Vaporization of chromium oxides from the surface of TD-NiCr under oxidizing conditions
Vaporization of chromium oxides from surface of TD-NiCr under oxidizing conditions
Kohl, F. J.↗
SEARCH · Engineering Papers
Results for “surface oxidation”
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Atomic Layer Deposition of Chemical Passivation Layers and High Performance Anti-Reflection Coatings on Back-Illuminated Detectors
A back-illuminated silicon photodetector has a layer of Al2O3 deposited on a silicon oxide surface that receives electromagnetic radiation to be detected. The Al2O3 layer has an antireflection coating deposited thereon. The Al2O3 layer provides a chemically resistant separation layer between the silicon oxide surface and the antireflection coating. The Al2O3 layer is thin enough that it is optically innocuous. Under deep ultraviolet radiation, the silicon oxide layer and the antireflection coating do not interact chemically. In one embodiment, the silicon photodetector has a delta-doped layer near (within a few nanometers of) the silicon oxide surface. The Al2O3 layer is expected to provide similar protection for doped layers fabricated using other methods, such as MBE, ion implantation and CVD deposition.
Hoenk, Michael E.↗
Ex Situ Photoelectron Emission Microscopy of Polycrystalline Bismuth and Antimony Telluride Surfaces Exposed to Ambient Oxidation
The surfaces of textured polycrystalline N-type bismuth telluride and P-type antimony telluride materials were investigated using ex situ photoelectron emission microscopy (PEEM). PEEM enabled imaging of the work function for different oxidation times due to exposure to air across sample surfaces. The spatially averaged work function was also tracked as a function of air exposure time. N-type bismuth telluride showed an increase in the work function around grain boundaries relative to grain interiors during the early stages of air exposure-driven oxidation. At longer time exposure to air, the surface became homogenous after a ~5 nm-thick oxide formed. X-ray photoemission spectroscopy was used to correlate changes in PEEM imaging in real space and work function evolution to the progressive growth of an oxide layer. The observed work function contrast is consistent with the pinning of electronic surface states due to the defects at a grain boundary.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Origins of enhanced oxygen reduction activity of transition metal nitrides
Transition metal nitride (TMN-) based materials have recently emerged as promising non-precious-metal-containing electrocatalysts for the oxygen reduction reaction (ORR) in alkaline media. However, the lack of fundamental understanding of the oxide surface has limited insights into structure–(re)activity relationships and rational catalyst design. Here, in this work, we demonstrate how a well-defined TMN can dictate/control the as-formed oxide surface and the resulting ORR electrocatalytic activity. Structural characterization of MnN nanocuboids revealed that an electrocatalytically active Mn 3 O 4 shell grew epitaxially on the MnN core, with an expansive strain along the [010] direction to the surface Mn 3 O 4 . The strained Mn 3 O 4 shell on the MnN core exhibited an intrinsic activity that was over 300% higher than that of pure Mn 3 O 4 . A combined electrochemical and computational investigation indicated/suggested that the enhancement probably originates from a more hydroxylated oxide surface resulting from the expansive strain. This work establishes a clear and definitive atomistic picture of the nitride/oxide interface and provides a comprehensive mechanistic understanding of the structure–reactivity relationship in TMNs, critical for other catalytic interfaces for different electrochemical processes.
