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At least 1,567 records · Page 87

Enhanced Stability of Pt-Cu Single-Atom Alloy Catalysts: In Situ Characterization of the Pt/Cu(111) Surface in an Ambient Pressure of CO

The interaction between a catalyst and reactants often induce changes in the surface structure and composition of the catalyst, which, in turn, affect its reactivity. Therefore, it is important to study such changes using in situ techniques under well-controlled conditions. We have used ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to study the surface stability of a Pt/Cu(111) single atom alloy (SAA) in an ambient pressure of CO. By directly probing the Pt atoms, we found that CO causes a slight surface segregation of Pt atoms at room temperature. In addition, while the Pt/Cu(111) surface demonstrates poor thermal stability in UHV, where surface Pt starts to diffuse to the subsurface layer above 400 K, the presence of adsorbed CO enhances the thermal stability of surface Pt atoms. Furthermore, we also found that temperatures above 450 K cause a restructuring of the subsurface layer, which consequently strengthens the CO binding to the surface Pt sites, likely due to the presence of neighboring subsurface Pt atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characteristics and Current Status of Near Infrared Spectrometer for Hayabusa Mission

NIRS is a near infrared spectrometer on-boarded the spacecraft HAYABUSA (MUSESC), which aims to return samples from a near-earth asteroid, (25143) Itokawa (1998 SF36). HAYABUSA was successfully launched by Japanese M-V-5 rocket on May 19, 2003. After the earth swing-by in Jun 2004, the spacecraft will arrive at the asteroid in summer 2005. During the rendezvous phase with the asteroid, we will observe the asteroid surface using NIRS and obtain reflectance spectra of the surface materials across the wavelength range of 850nm to 2100nm. Based on ground-based observations [1],[2],[3], (25143) Itokawa appears to be an S(IV) type asteroid. NIRS can detect absorption bands due to olivine and pyroxene and investigate the mineralogical composition of the surface materials. Combining with the data from asteroid multiband imaging camera (AMICA) and X-ray spectrometer (XRS), we can reveal a relationship between asteroids and meteorites.

Abe, M.↗

Observations with Near Infrared Spectrometer for Hayabusa Mission in the Cruising Phase

NIRS is a near infrared spectrometer on-board the spacecraft HAYABUSA, which aims to return samples from a near-earth asteroid, 25143 Itokawa. HAYABUSA was successfully launched by Japanese M-V-5 rocket on May 9, 2003. After the successful earth swing-by on May 19, 2004, the spacecraft is now on the way toward the asteroid, where it will arrive in this summer. During the rendezvous phase with the asteroid, we will observe the asteroid surface using NIRS and obtain reflectance spectra of the surface materials across the wavelength range of 850nm to 2100nm. Based on ground-based observations [1],[2],[3], 25143 Itokawa appears to be an S(IV) type asteroid. NIRS can detect absorption bands due to olivine and pyroxene and investigate the mineralogical composition of the surface materials, and reveal a relationship between asteroids and meteorites.

Abe, M.↗

Porous thermally insulating compositions containing hollow spherical nanoparticles

A method of thermally insulating a surface, the method comprising applying a coating of a thermally insulating composition onto said surface, wherein said thermally insulating composition comprises: (i) hollow spherical nanoparticles having a mean particle size of less than 800 nm in diameter and a particle size distribution in which at least 90% of the hollow spherical nanoparticles have a size within ±20% of said mean particle size, and a first layer of cationic or anionic molecules attached to said surfaces of the hollow spherical nanoparticles; and (ii) a second layer of molecules of opposite charge to the first layer of molecules, wherein said second layer of molecules of opposite charge are ionically associated with said first layer of molecules, wherein the molecules in said second layer have at least eight carbon atoms.

36 MATERIALS SCIENCE↗

Violation of light beam reversibility principle in optical media with a random quasi-zero refractive index

We report on experimental and theoretical evidence of the violation of one of the fundamental principles in the Fresnel optics, namely, light beam reversibility, in new nanostructured composite metamaterials with silver nanoparticle in a polymer matrix. It is shown that optical transmittance of (PMMA + Ag)/glass samples in counter directions is not the same. We propose a theoretical explanation of this phenomenon based on the effect of photon localization on the surface of the composite layer with a random quasizero refractive index.

