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At least 577 records · Page 32

Application of modern surface analytical tools in the investigation of surface deterioration processes

Surface profilometry and scanning electron microscopy were utilized to study changes in the surface of polymers when eroded. The X-ray photoelectron spectroscopy (XPS) and depth profile analysis indicate the corrosion of metal and ceramic surfaces and reveal the diffusion of certain species into the surface to produce a change in mechanical properties. Ion implantation, nitriding and plating and their effects on the surface are characterized. Auger spectroscopy analysis identified morphological properties of coatings applied to surfaces by sputter deposition.

Buckley, D. H.↗

Reaction paths of methane activation and oxidation of surface intermediates over NiO on Ceria-Zirconia catalysts studied by In-situ FTIR spectroscopy

Methane activation over NiO/Ce 0.82 Zr 0.18 O 2 catalysts synthesized by combustion synthesis is studied by in-situ IR spectroscopy and correlated to the properties and oxygen speciation of the catalyst. Through XRD, H 2 -TPR, and pyridine adsorption followed by FTIR spectroscopy, the reducibility and Lewis acidity of the catalysts are assessed. In-situ FTIR spectroscopy is used to monitor the methane activation on catalyst surfaces. Complex IR features of methane-derived surface species are observed and are attributed to the formation of surface alkyl/alkoxy, aldehyde, formate/carbonate, and aromatic species. A data analysis algorithm is developed to evaluate the evolution of different surface species over time. The formation of formate and carbonate species is driven by adsorbed surface oxygen, while less reactive oxygen species associated with NiO allow for the production of aromatics and alkoxy intermediates. Finally, by tuning the reducibility and Lewis acidity of the catalyst, the selectivity to alkoxy intermediates can be improved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxidation of Alloy X in Subcritical, Transition, and Supercritical Water

This work investigates the oxidation of a nickel-based superalloy, namely Alloy X, in water at elevated temperatures: subcritical water at 261°C and 27 MPa, the transition between subcritical and supercritical water at 374°C and 27 MPa, and supercritical water at 380°C and 27 MPa for 100 h. The morphology of the sample surfaces were studied using scanning electron microscopy coupled with focused ion beam milling, and the surface chemistry was investigated using x-ray diffraction, Raman spectroscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy before and after exposure studies. Surfaces of all samples were identified to comprise of a ferrite spinel containing aluminum.

Materials Science↗

Metal-dielectric interactions

Metal direlectric surface interactions and dielectric films on metal substrates were investigated. Since interfacial interaction depends so heavily on the nature of the surfaces, analytical surface tools such as Auger emission spectroscopy, X-ray photoelectron spectroscopy and field ion microscopy were used to assist in surface and interfacial characterization. The results indicate that with metals contacting certain glasses in the clean state interfacial, bonding produces fractures in the glasses while when a film such as water is present, fractures occur in the metal near the interface. Friction forces were used to measure the interfacial bond strengths. Studies with metals contacting polymers using field ion microscopy revealed that strong bonding forces could develop being between a metal and polymer surface with polymer transferring to the metal surface in various ways depending upon the forces applied to the surface in contact. With the deposition of refractory carbides, silicides and borides onto metal and alloy substrates the presence of oxides at the interface or active gases in the deposition plasma were shown to alter interfacial properties and chemistry. Auger ion depth profile analysis indicated the chemical composition at the interface and this could be related to the mechanical, friction, and wear behavior of the coating.

Buckley, D. H.↗

Reflectance spectroscopy in planetary science: Review and strategy for the future

Reflectance spectroscopy is a remote sensing technique used to study the surfaces and atmospheres of solar system bodies. It provides first-order information on the presence and amounts of certain ions, molecules, and minerals on a surface or in an atmosphere. Reflectance spectroscopy has become one of the most important investigations conducted on most current and planned NASA Solar System Exploration Program space missions. This book reviews the field of reflectance spectroscopy, including information on the scientific technique, contributions, present conditions, and future directions and needs.

