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At least 343 records · Page 19

Alteration of pool boiling heat transfer on metallic surfaces by in situ oxidation

The critical heat flux during pool boiling has been investigated for a range of applications including electrical power generation and thermal management. Reported experimental CHF values during pool boiling of water on flat metallic surfaces, however, show a large discrepancy across studies. Here, we address this discrepancy in CHF values by accounting for oxidation of metallic surfaces during boiling. We studied the effect of in situ oxidation on flat Cu and Ni surfaces by changing the duration that samples were held in saturated water before conducting boiling experiments. The morphology and chemical composition of surfaces after the boiling experiments were analyzed by atomic force microscopy and X-ray photoelectron spectroscopy, respectively. Cu surfaces showed gradually increasing CHF values as the duration in saturated water increased, which could be attributed to the increase in roughness due to the formation of Cu 2 O nanostructures. Conversely, Ni surfaces showed relatively stable CHF and morphology as a nearly flat layer of NiO formed, with one exception: formation of a highly wetting hydroxide, Ni(OH) 2 , on a Ni coupon held in saturated water for 24 h resulted in a uniquely high CHF value, signifying the importance of surface chemistry in addition to morphology. Finally, the fundamental mechanisms resulting in the wide spread of CHF values on metallic surfaces elucidated in this work will lead to more accurate estimation of CHF as well as a deeper mechanistic understanding of CHF values on engineered surfaces.

42 ENGINEERING↗

Improving Rare-Earth Mineral Separation with Insights from Molecular Recognition: Functionalized Hydroxamic Acid Adsorption onto Bastnäsite and Calcite

Enhancing the separation of rare-earth elements (REEs) from gangue materials in mined ores requires an understanding of the fundamental interactions driving the adsorption of collector ligands onto mineral interfaces. In this work, we examine five functionalized hydroxamic acid ligands as potential collectors for the REE-containing bastnäsite mineral in froth flotation using density functional theory calculations and a suite of surface-sensitive analytical spectroscopies. These include vibrational sum frequency generation, attenuated total reflectance Fourier transform infrared, Raman, and X-ray photoelectron spectroscopies. Differences in the chemical makeup of these ligands on well-defined bastnäsite and calcite surfaces allow for a systematic relationship connecting the structure to adsorption activity to be framed in the context of interfacial molecular recognition. Here we show how the intramolecular hydrogen bonding of adsorbed ligands requires the inclusion of explicit water solvent molecules to correctly map energetic and structural trends measured by experiments. We anticipate that the results and insights from this work will motivate and inform the design of improved flotation collectors for REE ores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atmospheric and surface properties of Mars obtained by infrared spectroscopy on Mariner 9

The infrared spectroscopy experiment on Mariner 9 obtained data over much of Mars. Interpretation of the thermal emission of Mars in terms of atmospheric temperatures, wind fields and dynamics, surface temperatures, surface pressure and topography, mineral composition, and minor atmospheric constituents including isotopic ratios, as well as a search for unexpected phenomena are reported.

Conrath, B.↗

Anisotropic surface state in a topological semimetal candidate Ta 3 SiTe 6

Using high-resolution angle-resolved photoemission spectroscopy, we studied the surface state of Ta 3 SiTe 6 , a candidate of topological semimetal protected by nonsymmorphic symmetry. Through photon-energy dependent measurements, the surface state near the Fermi level was detected. By determining the band dispersions, we found that the surface state is topological trivial. Around the surface Brillouin zone center, the surface bands disperse linear-like, forming a band crossing (zero energy gap) point at about 0.2 eV below the Fermi level. In Ta 3 SiTe 6 's rectangular surface Brillouin zone, the surface bands only cross the Fermi level along one axis, forming two hole-like Fermi pockets near surface Brillouin zone boundaries. Although the observed surface state is not topological, we proposed that its anisotropic Fermi surface topography could be potentially useful for future applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Ultrafast Dynamics of Molecules on Surfaces Studied with Time-Resolved XUV Photoelectron Spectroscopy (Final Report)

In this project we set out to make technical advances in time-resolved photoemission from surfaces and study molecule-surface charge transfer processes. Combining a novel light source developed at Stony Brook with a new type of time-of-flight photoemission electron microscope (TOF k-mic) developed in Mainz, Germany, we achieved the former goal. Our light source, based on cavity-enhanced high harmonic generation at 61 MHz repetition rate, enables ultrafast time-resolved photoemission experiments to be conducted with orders of magnitude higher photocurrents than otherwise possible. Critically, this provides the high dynamic range necessary to study perturbatively excited samples, such that one can study the intrinsic dynamics of electrons and holes as they would occur in a device. Combining our light source with the TOF k-mic, we’ve achieved an overall improvement in data rate of time- and angle-resolved photoemission (tr-ARPES) of approximately four orders of magnitude over the previous state-of-the-art using kHz-repetition rate sources and conventional hemispherical electron analyzers. This new instrument is now being used in experiments on 2D materials and organic semiconductors.

