast to (24) Themis, other Themis family members (Licandro, J. et al. [2012]. Astron. Astrophys. 537, A73), and Jupiter Trojans (e.g. Emery, J.P., Cruikshank, D.P., Van Cleve, J. [2006]. Icarus 182, 496–512). We conclude that the surface structure of (90) Antiope is most similar to Cybele Asteroid (121) Hermione (Hargrove, K.D. et al. [2012]. Icarus 221, 453–455).

Asteroids↗

Effect of High-Dose Carbon Implantation on the Phase Composition, Morphology, and Field-Emission Properties of Silicon Crystals

The study of high-dose carbon-ion implantation without post-process annealing reveals significant modification of the morphology, surface-layer phase composition, and field-emission properties of silicon wafers. The effect of the electrical conductivity type on the evolution of the silicon-crystal surface morphology, upon a variation in the irradiation dose, and a high content of diamond-like phases in the region of microprotrusions at the maximum dose regardless of the electrical conductivity type are found. It is demonstrated that the high-dose implantation of carbon in silicon wafers with a pre-structured surface increases the maximum density of field-emission currents by more than two orders of magnitude.

36 MATERIALS SCIENCE↗

Tritium diffusion and formation in the bulk and defective surface of γ-LiAlO2 pellets: First-principles investigation

In tritium-producing burnable absorber rods (TPBAR), γ-LiAlO2 is used in the form of an annular ceramic pellet enriched with the 6Li isotope. When irradiated in a pressurized water reactor (PWR), the <sup>6</sup>Li pellets absorb neutrons and produce tritium (<sup>3</sup>H) through <sup>6</sup>Li + n <sup>3</sup>H + α. The 3H chemically reacts with the metal getter where it is captured and leads to formation of a metal hydride. For TPBARs to enable effective tritium production in PWRs, we investigated the <sup>3</sup>H diffusion pathways in the bulk and surface of γ-LiAlO<sub>2</sub> with different concentrations of lithium defects. The calculated results for bulk and low-index surfaces, thermal conductivity, 3H activation energy barriers, and the 3H diffusion coefficients in γ-LiAlO<sub>2</sub> are in good agreement with the available experimental values. In the bulk, our results show that the smallest activation energy barrier is 0.63 eV for substitutional <sup>3</sup>H diffusion with a diffusion coefficient of 3.25x10<sup>-12</sup> m<sup>2</sup>/s. After <sup>3</sup>H diffused from bulk to the surface, it could form different species (such as <sup>3</sup>H<sub>2</sub>, <sup>3</sup>H<sub>2</sub>O, C<sup>3</sup>H<sub>4</sub>) depending on the surface structure, vacancy types and the impurity carbon. Our results indicate that the <sup>3</sup>H<sub>2</sub> is the main product from γ-LiAlO<sub>2</sub> pellets. As the number of V<sub>Li</sub> vacancies and <sup>3</sup>H atoms increases under irradiation (<sup>3</sup>H-rich condition), <sup>3</sup>H<sub>2</sub>O release could increase from the surface of γ-LiAlO<sub>2</sub> pellets.

Jia, Ting↗

Evidence for Subauroral Electric Fields from IMAGE EUV

The IMAGE Mission Extreme Ultraviolet Imager routinely provides global snapshots of the plasmasphere from high latitude. In these 10-minute images, intensity edges have been identified with the plasmapause and other strong gradients in plasmaspheric density. In addition to the classic sunward directed convection tail and its entrainment in corotation during storm-time recovery, the plasmapause boundary reveals a wide variety of structures thought to result from penetration of the solar wind induced convection electric field to subauroral latitudes. The so-called shoulder feature has most prominently been discussed in the context of under shielding in response to changes in the convection electric field strength. It is not yet clear whether all of the observed surface structures on the plasmasphere can be explained in this manner. The types of structures observed and their frequency of occurrence will be presented. A statistical view of these structures and associated solar wind conditions will also be presented.

Six, N. Frank↗

Fundamental Studies of Crystal Growth of Microporous Materials

Microporous materials are framework structures with well-defined porosity, often of molecular dimensions. Zeolites contain aluminum and silicon atoms in their framework and are the most extensively studied amongst all microporous materials. Framework structures with P, Ga, Fe, Co, Zn, B, Ti and a host of other elements have also been made. Typical synthesis of microporous materials involve mixing the framework elements (or compounds, thereof) in a basic solution, followed by aging in some cases and then heating at elevated temperatures. This process is termed hydrothermal synthesis, and involves complex chemical and physical changes. Because of a limited understanding of this process, most synthesis advancements happen by a trial and error approach. There is considerable interest in understanding the synthesis process at a molecular level with the expectation that eventually new framework structures will be built by design. The basic issues in the microporous materials crystallization process include: (a) Nature of the molecular units responsible for the crystal nuclei formation; (b) Nature of the nuclei and nucleation process; (c) Growth process of the nuclei into crystal; (d) Morphological control and size of the resulting crystal; (e) Surface structure of the resulting crystals; and (f) Transformation of frameworks into other frameworks or condensed structures.