electrocatalysis↗
Heteroepitaxial chemistry of zinc chalcogenides on InP nanocrystals for defect-free interfaces with atomic uniformity
Heteroepitaxy on colloidal semiconductor nanocrystals is an essential strategy for manipulating their optoelectronic functionalities. However, their practical synthesis typically leads to scattered and unexpected outcomes due to the intervention of multiple reaction pathways associated with complicated side products of reactants. Here, the heteroepitaxy mechanism of zinc chalcogenide initiated on indium phosphide (InP) colloidal nanocrystals is elucidated using the precursors, zinc carboxylate and trialkylphosphine selenide. The high magnetic receptivity of 77 Se and the characteristic longitudinal optical phonon mode of ZnSe allowed for monitoring the sequence of epilayer formation at the molecular level. The investigation revealed the sterically hindered acyloxytrialkylphosphonium and diacyloxytrialkylphosphorane to be main intermediates in the surface reaction, which retards the metal ion adsorption by a large steric hindrance. The transformation of adsorbates to the crystalline epilayer was disturbed by surface oxides. Raman scattering disclosed the pathway of secondary surface oxidation triggered by carboxylate ligands migrated from zinc carboxylate. The surface-initiated heteroepitaxy protocol is proposed to fabricate core/shell heterostructured nanocrystals with atomic-scale uniformity of epilayers. Despite the large lattice mismatch of ZnS to InP, we realised a uniform and interface defect-free ZnS epilayer (~0.3 nm thickness) on InP nanocrystals, as evidenced by a high photoluminescence quantum yield of 97.3%.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Investigation of N2 adsorption on Fe3O4(001) using ambient pressure X-ray photoelectron spectroscopy and density functional theory
Reactions on iron oxide surfaces are prevalent in various chemical processes from heterogeneous catalysts to minerals. Nitrogen (N2) is known to dissociate on iron surfaces, a precursor for ammonia production in the Haber–Bosch process, where the dissociation of N2 is the limiting step in the reaction under equilibrium conditions. However, little is known about N2 adsorption on other iron-based materials, such as iron oxide surfaces that are ubiquitous in soils, steel pipelines, and other industrial materials. An atomistic description is reported for the binding of N2 on the Fe3O4(001) surface using first principles calculations with ambient pressure X-ray photoelectron spectroscopy. Two primary adsorption sites are experimentally identified from N2 dissociation on Fe3O4(001). The electronic signatures associated with the valence band region unambiguously show how the electronic structure of magnetite transforms near ambient pressures due to the binding of atomic nitrogen to different surface sites. Overall, the experimental and theoretical results of our study bridge the gap between ultra-high vacuum studies and reaction conditions to provide insight into other nitrogen-based chemistry on iron oxide surfaces that impact the agriculture and energy industries.
Degaga, Gemechis D. (ORCID:0000000205097118)↗
Surface effects of corrosive media on hardness, friction, and wear of materials
Hardness, friction, and wear experiments were conducted with magnesium oxide exposed to various corrosive media and also with elemental iron and nickel exposed to water and NaOH. Chlorides such as MgCl2 and sodium containing films were formed on cleaved magnesium oxide surfaces. The MgCl2 films softened the magnesium oxide surfaces and caused high friction and great deformation. Hardness was strongly influenced by the pH value of the HCl-containing solution. The lower the pH, the lower the microhardness. Neither the pH value of nor the immersion time in NaOH containing, NaCl containing, and HNO3 containing solutions influenced the microhardness of magnesium oxide. NaOH formed a protective and low friction film on iron surfaces. The coefficient of friction and the wear for iron were low at concentrations of NaOH higher than 0.01 N. An increase in NaOH concentration resulted in a decrease in the concentration of ferric oxide on the iron surface. It took less NaOH to form a protective, low friction film on nickel than on iron.
Miyoshi, K.↗
Surface effects of corrosive media on hardness, friction, and wear of materials
Hardness, friction, and wear experiments were conducted with magnesium oxide exposed to various corrosive media and also with elemental iron and nickel exposed to water and NaOH. Chlorides such as MgCl2 and sodium containing films were formed on cleaved magnesium oxide surfaces. The MgCl2 films softened the magnesium oxide surfaces and caused high friction and great deformation. Hardness was strongly influenced by the pH value of the HCl-containing solution. The lower the pH, the lower the microhardness. Neither the pH value of nor the immersion time in NaOH containing, NaCl containing, and HNO3 containing solutions influenced the microhardness of magnesium oxide. NaOH formed a protective and low friction film on iron surfaces. The coefficient of friction and the wear for iron were low at concentrations of NaOH higher than 0.01 N. An increase in NaOH concentration resulted in a decrease in the concentration of ferric oxide on the iron surface. It took less NaOH to form a protective, low friction film on nickel than on iron.