Mccord, Thomas B.↗

Interplay of Kondo physics with incommensurate charge density waves in CeTe 3

CeTe 3 is a 2-dimensional (2D) Van der Waals (VdW) material with incommensurate charge density waves (CDW), extremely high transition temperature (T CDW ), and a large momentum-dependent CDW gap that leaves a significant portion of the Fermi surface intact. It is also considered to be a weak Kondo system, a property unexpected for a material with incommensurate CDW, where each atomic site is slightly different. Here, we study the properties of the CDW state in several RTe3 (R is rare earth) materials and examine the hybridization of itinerant states with the localized Ce 4f multiplet in CeTe 3 by using angle resolved photoemission spectroscopy. We find that the renormalization of the itinerant states originating from the hybridization with the deeper localized 4f states at −260 meV is k−dependent and extends to the Fermi level. As these localized states are far from the Fermi level, the observed hybridization affects the effective masses only marginally and does not lead to heavy fermions. However, since the same renormalizing mechanism normally leads to the heavy fermion physics when the localized 4f states are near the Fermi level, our observation of its strong k−dependence suggests that this could be the reason for discrepancy between the heavy masses in specific heat and light ones in Shubnikov de Haas oscillations, often observed in heavy fermions.

36 MATERIALS SCIENCE↗

Aluminum hydroxide, bayerite, boehmite, and gibbsite ToF-SIMS spectra in the negative ion mode. I

We report time-of-flight secondary ion mass spectrometry (ToF-SIMS) was performed for boehmite (AOH-60) and its potential products of oxidation including pseudo-boehmite (AOH-180), α- and γ-Al 2 O 3 , and α- and γ-Al(OH) 3 . Since boehmite is often incorporated on cladding materials to prevent corrosion, surface analysis techniques are performed to determine the amount of oxidation present. This ToF-SIMS spectral library is of significance because it includes boehmite and its potential oxidation products (i.e., aluminum oxide and hydroxide), which can be used to compare to spectra obtained for real-world samples containing boehmite. Furthermore, ToF-SIMS is often used as a complementary technique to x-ray photoelectron spectroscopy due to its surface sensitivity and ability to compare spectra via a multivariate analysis, therefore establishing that the molecular signatures of boehmite and relevant compounds are essential for peak identification. The SIMS spectra shown are acquired from commercially available powders, which were deposited onto a silicon wafer substrate via liquid slurry drop casting. This library of SIMS mass spectra will serve as a comparison of boehmite [γ-AlO(OH)], pseudo-boehmite [AlOOH∙nH 2 O], α- and γ-Al 2 O 3 aluminum oxide, and α- and γ-Al 2 O 3 aluminum hydroxide in the negative ion mode, which compliments those reported in the positive ion mode.

36 MATERIALS SCIENCE↗

Surface Ligand Effects on Energetics, Charge Transfer, and Stability at Interfaces Between Metal Halide Perovskites and Organic Semiconductors

Chemistry at organic-inorganic interfaces plays a major role in determining the performance of electronic and optoelectronic devices. Understanding, developing, and using surface chemistry is thus essential for creating improved and novel materials and devices. Organic metal halide perovskites (HPs) are inexpensive semiconductors that can be printed from solution to make efficient photovoltaic cells for harvesting solar energy, light emitting diodes for energy efficient solid-state lighting applications, solid-state lasers, and even spin selective devices with applications to quantum computing. To realize the potential of HPs, their surface chemistry and interfacial properties must be better understood and appropriately adjusted to meet the needs of the targeted application. For example, surface chemistry influences non-radiative recombination, which influences the efficiency of light emission and solar energy conversion, charge-carrier injection and extraction from optoelectronic devices, and material and device stability. This research project centered around determining how the surface chemistry of HP thin films and nanoparticles influences optical properties, charge transfer processes, energetics, and stability. In this project we characterized ligand binding strengths to HPs; determined how surface ligand chemistry influences photoluminescence properties, energetics, and charge transfer processes; determined that surface ligands often penetrate into HPs and uncovered methods of reducing surface ligand penetration through structural modifications; and discovered how interfacial energetics impact charge transfer processes and photovoltaic performance parameters. Overall, this research established important insights into how surface ligands interact with HPs to influence their optical properties, electronic properties, stability, and device level performance.

14 SOLAR ENERGY↗

Infrared variability of Jupiter and Saturn

Infrared spectroscopy provides unique insights into the chemistry and dynamics of the atmospheres of Jupiter and Saturn, and of the enigmatic satellite of Saturn, Titan. The 5 micron spectral region of these objects is transparent to deep levels, and is therefore particularly useful for the identification of molecules that are present at very low (parts per billion) concentrations. In Titan, 5 micron observations probe atmospheric layers at or near the surface. Ground-based spectroscopy complements Voyager, Galileo, and Cassini measurements. The spectroscopy is sensitive to lower mixing ratios for selected molecules, while the on-board mass and infrared spectrometers probe molecules and levels that are inaccessible form the ground. The observations also provide time-based data for preparation of the upcoming missions.