Singh, Ramsharan↗

Structural analysis of bioceramic materials for denture application

Structural analysis has been performed on bioceramic materials for denture application by using X-ray diffraction (XRD), X-ray fluorescence (XRF), and Scanning Electron Microscopy (SEM). XRF is using for analysis chemical composition of raw materials. XRF shows the ratio 1 : 1 : 1 : 1 between feldspar, quartz, kaolin and eggshell, respectively, resulting composition CaO content of 56.78 %, which is similar with natural tooth. Sample preparation was carried out on temperature of 800 °C, 900 °C and 1000 °C. X-ray diffraction result showed that the structure is crystalline with trigonal crystal system for SiO{sub 2} (a=b=4.9134 Å and c=5.4051 Å) and CaH{sub 2}O{sub 2} (a=b=3.5925 Å and c=4.9082 Å). Based on the Scherrer’s equation showed the crystallite size of the highest peak (SiO{sub 2}) increase with increasing the temperature preparation. The highest hardness value (87 kg/mm{sup 2}) and match with the standards of dentin hardness. The surface structure was observed by using SEM also discussed.

36 MATERIALS SCIENCE↗

Effect of Cationic (Na + ) and Anionic (F – ) Co-Doping on the Structural and Electrochemical Properties of LiNi 1/3 Mn 1/3 Co 1/3 O 2 Cathode Material for Lithium-Ion Batteries

Elemental doping for substituting lithium or oxygen sites has become a simple and effective technique to improve the electrochemical performance of layered cathode materials. Compared with single-element doping, this work presents an unprecedented contribution to the study of the effect of Na + /F – co-doping on the structure and electrochemical performance of LiNi 1/3 Mn 1/3 Co 1/3 O 2 . The co-doped Li 1-z Na z Ni 1/3 Mn 1/3 Co 1/3 O 2-z F z (z = 0.025) and pristine LiNi 1/3 Co 1/3 Mn 1/3 O 2 materials were synthesized via the sol–gel method using EDTA as a chelating agent. Structural analyses, carried out by X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy, revealed that the Na + and F – dopants were successfully incorporated into the Li and O sites, respectively. The co-doping resulted in larger Li-slab spacing, a lower degree of cation mixing, and the stabilization of the surface structure, which substantially enhanced the cycling stability and rate capability of the cathode material. The Na/F co-doped LiNi 1/3 Mn 1/3 Co 1/3 O 2 electrode delivered an initial specific capacity of 142 mAh g –1 at a 1C rate (178 mAh g –1 at 0.1C), and it maintained 50% of its initial capacity after 1000 charge–discharge cycles at a 1C rate.

25 ENERGY STORAGE↗

Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer

The main challenge for gas storage and separation in nanoporous materials is that many molecules of interest adsorb too weakly to be effectively retained. Instead of synthetically modifying the internal surface structure of the entire bulk—as is typically done to enhance adsorption—here we show that post exposure of a prototypical porous metal-organic framework to ethylenediamine can effectively retain a variety of weakly adsorbing molecules (for example, CO, CO 2 , SO 2 , C 2 H 4 , NO) inside the materials by forming a monolayer-thick cap at the external surface of microcrystals. Furthermore, this capping mechanism, based on hydrogen bonding as explained by ab initio modelling, opens the door for potential selectivity. For example, water molecules are shown to disrupt the hydrogen-bonded amine network and diffuse through the cap without hindrance and fully displace/release the retained small molecules out of the metal-organic framework at room temperature. Lastly, these findings may provide alternative strategies for gas storage, delivery and separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Rotation on Internal Structure and Dynamics of Main-Sequence Stars

Current state-of-the-art computer simulations allow us to build 3D dynamical and radiative models of stars from physical first principles with a high degree of realism. The radiative 3D dynamical stellar models obtained with the StellarBox code take into account the effects of turbulence, stellar abundances, a realistic equation of state, and radiative energy transport. In this talk, I will discuss the effects of rotation on the turbulent dynamics and surface structure for a 1.47Msun star for rotational periods of 1 and 14 days. The simulations are performed with the computational domain at various latitudes. The models reproduce stellar granulation, the subsurface shear layer, structural changes in convection, and the tachocline, which is the interface between the inner radiative zone and the outer convection zone and plays a crucial role in stellar variability. In particular, the model results reveal the formation of differential rotation and meridional circulation.