Miyoshi, K.↗
Surface effects on deuterium permeation through vanadium membranes
Dense vanadium-based membranes offer high permeability and perfect selectivity to hydrogen isotopes, maintain favorable neutronic properties, and are compatible with liquid metals such as PbLi. These properties make vanadium membranes a promising fusion fuel cycle technology for processes such as tritium extraction from PbLi and exhaust processing. Surface contamination has a deleterious effect on the gas-phase hydrogen permeation through vanadium, and the reported permeabilities range from 10 -14 to 10 -7 mol m -1 s -1 Pa -0.5 . Thin dense films of palladium applied to clean vanadium surfaces enable a consistently high hydrogen permeability. In this study, uncoated vanadium resulted in deuterium permeabilities ranging from 2.8 × 10 -11 to 6.4 × 10 -9 mol m -1 s -1 Pa -0.5 at 300 °C–700 °C, respectively. Post-test analysis revealed a VO x surface layer and VC x subsurface layer formed on the feed side, while the as-received surface oxide dissolved leaving a submonolayer oxide on the permeate surface. Furthermore, the Pd-coated V resulted in a maximum deuterium permeability of 2.1 × 10 -7 m -1 s -1 Pa -0.5 at 375 °C upon activation of the Pd surface by oxidation and reduction. The deuterium permeation declined upon heating to 500 °C due to intermetallic diffusion between the Pd and V. The Mo 2 C-coated V resulted in deuterium permeabilities ranging from 2.7 × 10 -10 to 1.8 × 10-9 at 500 °C–700 °C, respectively, and a post-test analysis found the carbon in the Mo 2 C layer had dissolved into the V near the interface.
13 HYDRO ENERGY↗
Gas Shielding Technology for Welding and Brazing
Welding is a common method that allows two metallic materials to be joined together with high structural integrity. When joints need to be leak-tight, light-weight, or free of contaminant-trapping seams or surface asperities, welding tends to be specified. There are many welding techniques, each with its own advantages and disadvantages. Some of these techniques include Forge Welding, Gas Tungsten Arc Welding, Friction Stir Welding, and Laser Beam Welding to name a few. Whichever technique is used, the objective is a structural joint that meets the requirements of a particular component or assembly. A key practice in producing quality welds is the use of shielding gas. This article discusses various weld techniques, quality of the welds, and importance of shielding gas in each of those techniques. Metallic bonds, or joints, are produced when metals are put into intimate contact. In the solid-state "blacksmith welding" process, now called Forge Welding (FOW), the site to be joined is pounded into intimate contact. The surfaces to be joined usually need to be heated to make it easier to deform the metal. The surfaces are sprinkled with a flux to melt surface oxides and given a concave shape so that surface contamination can be squeezed out of the joint as the surfaces are pounded together; otherwise the surface contamination would be trapped in the joint and would weaken the weld. In solid-state welding processes surface oxides or other contamination are typically squeezed out of the joint in "flash."
Nunes, Arthur J.↗
Controlling Heterogeneous Catalysis with Organic Monolayers on Metal Oxides
A key theme of heterogeneous catalysis research is achieving control of the environment surrounding the active site to precisely steer the reactivity toward desired reaction products. One method toward this goal has been the use of organic ligands or self-assembled monolayers (SAMs) on metal nanoparticles. Metal-bound SAMs are typically employed to improve catalyst selectivity but often decrease the reaction rate as a result of site blocking from the ligands. Recently, the use of metal oxide-bound organic modifiers such as organophosphonic acid (PA) SAMs has shown promise as an additional method for tuning reactions on metal oxide surfaces as well as modifying oxide-supported metal catalysts. In this Account, we summarize recent approaches to enhance catalyst performance with oxide-bound monolayers. These approaches include (1) modification of metal oxide catalysts to tune surface reactions, (2) formation of SAMs on the oxide component of supported metal catalysts to modify sites at the metal–support interface, and (3) enhancement of catalyst performance (e.g., stability) through modification of sites remote from the active sites. Further, both the headgroups and organic tail groups of PA SAMs or other ligands can influence reactions on metal oxide surfaces. Binding of the headgroup can selectively poison certain active sites, altering the selectivity in a manner analogous to metal-bound ligands (at the expense of active site quantity). Moreover, tail groups can be functionalized to interact favorably with reactants and intermediates, for instance through dipole–dipole interactions. On supported metal catalysts like Pt/Al 2 O 3 , PA SAMs can selectively form on the oxide support. This selective deposition allows for modification of the metal–support interface with