74 ATOMIC AND MOLECULAR PHYSICS↗

MoS 2 Nanoplatelets on Hybrid Core-Shell (HyCoS) AuPd NPs for Hybrid SERS Platform for Detection of R6G

In this work, a novel hybrid SERS platform incorporating hybrid core-shell (HyCoS) AuPd nanoparticles (NPs) and MoS 2 nanoplatelets has been successfully demonstrated for strong surface-enhanced Raman spectroscopy (SERS) enhancement of Rhodamine 6G (R6G). A significantly improved SERS signal of R6G is observed on the hybrid SERS platform by adapting both electromagnetic mechanism (EM) and chemical mechanism (CM) in a single platform. The EM enhancement originates from the unique plasmonic HyCoS AuPd NP template fabricated by the modified droplet epitaxy, which exhibits strong plasmon excitation of hotspots at the nanogaps of metallic NPs and abundant generation of electric fields by localized surface plasmon resonance (LSPR). Superior LSPR results from the coupling of distinctive AuPd core-shell NP and high-density background Au NPs. The CM enhancement is associated with the charge transfer from the MoS 2 nanoplatelets to the R6G. The direct contact via mixing approach with optimal mixing ratio can effectively facilitate the charges transfer to the HOMO and LUMO of R6G, leading to the orders of Raman signal amplification. The enhancement factor (EF) for the proposed hybrid platform reaches ~10 10 for R6G on the hybrid SERS platform.

36 MATERIALS SCIENCE↗

Reflectance spectroscopy of palagonite and iron-rich montmorillonite clay mixtures: Implications for the surface composition of Mars

Because of the power of remote sensing reflectance spectroscopy in determining mineralogy, it was used as the major method of identifying possible mineral analogs of the Martian surface. A summary of proposed Martian surface compositions from reflectance spectroscopy before 1979 was presented. Since that time, iron-rich montmorillonite clay, nanocrystalline or nanophase hematite, and palagonite were suggested as Mars soil analog materials.

Orenberg, J. B.↗

Enhanced Raman spectroscopic study of rotational isomers on metal surfaces

Surfaced-enhanced Raman spectroscopy has been used to study rotational isomers of succinonitrile and N-methyl-thioacetamide on Cu and Ag surfaces. Both the gauche and trans conformers of succinonitrile are found to chemisorb on the metal surface. The doubly degenerate nu(C-triple bond-N) in the free molecules is removed when succinonitrile adsorbs on copper, which indicates that the two (C-triple bond-N) groups are no longer chemically equivalent. Both conformers are found to coordinate to the copper surface through the pi system of one of the two (C-triple bond-N) groups. In the case of N-methyl-thioacetamide, the population of the cis isomer is greatly increased on Cu and Ag surfaces. This is probably due to surface-induced cis-trans isomerization, in which the predominant trans isomer is converted to the cis isomer.

Loo, B. H.↗

Surface Evaluation by X-Ray Photoelectron Spectroscopy of High Performance Polyimide Foams After Exposure to Oxygen Plasma

Aromatic polyimides have been attractive in the aerospace and electronics industries for applications such as cryogenic insulation, flame retardant panels and structural subcomponents. Newer to the arena of polyimides is the synthesis of polyimide foams and their applications. In the present work, three different, closely related, polyimide foams developed by NASA Langley Research Center (LaRC) are studied by X-ray Photoelectron Spectroscopy (XPS) after exposure to radio frequency generated Oxygen Plasma. Although polyimide films exposure to atomic oxygen and plasma have been studied previously and reported, the data relate to films and not foams. Foams have much more surface area and thus present new information to be explored. Understanding degradation mechanisms and properties versus structure, foam versus solid is of interest and fundamental to the application and protection of foams exposed to atomic oxygen in Low Earth Orbit (LEO).