36 MATERIALS SCIENCE↗

Decomposition of Electron Ionization Mass Spectra for Space Application Using a Monte-Carlo approach

Rationale: Quadrupole mass spectrometers equipped with an electron ionization (EI) sources have been widely used in space exploration to investigate the composition of planetary surfaces and atmospheres. However, the complexity of the samples and the minimal calibration for the fragmentation of molecules in the ionization chambers have prevented the deconvolution of the majority of the mass spectra obtained at different targets, thus limiting the determination of the exact composition of the samples analyzed. We propose a Monte‐Carlo approach to solve this issue mathematically. Methods: We decomposed simulated mass spectra of mixtures acquired with unit resolving power mass spectrometers and EI sources into the sum of the single components fragmentation patterns weighted by their relative concentration using interior‐point least‐square fitting. To fit compounds with poorly known fragmentation patterns, we used a Monte‐Carlo method to vary the intensity of individual fragment ions. We then decomposed the spectrum thousands of times to obtain a statistical distribution. Results: By performing the deconvolution on a mixture of seven different molecules with interfering fragmentation patterns (H2O, O2, CH4, Ar, N2, C2H4, and C2H6) we show that this approach retrieves the mixing ratio of the individual components more accurately than regular mass spectra decomposition methods that rely on fragmentation patterns from general databases. It also provides the probability density function for each species's mixing ratio. Conclusions: By removing the solution degeneracy in the decomposition of mass spectra, the method described herein could significantly increase the scientific retrieval from archived space flight mass spectrometry data, where calibration of the ionization source is no longer an option.

Thomas Gautier↗

Simultaneous ambient pressure x-ray photoelectron spectroscopy and grazing incidence x-ray scattering in gas environments

We have developed an experimental system to simultaneously measure surface structure, morphology, composition, chemical state, and chemical activity for samples in gas phase environments. This is accomplished by simultaneously measuring x-ray photoelectron spectroscopy (XPS) and grazing incidence x-ray scattering in gas pressures as high as the multi-Torr regime while also recording mass spectrometry. Scattering patterns reflect near-surface sample structures from the nano-scale to the meso-scale, and the grazing incidence geometry provides tunable depth sensitivity of structural measurements. Scattered x rays are detected across a broad range of angles using a newly designed pivoting-UHV-manipulator for detector positioning. At the same time, XPS and mass spectrometry can be measured, all from the same sample spot and under ambient conditions. To demonstrate the capabilities of this system, we measured the chemical state, composition, and structure of Ag-behenate on a Si(001) wafer in vacuum and in O 2 atmosphere at various temperatures. These simultaneous structural, chemical, and gas phase product probes enable detailed insights into the interplay between the structure and chemical state for samples in gas phase environments. The compact size of our pivoting-UHV-manipulator makes it possible to retrofit this technique into existing spectroscopic instruments installed at synchrotron beamlines. Because many synchrotron facilities are planning or undergoing upgrades to diffraction limited storage rings with transversely coherent beams, a newly emerging set of coherent x-ray scattering experiments can greatly benefit from the concepts we present here.

47 OTHER INSTRUMENTATION↗

Investigating relationship between surface topography and emissivity of metallic additively manufactured parts

Due to the direct relationship between thermal history and mechanical behavior, in situ thermal monitoring is key in gauging quality of parts produced with additive manufacturing (AM). Accurate monitoring of temperatures in an AM process requires knowledge of environment and object parameters including object emissivity. The emissivity is dependent on several variables, including: wavelength, material composition, temperature, and surface topography. Researchers have been concerned with the thermal emissivity dependence on temperature since large ranges are seen in metal powder bed processes, but there is also an extensive range of surfaces produced by AM. This work focused on discovering what roughness characteristics control thermal emissivity through investigation of prototypic 316 stainless steel AM samples produced with a range of build conditions on a laser powder bed fusion machine. Through experimental measurements of emissivity using hemispherical directional reflectance (HDR), guided by simulations using a finite-difference time-domain (FDTD) Maxwell solver, it was found that combinations of existing roughness parameters describing both height and slope of the surface correlate well with emissivity changes. Furthermore, these parameters work well due to their apt description of surface features encouraging internal reflection, which is the phenomenon that increases emissivity when a surface falls under the geometric optical region conditions.