minimal blockage of metal sites. PA headgroups were shown to provide tunable acid sites at the interface, dramatically improving hydrodeoxygenation rates of various alcohols. Additionally, organic tail functionality was used to activate or stabilize specific reactants at the interface, such as with the use of amine-functionalized PAs to stabilize chemisorption of CO 2 during the reverse water gas shift reaction. PAs have also been found to affect the electronic properties of bulk metal sites through long-range electron withdrawal via the oxide, providing an additional avenue to tune catalytic behavior. Finally, organic modifiers were shown to enhance catalytic performance without directly modifying the active site. For instance, in biphasic liquid environments the modification of catalyst particles with hydrophobic or hydrophilic SAMs shifts the selectivity of multipath reactions on the basis of the hydrophobicities of different intermediates and products. As another “long-range” effect, the deposition of ligands on oxide supports improved catalyst stability through both improved resistance to sintering and suppression of active site poisoning. The recent contributions discussed in this Account demonstrate the versatility and significant potential for the approach of modifying catalysts with oxide-bound organic monolayers.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The Role of Surface Hydroxyls in Dehydration and Dehydrogenation of Formic Acid on Fe 3 O 4 (001)
Understanding the role of surface structure and hydroxylation in catalytic reactions on metal oxide surfaces is important for developing a mechanistic insight into the complex interface processes. Here, we investigate the reactivity of formic acid on reconstructed Fe 3 O 4 (001) using a combination of X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, temperature-programmed reaction spectroscopy, low energy electron diffraction, and electronic structure calculations. We find that formic acid initially dissociates at low temperatures (< 80 K) into bidentate formate and a hydroxyl up to an initial dosed coverage of two HCOOH per Fe 3 O 4 (001) unit cell. At higher temperatures (> 450 K), formate largely decomposes along the dehydration pathway, producing CO and H 2 O, with dehydrogenation to CO 2 being a minority side reaction. As a first step, water formation leads to surface oxygen extraction via the Mars-van Krevelen mechanism. Computational studies reveal formate embedded in oxygen vacancies as a key intermediate in the CO formation mechanism. CO formation proceeds via two reaction pathways with desorption that peaks at 530 K on the hydroxyl-rich surface and 560 K on the hydroxyl-deficient surface. Atomic hydrogen coadsorption experiments and ab initio calculations reveal that the presence of surface hydroxyls reduces the CO formation barrier. Furthermore, these results highlight the complex interactions between substrate and intermediate species occurring during reactions on metal oxide surfaces.
Adsorption↗
A conformal oxidation-resistant, plasma-polymerized coating
A comparative study was made of the surface recession (etching) of thin films of plasma polymerized tetrafluoro ethylene (PPTFE), polytetrafluoro ethylene (PTFE), and ion-beam sputter deposited polytetrafluoro ethylene (SPTFE) exposed to ground-state atomic oxygen downstream from a nonequilibrium radio-frequency O2 plasma. At 22 C, the etch rates for PTFE, SPTFE, and PPTFE were in the ratio of 8.7:1.8:1.0. A thin, conformal coating of PPTFE (etch rate of 0.3 nm/h at 22 C) was found to protect an underlying cast film of a reactive polymer, cis-1,4 polybutadiene, against ground-state atomic oxygen attack for the time required to fully etch away the PPTFE coating. From ESCA analysis, PTFE exhibited only minor surface oxidation (uptake of 0.5 atom percent O) upon etching, its F/C ratio decreasing slightly from 2.00 to 1.97; PPTFE exhibited considerable surface oxidation (uptake of 5.9 atom percent O) intermediate between those of PTFE and PPTFE, with a decrease in F/C ratio from 1.73 to 1.67. A plasma-polymerized fluorocarbon coating such as PPTFE might be useful for space applications to protect polymers that are vulnerable to oxidation or degradation by oxygen atoms.
Golub, Morton A.↗
Interface states and internal photoemission in p-type GaAs metal-oxide-semiconductor surfaces
An interface photodischarge study of p-type GaAs metal-oxide-semiconductor (MOS) structures revealed the presence of deep interface states and shallow donors and acceptors which were previously observed in n-type GaAs MOS through sub-band-gap photoionization transitions. For higher photon energies, internal photoemission was observed, i.e., injection of electrons to the conduction band of the oxide from either the metal (Au) or from the GaAs valence band; the threshold energies were found to be 3.25 and 3.7 + or - 0.1 eV, respectively. The measured photoemission current exhibited a thermal activation energy of about 0.06 eV, which is consistent with a hopping mechanism of electron transport in the oxide.