Knacke, Roger↗

Mixed Ligand Passivation as the Origin of Near-Unity Emission Quantum Yields in CsPbBr 3 Nanocrystals

Key features of syntheses, involving the quaternary ammonium passivation of CsPbBr 3 nanocrystals (NCs), include stable, reproducible and large (often near-unity) emission quantum yields (QYs). The archetypical example involves didodecyl dimethyl ammonium (DDDMA + ) passivated CsPbBr 3 NCs where robust QYs stem from interactions between DDDMA + and NC surfaces. Despite widespread adoption of this synthesis, specific ligand-NC surface interactions responsible for large DDDMA + -passivated NC QYs have not been fully established. Multidimensional nuclear magnetic resonance experiments now reveal a new DDDMA + -NC surface interaction, beyond established “tightly-bound” DDDMA + interactions, which strongly affects observed emission QYs. Depending upon the existence of this new DDDMA + coordination, NC QYs vary broadly between 60% and 85%. More importantly, these measurements reveal surface passivation through unexpected didodecyl ammonium (DDA + ) that works in concert with DDDMA + , to produce near unity (i.e. >90%) QYs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reflectance and Thermal Infrared Spectroscopy of Mars: Relationship Between ISM and TES for Compositional Determinations

Reflectance spectroscopy has demonstrated that high albedo surfaces on Mars contain heavily altered materials with some component of hematite, poorly crystalline ferric oxides, and an undefined silicate matrix. The spectral properties of many low albedo regions indicate crystalline basalts containing both low and high calcium pyroxene, a mineralogy consistent with the basaltic SNC meteorites. The Thermal Emission Spectrometer (TES) experiment on the Mars Geochemical Surveyor has acquired critical new data relevant to surface composition and mineralogy, but in a wavelength region that is complementary to reflectance spectroscopy. The essence of the completed research was to analyze TES data in the context of reflectance data obtained by the French ISM imaging spectrometer experiment in 1989. This approach increased our understanding of the complementary nature of these wavelength regions for mineralogic determinations using actual observations of the martian surface. The research effort focused on three regions of scientific importance: Syrtis Major-Isidis Basin, Oxia Palus-Arabia, and Valles Marineris. In each region distinct spatial variations related to reflectance, and in derived mineralogic information and interpreted compositional units were analyzed. In addition, specific science questions related to the composition of volcanics and crustal evolution, soil compositions and pedogenic processes, and the relationship between pristine lithologies and weathering provided an overall science-driven framework for the work. The detailed work plan involved colocation of TES and ISM data, extraction of reflectance and emissivity spectra from areas of known reflectance variability, and quantitative analysis using factor analysis and statistical techniques to determine the degree of correspondence between these different wavelength regions. Identified coherent variations in TES spectroscopy were assessed against known atmospheric effects to validate that the variations are due to surface properties. With this new understanding of reflectance and emission spectroscopy, mineralogic interpretations were derived and applied to the science objectives of the three regions.

Boyce, Joseph↗

Characterization of In-Situ BN Interface Formed by Nitridation of Nextel 312

Treatment of Nextel (TM) 312 in a reactive environment has been used as a low cost approach to the formation of BN on the fiber surface. Although the BN enriched surface region is extremely thin (less than 40 run), it is effective in providing debonding and composite behavior. Variation in mechanical behavior of Nextel (TM) 312/BN/Blackglas (TM) composites has been noted among panels fabricated with AF-10 cloth treated in different nitridation runs, Understanding this variation became the rationale for undertaking a detailed characterization of the nitrided fiber using field emission scanning electron microscopy, low voltage energy dispersive x-ray and Auger electron spectroscopy. Chemical composition and surface morphology are discussed in relation to observed mechanical behavior of NeXtel (TM) 312/Blackglas (TM) composites tested in bending.