Melendez, Orlando↗

Understanding the Effect of Lead Iodide Excess on the Performance of Methylammonium Lead Iodide Perovskite Solar Cells

The presence of unreacted lead iodide in organic-inorganic lead halide perovskite solar cells is widely correlated with an increase in power conversion efficiency. We investigate the mechanism for this increase by identifying the role of surfaces and interfaces present between methylammonium lead iodide perovskite films and excess lead iodide. We show how type I and II band alignments arising under different conditions result in either passivation of surface defects or hole injection. Through first-principles simulations of solid-solid interfaces, we find that lead iodide captures holes from methylammonium lead iodide and modulates the formation of defects in the perovskite, affecting recombination. Using surface-sensitive optical spectroscopy techniques, such as transient reflectance and time-resolved photoluminescence, we show how excess lead iodide affects the diffusion and surface recombination velocity of charge carriers in methylammonium lead iodide films. Our coupled experimental and theoretical results elucidate the role of excess lead iodide in perovskite solar cells.

14 SOLAR ENERGY↗

ATR-SEIRAS Reveals Potential Inversion and Associated Electron Transfer Kinetics in the Reduction of Surface-Confined Anthraquinone

The detection of stable semiquinone radicals on an anthraquinone (AQ) layer chemically grafted to an electrode surface in aqueous electrolytes has been elucidated by using attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS). In very alkaline conditions (pH 13), the reduction of the AQ involves no proton transfer, but surface sensitive infrared spectroscopy reveals that the anthraquinone dianion forms a strong hydrogen bonding network with coadsorbed water, leading to irreversible features in the voltammetry. The potential dependence of the IR band assigned to the AQ radical is consistent with the enhanced hydrogen bonding network causing increased stabilization of the quinone radical and supports the predicted response of a system under mild potential inversion, whereby the formal potential for the reduction of the anthraquinone radical is positive of the reduction potential of the neutral AQ molecule. Time-resolved ATR-SEIRAS is used to measure the transient formation of the AQ •– radical, from which rate constant information can be extracted using the Butler–Volmer model involving two one-electron transfers without a direct disproportionation reaction. The potential dependence of the rate constants is consistent with the potential inversion and can be used to qualitatively simulate the measured cyclic voltammograms. In conclusion, the thermodynamic and kinetic analyses re-emphasize long established deficiencies associated with using one-electron reaction formalisms to characterize multi-electron systems.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

Determining the hydronium pKα at platinum surfaces and the effect on pH-dependent hydrogen evolution reaction kinetics

Electrocatalytic hydrogen evolution reaction (HER) is critical for green hydrogen generation and exhibits distinct pH-dependent kinetics that have been elusive to understand. A molecular-level understanding of the electrochemical interfaces is essential for developing more efficient electrochemical processes. Here we exploit an exclusively surface-specific electrical transport spectroscopy (ETS) approach to probe the Pt-surface water protonation status and experimentally determine the surface hydronium pK a = 4.3. Quantum mechanics (QM) and reactive dynamics using a reactive force field (ReaxFF) molecular dynamics (RMD) calculations confirm the enrichment of hydroniums (H 3 O + * ) near Pt surface and predict a surface hydronium pK a of 2.5 to 4.4, corroborating the experimental results. Importantly, the observed Pt-surface hydronium pK a correlates well with the pH-dependent HER kinetics, with the protonated surface state at lower pH favoring fast Tafel kinetics with a Tafel slope of 30 mV per decade and the deprotonated surface state at higher pH following Volmer-step limited kinetics with a much higher Tafel slope of 120 mV per decade, offering a robust and precise interpretation of the pH-dependent HER kinetics. These insights may help design improved electrocatalysts for renewable energy conversion.

Zhong, Guangyan↗

Constructing a Raman Spectroscopy System

The project aims to understand how Raman spectroscopy works by constructing a system based on existing concepts of the technique and utilizing NASA’s available tools and software to analyze the collected data. Once the data is successfully interpreted and proven, other improvements to the assembled system will then be explored. Part of the paper goes through several phases of construction of the system and improvements made. Nevertheless, the data obtained and the results were unsatisfactory as they need to be further analyzed for accuracy. The ultimate ambition was to be able to assist NASA with its objective of implementing a remote and compact Raman spectroscopy system on a rover for future planetary surface characterization such as Mars and lunar surfaces via a Raman spectroscopy system that the agency’s Senior Engineer, Dr. M. Nurul Abedin, has been working on since the early 2000s [2,3,4].