36 MATERIALS SCIENCE↗

Containerless, Low-Gravity Undercooling of Ti-Ce Alloys in the MSFC Drop Tube

Previous tests of the classical nucleation theory as applied to liquid-liquid gap miscibility systems found a discrepancy between experiment and theory in the ability to undercool one of the liquids before the L1-L2 separation occurs. To model the initial separation process in a two-phase liquid mixture, different theoretical approaches, such as free-energy gradient and density gradient theories, have been put forth. If there is a large enough interaction between the critical liquid and the crucible, both models predict a wetting temperature (T(sub w)) above which the minority liquid perfectly wets and layers the crucible interface, but only on one side of the immiscibility dome. Materials with compositions on the other side of the dome will have simple surface adsorption by the minority liquid before bulk separation occurs when the coexistence (i.e., binoidal) line in reached. If the interaction between the critical liquid and the crucible were to decrease, T(sub w) would increase, eventually approaching the critical consolute temperature (T(sub cc)). If this situation occurs, then there could be large regions of the miscibility gap where non-perfect wetting conditions prevail resulting in droplets of L1 liquid at the surface having a non-zero contact angle. The resulting bulk structure will then depend on what happens on the surface and the subsequent processing conditions. In the past several decades, many experiments in space have been performed on liquid metal binary immiscible systems for the purpose of determining the effects that different crucibles may have on the wetting and separation process of the liquids. Potard performed experiments that showed different crucible materials could cause the majority phase to preferentially wet the container and thus produce a dispersed microstructure of the minority phase. Several other studies have been performed on immiscibles in a semi-container environment using an emulsion technique. Only one previous study was performed using completely containerless processing of immiscible metals and the results of that investigation are similar to some of the emulsion studies. In all the studies, surface wetting was attributed as the cause for the similar microstructures or the asymmetry in the ability to undercool the liquid below the binoidal on one side of the immiscibility dome. By removing the container completely from the separation process, it was proposed that the loss of the crucible/liquid interaction would produce a large shift in T(sub w) and thus change the wetting characteristics at the surface. By investigating various compositions across the miscibility gap, a change in the type and amount of liquid wetting at the surface of a containerless droplet should change the surface nucleating behavior of the droplet - whether it be the liquid-liquid wetting or the liquid-to-solid transition. Undercooling of the liquid into the metastable region should produce significant differences in the separation process and the microstructure upon solidification. In this study, we attempt to measure these transitions by monitoring the temperature of the sample by optical pyrometry. Microstructural analysis will be made to correlate with the degree of undercooling and the separation mechanisms involved.

Robinson, M. B.↗

Synthesis of a novel multifunctional organic–inorganic nanocomposite for metal ions and organic dye removals

In this study, we used solvent assisted mechano-synthesis strategies to form multifunctional organic–inorganic nanocomposites capable of removing both organic and inorganic contaminants. A zeolite X (Ze) and activated carbon (AC) composite was synthesized via state-of-the-art mechanical mixing in the presence of few drops of water to form Ze/AC. The second composite (Ze/L/AC) was synthesized in a similar fashion, however this composite had the addition of disodium terephthalate as a linker. Both materials, Ze/AC and Ze/L/AC, were characterized using scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), Powdered X-ray diffraction (P-XRD), Fourier-transform infrared spectrometry (FTIR), Accelerated Surface Area and Porosimetry System (ASAP), and thermal gravimetric analysis (TGA). The SEM–EDS displayed the surface structure and composition of each material. The sodium, oxygen and carbon contents increased after linker connected Ze and AC. The P-XRD confirmed the crystallinity of each material as well as the composites, while FTIR indicated the function groups (C=C, O–H) in Ze/L/AC. The contaminant adsorption experiments investigated the effects of pH, temperature, and ionic strength on the adsorption of methylene blue (MB) and Co(II) for each material. In MB adsorption, the first-order reaction rate of Ze/L/AC (0.02 h -1 ) was double that of Ze/AC (0.01 h -1 ). The reaction rate of Ze/L/AC (4.8 h -1 ) was also extraordinarily higher than that of Ze/AC (0.6 h -1 ) in the adsorption of Co(II). Ze/L/AC composite achieved a maximum adsorption capacity of 44.8 mg/g for MB and 66.6 mg/g for Co(II) ions. The MB adsorption of Ze/AC and Ze/L/AC was best fit in Freundlich model with R 2 of 0.96 and 0.97, respectively, which indicated the multilayer adsorption. In the Co(II) adsorption, the data was highly fit in Langmuir model with R 2 of 0.94 and 0.92 which indicated the monolayer adsorption. These results indicated both materials exhibited chemisorption. The activation energy of Ze/L/AC in MB adsorption (34.9 kJ mol -1 ) was higher than that of Ze/L/AC in Co (II) adsorption (26 kJ mol -1 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Precision surface modification of solid oxide fuel cells via layer-by-layer surface sol–gel deposition