Hurwitz, Fances I.↗

The Use of Tribocharging in the Electrostatic Beneficiation of Lunar Simulant

Any future lunar base and habitat must be constructed from strong dense materials in order to provide for thermal and radiation protection. Lunar soil may meet this need. Lunar regolith has high concentrations of aluminum, silicon, calcium, iron, sodium, and titanium oxides. Refinement or enrichment of specific minerals in the soil before it is chemically processed may be more desirable as it would reduce the size and energy requirements required to produce the virgin material and it may significantly reduce the process' complexity. Also, investigations into the potential production of breathable oxygen from oxidized mineral components are a major research initiative by NASA. In this study. the objective was to investigate the use of tribocharging to charge lunar simulants and pass them through a parallel plate separator to enrich different mineral fractions. This technique takes advantage of the high Lunar vacuum in which much higher voltages can be used on the separation plates than in air. Additionally, the Lunar g1avity, only being 1/6 that of Earth, allows the particles more separation time between the plates and therefore enhances separation. For the separation studies, two lunar stimulants were used. The first simulant was created in-house, labeled KSC-1. using commercially supplied (sieved to 325 mesh) materials, and was composed of 40 wt. % feldspar ((Na,K,Ca)AlSi3O8;SiO2), 40 wt. % olivine ((Mg,Fe)2SiO4), 10 wt. % ilmenite (FeTiO3). and 10 wt. % spodumene (LiAlSi2O6) (pyroxene). The advantage of the in-house mixture is that the composition can he varied to simulate different soil compositions from different areas on the moon. This simulant was used to show proof-of-concept using the designed separator in air. The second stimulant was JSC-1. used for the vacuum experiments. JSC-1 is principally basalts, containing phases of plagioclase. pyroxene. olivine, and ilmenite. The JSC-1 was sieved to provide a 50-75 micron size range to correlate with the mean grain size found on the moon's surface [1]. Four different materials were investigated for the triboelectrification process; aluminum, copper. stainless steel, and PTFE. These materials were selected because they offer a wide variation in work functions (aluminum 4.28 eV, copper 4.65 eV. stainless steel 5.04 eV, and PTFE 5.75 eV). The difference between the work function of each material and the simulant influences the charge obtained by the grains. Each simulant was analyzed before and after separation using X-ray Photoelectron Spectroscopy (XPS) to determine mineral surface composition. In addition. Raman spectroscopy was performed on the JSC-1 before and after separation in vacuum to determine the mineral composition. Charge-to-mass (Q/M) measurements were performed using a fluidizing bed in air and passing the simulant through a static mixer of a particular material and collecting it in a Faraday pail grounded through an electrometer. To measure the Q/M in vacuum, a special device was constructed consisting of a heater/shaker cup that fed into a solid block of material (either PTFE, copper, or aluminum) in which a channel composed of a "zig-zag" series of inclines greater than 50 degrees has been cut. The voltage to the vibrating motor can be varied to control the amount of simulant passing through the channel. Figure I shows the Q/M measurements for JSC-1 tribocharged using the static mixers and the incline plane chargers in air, and the incline plane chargers in vacuum.

Trigwell, S.↗

All-epitaxial long-range surface plasmon polariton structures with integrated active materials

We demonstrate all-epitaxial structures capable of supporting short- and long-range surface plasmon polariton (SRSPP and LRSPP) modes in the long-wave infrared region of the electromagnetic spectrum. The SRSPP and LRSPP modes are bound to the interfaces of a buried heavily doped (n ++ ) semiconductor layer and surrounding quantum-engineered type-II superlattice (T2SL) materials. The surrounding T2SLs are designed to allow optical transitions across the frequency dispersion of the SPP modes. We map the SPP dispersion in our structure using grating-coupled angle- and polarization-dependent reflection and photoluminescence spectroscopy. The epitaxial structures are analytically described using a simplified three-layer system (T2SL/n ++ /T2SL) and modeled using rigorous coupled wave analysis with excellent agreement to our experimental results. The presented structures offer the potential to serve as long-range interconnects or waveguides in all-epitaxial plasmonic/optoelectronic systems operating in the long-wave infrared.

36 MATERIALS SCIENCE↗

Observation of spin-momentum locked surface states in amorphous Bi 2 Se 3

Crystalline symmetries have played a central role in the identification and understanding of quantum materials. Here we investigate whether an amorphous analogue of a well-known three-dimensional strong topological insulator has topological properties in the solid state. We show that amorphous Bi 2 Se 3 thin films host a number of two-dimensional surface conduction channels. Our angle-resolved photoemission spectroscopy data are consistent with a dispersive two-dimensional surface state that crosses the bulk gap. Spin-resolved photoemission spectroscopy shows this state has an anti-symmetric spin texture, confirming the existence of spin-momentum locked surface states. We discuss these experimental results in light of theoretical photoemission spectra obtained with an amorphous topological insulator tight-binding model, contrasting it with alternative explanations. In conclusion, the discovery of spin-momentum locked surface states in amorphous materials opens a new avenue to characterize amorphous matter and triggers the search for an overlooked subset of quantum materials outside of current classification schemes.