Jake Nguyen↗

Analysis of the Solid Products from the OSCAR and the AOWG Trash Processing Systems

Two trash conversion systems that process space logistical trash for conversion into gases and liquids have minor solid product formation consisting of primarily high carbon ash, inorganic salts, and aluminum metal flakes. These solid products necessarily comprise part of the system output because the thermal degradation processes intentionally operate at temperatures below aluminum vaporization and do not convert all solid inorganics or carbon-based compounds into gaseous compounds (i.e., CO 2 or CH 4 ). The two systems included the Orbital Syngas/Commodity Augmentation Reactor (OSCAR) combustion system funded by the NASA Space Technology Mission Directorate (STMD) located at NASA’s Kennedy Space Center, and the Advanced Organic Waste Gasifier (AOWG) steam reforming system developed by Pioneer Astronautics in Lakewood, Colorado, and funded by the NASA Small Business Innovation Research (SBIR) Exploration Systems Development Mission Directorate (ESDMD). OSCAR residual solids were collected from suborbital flight and ground-based laboratory testing, while all AOWG samples were collected from ground testing. This report discusses the solid product characterization, including elemental analyses performed with scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), and a surface chemistry performed with x-ray photoelectron spectroscopy (XPS). A particle size analysis was performed with sieves, followed by SEM analyses. These analyses were performed to elucidate what high value products can be extracted or utilized from the solid products for follow on infusion into chemical feedstocks, manufacturing additives, or in-situ construction-based material needs.

OSCAR↗

Scanning tunneling microscopy characterization of the geometric and electronic structure of hydrogen-terminated silicon surfaces

Scanning tunneling microscopy (STM) methods are used to characterize hydrogen-terminated Si surfaces prepared by a novel method. The surface preparation method is used to expose the Si-SiO2 interface. STM images directly reveal the topographic structure of the Si-SiO2 interface. The dependence of interface topography on oxide preparation conditions observed by STM is compared to the results of conventional surface characterization methods. Also, the electronic structure of the hydrogen-terminated surface is studied by STM spectroscopy. The near-ideal electronic structure of this surface enables direct tunnel spectroscopy measurements of Schottky barrier phenomena. In addition, this method enables probing of semiconductor subsurface properties by STM.

Kaiser, W. J.↗

Microfluidics, Chromatography, and Atomic-Force Microscopy

A Raman-and-atomic-force microscope (RAFM) has been shown to be capable of performing several liquid-transfer and sensory functions essential for the operation of a microfluidic laboratory on a chip that would be used to perform rapid, sensitive chromatographic and spectro-chemical analyses of unprecedentedly small quantities of liquids. The most novel aspect of this development lies in the exploitation of capillary and shear effects at the atomic-force-microscope (AFM) tip to produce shear-driven flow of liquids along open microchannels of a microfluidic device. The RAFM can also be used to perform such functions as imaging liquids in microchannels; removing liquid samples from channels for very sensitive, tip-localized spectrochemical analyses; measuring a quantity of liquid adhering to the tip; and dip-pen deposition from a chromatographic device. A commercial Raman-spectroscopy system and a commercial AFM were integrated to make the RAFM so as to be able to perform simultaneous topographical AFM imaging and surface-enhanced Raman spectroscopy (SERS) at the AFM tip. The Raman-spectroscopy system includes a Raman microprobe attached to an optical microscope, the translation stage of which is modified to accommodate the AFM head. The Raman laser excitation beam, which is aimed at the AFM tip, has a wavelength of 785 nm and a diameter of about 5 m, and its power is adjustable up to 10 mW. The AFM is coated with gold to enable tip-localized SERS.

Anderson, Mark↗

Demonstration of Portable X-ray Fluorescence Spectroscopy for High-Throughput In-Situ Quantification of Surface Lunar Dust for Testing and Future Surface Missions

In this paper, we present a new method of quantification for surface concentrations of lunar dust and lunar simulant for use and deployment for development testing and potential eventual use for verification and development testing and lunar surface missions. This technique demonstrates the use of portable X-ray fluorescence spectroscopy (pXRF) to quantify lunar dust loading on surfaces using an adaption of existing pXRF techniques. This paper shows the background in current methodologies for quantification of lunar dust in tests as well as current and potential future techniques for lunar surface missions, as well as current applications of commercial off-the-shelf (COTS) pXRF technology. The methodology for adapting current pXRF techniques is presented, followed by a demonstration of this new method on a variety of materials related to spaceflight or lunar surface missions. This technique shows high fidelity for immediate utilization as well as a demonstration of high potential for future surface missions.

Spectroscopy↗