While solid oxide fuel cells (SOFCs) are a promising technology for a clean and sustainable future, their commercialization is hindered by limited durability and performance. Here, we report our findings on the application of a layer-by-layer surface sol–gel (SSG) coating of catalysts to dramatically enhance the electro-catalytic activity and durability of SOFC cathodes. The SSG process is capable of penetrating and preserving complex backbone microstructures of porous electrodes, creating highly conformal coatings of controlled morphology, while tailoring the composition of the surface to improve catalytic properties and durability. For example, the application of an SSG coating of PrO x to a La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3–δ (LSCF) cathode has reduced the polarization resistance from 1.136 to 0.117 Ω cm 2 at 600 °C and the degradation rate from 1.13 × 10 –3 to 2.67 × 10 –4 Ω cm 2 h –1 at 650 °C. In addition, a continuous improvement in electrode performance is demonstrated as the thickness of the coating is increased, corresponding to the linear addition of catalyst. Furthermore, this first application of the SSG technique to SOFC systems opens the door for the controlled surface modification of porous components in electrochemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Composite lithium electrode with mesoscale skeleton via simple mechanical deformation

Lithium metal–based batteries are attractive energy storage devices because of high energy density. However, uncontrolled dendrite growth and virtually infinite volume change, which cause performance fading and safety concerns, have limited their applications. In this work, we demonstrate that a composite lithium metal electrode with an ion-conducting mesoscale skeleton can improve electrochemical performance by locally reducing the current density. In addition, the potential for short-circuiting is largely alleviated due to side deposition of mossy lithium on the three-dimensional electroactive surface of the composite electrode. Moreover, the electrode volume only slightly changes with the support of a rigid and stable scaffold. Therefore, this mesoscale composite electrode can cycle stably for 200 cycles with low polarization under a high areal current density up to 5 mA/cm 2 . Most attractively, the proposed fabrication process, which only involves simple mechanical deformation, is scalable and cost effective, providing a new strategy for developing high performance and long lifespan lithium anodes.

25 ENERGY STORAGE↗

Arsenic ambient conditions preventing surface degradation of GaAs during capless annealing at high temperatures

Changes in surface morphology and composition caused by capless annealing of GaAs were studied as a function of annealing temperature, T(GaAs), and the ambient arsenic pressure controlled by the temperature, T(As), of an arsenic source in the annealing ampul. It was established that any degradation of the GaAs surface morphology could be completely prevented, providing that T(As) was more than about 0.315T(GaAs) + 227 C. This empirical relationship is valid up to the melting point temperature of GaAs (1238 C), and it may be useful in some device-processing steps.

Kang, C. H.↗

Lunar surface - Sputtering and secondary ion mass spectrometry

Laboratory and Apollo observations are combined to describe the sputtering of the lunar surface and the composition of the ejecta with special reference to O. The atmospheric inventory appears to be dominated by micrometeorite vaporization of lunar grains. Sputtering effects are observable in the local plasma due to ion ejection, in the extended atmosphere through energetic neutral ejection, and on grain surfaces through the chemical fractionation of the redoposited sputter-ejecta. Ionization of the micrometeorite-vapor also contributes to the local plasma.