36 MATERIALS SCIENCE↗

Activating magnetite ores for aqueous ironmaking at high current densities

Low-temperature electrochemical cells reducing iron oxides to metal in alkaline electrolytes can support fully electrified steelmaking processes. Previous studies on these cells have primarily focused on high-surface-area hematite, Fe 2 O 3 , reactants whereas attempts to reduce suspensions of magnetite, Fe 3 O 4 —one of the two feedstocks for existing ironmaking reactors—have generally been limited to low rates of reaction (<30 mA cm −2 ). Here, in this study, we control the crystalline domain size of Fe 2 O 3 and Fe 3 O 4 particles in 10 M NaOH electrolytes to study how the nanoscale morphology of oxides controls the rate of electrochemical ironmaking. Rotating-ring disk electrode measurements of Fe 2+ , in situ Raman spectroscopy of the electrode surface, and ex situ electron microscopy were consistent with a hypothesized passivation process at Fe 3 O 4 surfaces that may prevent the continuous formation of soluble intermediates. Sufficiently small (<100 nm diameter) oxide particles yielded Fe partial current densities >160 mA cm −2 , a fivefold increase relative to previously reported rates for Fe 3 O 4 suspensions and comparable to active Fe 2 O 3 . Electron microscopy revealed that electrodeposited films were composed of micron-scale crystalline Fe domains with a porous film of Fe 3 O 4 nanoparticles and supports a model where Fe is grown primarily from soluble Fe 2+ intermediates. Based on these insights, inactive blast-furnace-grade iron-oxides were transformed into high surface area nanoparticles (1.6 to 229.2 m 2 g −1 ) via reprecipitation, leading to a ninefold enhancement in faradaic efficiency and an Fe partial current density of 120 mA cm −2 . When integrated with chlor-iron cells producing reagents for reprecipitation, this approach could lead to a cost-competitive process for electrochemical ironmaking from industrially relevant feedstocks.

TEM↗

Electrocatalytic Isoxazoline–Nanocarbon Metal Complexes

In this work, we report the synthesis of new carbon-nanomaterial-based metal chelates that enable effective electronic coupling to electrocatalytic transition metals. In particular, multiwalled carbon nanotubes (MWCNTs) and few-layered graphene (FLG) were covalently functionalized by a microwave-assisted cyclo-addition with nitrile oxides to form metal-binding isoxazoline functional groups with high densities. The covalent attachment was evidenced by Raman spectroscopy, and the chemical identity of the surface functional groups was confirmed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The functional carbon nanomaterials effectively chelate precious metals Ir(III), Pt(II), and Ru(III), as well as earth-abundant metals such as Ni(II), to afford materials with metal contents as high as 3.0 atom %. The molecularly dispersed nature of the catalysts was confirmed by X-ray absorption spectroscopy (XAS) and energy-dispersive X-ray spectroscopy (STEM-EDS) elemental mapping. The interplay between the chelate structure on the graphene surface and its metal binding ability has also been investigated by a combination of experimental and computational studies. The defined ligands on the graphene surfaces enable the formation of structurally precise heterogeneous molecular catalysts. The direct attachment of the isoxazoline functional group on the graphene surfaces provides strong electronic coupling between the chelated metal species and the conductive carbon nanomaterial support. We demonstrate that the metal-chelated carbon nanomaterials are effective heterogeneous catalysts in the oxygen evolution reaction with low overpotentials and tunable catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective hybridization between the main band and the superstructure band in the Bi 2 Sr 2 CaCu 2 O 8 + δ superconductor

High-resolution laser-based angle-resolved photoemission measurements have been carried out on Bi 2 Sr 2 CaCu 2 O 8+δ (Bi2212) and Bi 2 Sr 2–x La x CuO 6+δ (Bi2201) superconductors. Unexpected hybridization between the main band and the superstructure band in Bi2212 is clearly revealed. In the momentum space where one main Fermi surface intersects with one superstructure Fermi surface, four bands are observed instead of two. The hybridization exists in both the superconducting state and the normal state, and in Bi2212 samples with different doping levels. Such a hybridization is not observed in Bi2201. This phenomenon can be understood by considering the bilayer splitting in Bi2212, the selective hybridization of two bands with peculiar combinations, and the altered matrix element effects of the hybridized bands. These observations indicate that the origin of the superstructure bands is intrinsic to the CuO 2 planes. Furthermore, understanding physical properties and superconductivity in Bi2212 should consider the complete Fermi surface topology which involves the main bands, the superstructure bands, and their interactions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