SMD↗

The TriBeam system: Femtosecond laser ablation in situ SEM

Femtosecond laser ablation offers the unique ability to remove material at rates that are orders of magnitude faster than existing ion beam technologies with little or no associated damage. By combining ultrafast lasers with state-of-the-art electron microscopy equipment, we have developed a TriBeam system capable of targeted, in-situ tomography providing chemical, structural, and topographical information in three dimensions of near mm{sup 3} sized volumes. The origins, development, physics, current uses, and future potential for the TriBeam system are described in this tutorial review. - Graphical abstract: Display Omitted - Highlights: • An emerging tool, the TriBeam, for in situ femtosecond (fs) laser ablation is presented. • Fs laser ablation aided tomography at the mm{sup 3}-scale is demonstrated. • Fs laser induced deposition of Pt is demonstrated at sub-diffraction limit resolution. • Fs laser surface structuring is reviewed as well as micromachining applications.

36 MATERIALS SCIENCE↗

Single-Molecule Interfacial Electron Transfer

Interfacial electron transfer (ET) plays an important role in many chemical and biological processes. Specifically, interfacial ET in TiO 2 -based systems is important to solar energy technology, catalysis, and environmental remediation technology. However, the microscopic mechanism of interfacial ET is not well understood with regard to atomic surface structure, molecular structure, bonding, orientation, and motion. In this project, we used two complementary methodologies; single-molecule fluorescence spectroscopy, and scanning-tunneling microscopy and spectroscopy (STM and STS) to address this scientific need. The goal of this project was to integrate these techniques and measure the molecular dependence of ET between adsorbed molecules and TiO 2 semiconductor surfaces and the ET induced reactions such as the splitting of water. The scanning probe techniques, STM and STS, are capable of providing the highest spatial resolution but not easily time-resolved data. Single-molecule fluorescence spectroscopy is capable of good time resolution but requires further development to match the spatial resolution of the STM. The integrated approach involving Peter Lu at Bowling Green State University (BGSU) and Wilson Ho at the University of California, Irvine (UC Irvine) produced methods for time and spatially resolved chemical imaging of interfacial electron transfer dynamics and photocatalytic reactions. An integral aspect of the joint research was a significant exchange of graduate students to work at the two institutions. This project bridged complementary approaches to investigate a set of common problems by working with the same molecules on a variety of solid surfaces, but using appropriate techniques to probe under ambient (BGSU) and ultrahigh vacuum (UCI) conditions. The molecular level understanding of the fundamental interfacial electron transfer processes obtained in this joint project will be important for developing efficient light harvesting, solar energy conversion, and broadly applicable to problems in interface chemistry and surface physics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Role of clay-associated humic substances in catalyzing bioreduction of structural Fe(III) in nontronite by Shewanella putrefaciens CN32

Previous studies have shown that humic substances can serve as electron shuttle to catalyze bioreduction of structural Fe(III) in clay minerals, but it is unclear if clay-sorbed humic substances can serve the same function. It is unknown if the electron shuttling function is dependent on electron donor type and if humic substances undergo change as a result. Here, humic acid (HA) and fulvic acid (FA) were sorbed onto nontronite (NAu-2) surface. Structural Fe(III) in HA- and FA-coated NAu-2 samples was bioreduced by Shewanella putrefaciens CN32 using H 2 and lactate as electron donors. The results showed a contrasting effect of humic substances on bioreduction of structural Fe(III), depending on the electron donor type. With H 2 as electron donor, humic substances had little effect on bioreduction of Fe(III) (the reduction extent: 26.2%, 27.4%, 29.3% for HA-coated, FA-coated, and uncoated NAu-2, respectively). In contrast, these substances significantly enhanced bioreduction of Fe(III) with lactate as electron donor (the reduction extent: 20.2%, 20.7%, 11.5% for HA-coated, FA-coated, and uncoated NAu-2, respectively). This contrasting behavior is likely caused by the difference in reaction free energy and electron transport process between H 2 and lactate. When H 2 served as electron donor, more energy was released than when lactate served as electron donor. In addition, because of different cellular locations of lactate dehydrogenase (inner membrane) and H 2 hydrogenase (the periplasm), electrons generated by H 2 hydrogenase may pass through the electron transport chain more rapidly than those generated from lactate dehydrogenase. Through their functions as electron shuttle and/or carbon source, clay-sorbed HA/FA underwent partial transformation to amino acids and other compounds. The availability of external carbon source played an important role in the amount and type of secondary product generation. These results have important implications for coupled iron and carbon biogeochemical cycles in clay- and humic substance-rich environments.

54 ENVIRONMENTAL SCIENCES↗

Quantitative investigations of geologic surfaces utilizing airborne visible/infrared imaging spectrometer (AVIRIS) and polarimetric radar (AIRSAR) data for Death Valley, California

Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) and polarimetric radar (AIRSAR) data were collected over Death Valley, California, USA, in September 1989. These two data sets were used to quantitatively characterize both the mineralogy and surface structure of the valley floor. Field mapping and characterization of the salt flats across the valley identified 16 separate units. The AVIRIS data were calibrated using the 'empirical line' method, and spectra extracted for the 16 units. A water vapor map was generated from the AVIRIS data and showed spatial variations in its distribution due to evaporation of surface water. Unmixing of the 16 spectral units produced maps of endmember abundance.

Kierein-Young, Kathryn S.↗