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At least 811 records · Page 45

Hydrophobicity control by a supercritical drying technique in a sol–gel process with hybrid materials

Highlights: • Sol–gel route is combined with polymerization without using modifier. • Supercritical drying control is the key to obtain super-hydrophobic surfaces. • The whole fabrication is technologically controllable and with low costs. • The production rate is higher than 90%. • The method provides a cost-effective way for industry applications. - Abstract: We successfully synthesized one type of cheap super-hydrophobic hybrid porous materials in a sol–gel process. In this route, hydrophilic polymers and TEOS-base sol are used as precursors, the ultraviolet ray-initiated polymerization and supercritical fluid drying techniques are combined together to fulfill this task. All fabricated samples exhibit lotus-leaf-like surface structures with super-hydrophobicity. The underlying mechanisms are carefully investigated using a field-emission scanning electron microscopy (FESEM) and an X-ray photoelectron spectroscopy (XPS). We found that a well-controlled drying process is crucial to the formation of such super-hydrophobic surfaces. As high as 90% production rate is obtained in our route and thus, it might provide a cost-effective way to produce super-hydrophobic hybrid materials for industry applications.

36 MATERIALS SCIENCE↗

Unravelling the Correlation of Electronic Structure and Carrier Dynamics in CuInS 2 Nanoparticles

Here, we report the direct correlation of photoinduced carrier dynamics and electronic structure of CuInS 2 (CIS) nanoparticles (NPs) using the combination of multiple spectroscopic techniques including steady-state X-ray absorption spectroscopy (XAS), optical transient absorption (OTA), and X-ray transient (XTA) absorption spectroscopy. XAS results show that CIS NPs contain a large amount of surface Cu atoms with << four-coordination, which is more severe in CIS NPs with shorter nucleation times, indicating the presence of more Cu defect states in CIS NPs with smaller size particles. Using the combination of OTA and XTA spectroscopy, we show that electrons are trapped at states with mainly In or S nature while holes are trapped in sites characteristic of Cu. While there is no direct correlation of ultrafast trapping dynamics with NP nucleation time, charge recombination is significantly inhibited in CIS NPs with larger particles. These results suggest the key roles that Cu defect sites play in carrier dynamics and imply the possibility to control the carrier dynamics by controlling the surface structure at the Cu site in CIS NPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning the hydrogenation of CO 2 to CH 4 over mechano-chemically prepared palladium supported on ceria

CO 2 methanation reactivity, reaction mechanism, and surface structure were investigated on a mechanochemically prepared Pd/CeO 2 catalyst (PdAcCeO 2 -M), where an oxidative pretreatment (-o) increased methane yield by a factor of two compared to a reductive pretreatment (-h). Methanation rates were maintained for over 48 h and further increased upon oxidative regeneration treatments. The surface species of both PdAcCeO 2 -M-o and PdAcCeO 2 -M-h were explored via in situ CO 2 and CO hydrogenation DRIFTS, where CO hydrogenation effectively models the dissociative CO 2 mechanism (CO 2 → CO → CH 4 ). PdAcCeO 2 -M-o yielded distinct Pd-CO adsorption and the absence of monodentate carbonate at ~ 1400 cm -1 , while AP-XPS showed that PdAcCeO 2 -M-o yielded a unique Pd δ+ contribution at 335.9 eV. By gaining insights from various in situ spectroscopic techniques, and by breaking the CO 2 hydrogenation mechanism into piecewise steps, a deeper understanding of the direct CO 2 reduction towards methane and CO over mechanochemically prepared Pd/CeO 2 catalysts was obtained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Soft X-ray absorption spectroscopy investigation of the surface chemistry and treatments of copper indium gallium diselenide (CIGS)

The surface and near surface structure of copper-indium-gallium-selenide (CIGS) absorber layers is integral to the producing a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigates the effects of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces as normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (<19%). The results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.

14 SOLAR ENERGY↗

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↗