Johnson, R. E.↗

Phase-Imaging with a Sharpened Multi-Walled Carbon Nanotube AFM Tip: Investigation of Low-k Dielectric Polymer Hybrids

Phase shift tapping mode scanning force microscopy (TMSFM) has evolved into a very powerful technique for the nanoscale surface characterization of compositional variations in heterogeneous samples. Phase shift signal measures the difference between the phase angle of the excitation signal and the phase angle of the cantilever response. The signal correlates to the tip-sample inelastic interactions, identifying the different chemical and/or physical property of surfaces. In general, the resolution and quality of scanning probe microscopic images are highly dependent on the size of the scanning probe tip. In improving AFM tip technology, we recently developed a technique for sharpening the tip of a multi-walled carbon nanotube (CNT) AFM tip, reducing the radius of curvature of the CNT tip to less than 5 nm while still maintaining the inherent stability of multi-walled CNT tips. Herein we report the use of sharpened (CNT) AFM tips for phase-imaging of polymer hybrids, a precursor for generating nanoporous low-k dielectrics for on-chip interconnect applications. Using sharpened CNT tips, we obtained phase-contrast images having domains less than 10 nm. In contrast, conventional Si tips and unsharpened CNT tips (radius greater than 15 nm) were not able to resolve the nanoscale domains in the polymer hybrid films. C1early, the size of the CNT tip contributes significantly to the resolution of phase-contrast imaging. In addition, a study on the nonlinear tapping dynamics of the multi-walled CNT tip indicates that the multi-walled CNT tip is immune to conventional imaging instabilities related to the coexistence of attractive and repulsive tapping regimes. This factor may also contribute to the phase-contrast image quality of multi-walled CNT AFM tips. This presentation will also offer data in support of the stability of the CNT tip for phase shift TMSFM.

Nguyen, Cattien V.↗

Laser Time-of-Flight Mass Spectrometry for Future In Situ Planetary Missions

Laser desorption/ionization time-of-flight mass spectrometry (LD-TOF-MS) is a versatile, low-complexity instrument class that holds significant promise for future landed in situ planetary missions that emphasize compositional analysis of surface materials. Here we describe a 5kg-class instrument that is capable of detecting and analyzing a variety of analytes directly from rock or ice samples. Through laboratory studies of a suite of representative samples, we show that detection and analysis of key mineral composition, small organics, and particularly, higher molecular weight organics are well suited to this instrument design. A mass range exceeding 100,000 Da has recently been demonstrated. We describe recent efforts in instrument prototype development and future directions that will enhance our analytical capabilities targeting organic mixtures on primitive and icy bodies. We present results on a series of standards, simulated mixtures, and meteoritic samples.

Getty, S. A.↗

Effect of nanosized titania on the structure and properties of the composites based on butadienenitrile rubber

Nanocomposites based on butadienenitrile rubber (butadiene copolymer with 28% acrylonitrile) with functional titania nanoparticles of different nature have been obtained, and their complex study by X-ray diffractometry, small-angle X-ray scattering, scanning electron microscopy, electron probe X-ray microanalysis, and X-ray energy-dispersive spectroscopy has been performed. Differences in the morphology and composition of the surface and transverse cuts of nanocomposites in dependence of nanoparticle characteristics are established. It is found that the nanocomposites with the largest crystallite sizes have the lowest viscosity. It is also revealed that the nature of titania nanoparticles barely affects the vulcanization kinetics, and that the optimal vulcanization time for the composites is 25 min. Uniaxial extension tests have shown that nanocomposites with the best properties can be fabricated by introducing amorphous titania into the polymer (butadienenitrile rubber).

36 MATERIALS SCIENCE↗

Spatio-temporal ablation dynamics and plasma chemistry of aluminum induced by temporally modulated ytterbium fiber laser

Here, in this work, we studied single-pulse ablation dynamics of a temporally modulated continuous wave laser-material interaction with Al using in situ multimodal time-resolved diagnostics that describe in detail the associated physical and chemical processes. Time-resolved scattering, emission imaging, and optical emission spectroscopy unveiled a sequence of events spread out across three distinct phases: (i) early phase ablation process, associated with particle generation and liquid Al column formation (<20 μs), (ii) secondary detonation when sufficient ejected material is accumulated over the surface (20-50 μs), and (iii) molten liquid Al pool oscillation on the surface, followed by large droplet ejection from the liquid pool (100-500 μs). Atomic Al and AlO were observed with optical emission spectroscopy at different ratios during the entire lifetime of the event, verifying the formation of oxidized Al vapor upon its interaction with air. Morphological and compositional characterization confirmed surface oxidation and material re-solidification in the form of protrusions produced during the irradiation process. This work provides insights into the complex physical and chemical mechanisms of single-pulse ablation in the sub-millisecond laser pulse regime, which are critically important for parameter optimization in a variety of laser processing, microfabrication, and deposition applications.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