Kashkarov, P. K.↗
Surface electron modulation of metal oxide‐based electrochemical devices by surface additives—linking sensors and fuel cells
Abstract The interaction between ambient oxygen and the metal oxide surface is central to various electrochemical devices. Solid oxide fuel cell cathodes and semiconducting metal oxide gas sensors are two prominent examples. Parallels between these two systems are highlighted in this perspective. In both cases, the presence of foreign surface species has been found to significantly alter the interactions of the metal oxides’ surfaces with oxygen. On the one hand, interactions are hindered due to the presence of certain impurities, such as the degradation of fuel cell cathode by Si‐species that originate from processing or from operating environments. On the other hand, electrochemically active noble metal additives have been intentionally used to tune the sensor response of metal oxides. In the case of electrochemically active additives, the need for operando spectroscopies to elucidate the mechanism is discussed. Electronic coupling of the surface additive with the metal oxide is found to play a central role in both cases. We use these results to demonstrate that insights gained from either field can be effectively applied to the other.
Materials Science↗
Interaction of hydrogen with actinide dioxide (011) surfaces
The corrosion and oxidation of actinide metals, leading to the formation of metal-oxide surface layers with the catalytic evolution of hydrogen, impacts the management of nuclear materials. In this work, the interaction of hydrogen with actinide dioxide (AnO 2 , An = U, Np, or Pu) (011) surfaces by Hubbard corrected density functional theory (PBEsol+U) has been studied, including spin–orbit interactions and non-collinear 3k anti-ferromagnetic behavior. The actinide dioxides crystalize in the fluorite-type structure, and although the (111) surface dominates the crystal morphology, the (011) surface energetics may lead to more significant interaction with hydrogen. The dissociative adsorption of hydrogen on the UO 2 (0.44 eV), NpO 2 (-0.47 eV), and PuO 2 (-1.71 eV) (011) surfaces has been calculated. It is found that hydrogen dissociates on the PuO 2 (011) surface; however, UO 2 (011) and NpO 2 (011) surfaces are relatively inert. Recombination of hydrogen ions is likely to occur on the UO 2 (011) and NpO 2 (011) surfaces, whereas hydroxide formation is shown to occur on the PuO 2 (011) surface, which distorts the surface structure.
36 MATERIALS SCIENCE↗
Mechanisms of Oxide Formation in the Self-Reacting Friction Stir Weld Process
The initial objective of this study was to evaluate the effect of an extended delay time between preweld cleaning and the completion of a self-reacting friction stir welding (SRFSW) process on the resulting quality of various thickness panels of AA2219-T87. The current NASA standard specifies no more than a 48 hour delay between preweld cleaning and actual welding. The concern is whether increasing the cleaning delay time results in development of the residual oxide defect (ROD) in SRFSW. This concern emanates from the possibility of increased time correlating with increased oxide layer thickness on the faying surfaces. Oxide content on the faying surfaces has been reported to correlate with the occurrence of the ROD which reduces mechanical properties. When the SRFSW process was first adopted by the NASA Marshall Space Flight Center (MSFC), unexpected low tensile values that resulted were attributed to oxides within the weld that appeared to follow the former faying surface contours. Mitigation of the ROD was achieved through a combination of modifications to the processing parameters, tool designs, and incorporation of a weld seam offset. Two operations are involved in preweld cleaning: the first is removal of oil and grease, and the second is removal of surface oxides. In arc welding, improper cleaning of the faying surfaces of aluminum welded joints can increase the sensitivity toward development of defects. As the aluminum is locally melted, these contaminants contribute toward the development of porosity, inclusions, entrapped oxides, and other discontinuities which can degrade the strength of the weld joint. For weldment of large structures, the weld joint is typically cleaned, fit-up, and tack welded prior to the final full penetration welding pass. Because of the stringent joint fit-up requirements for mismatch and peaking for launch vehicle structures, the joint fit-up can sometimes contribute to lengthy delays between cleaning and tack welding, especially for circumferential weld joints on large diameter components. When the conventional friction stir welding (CFSW) process was introduced at the NASA MSFC, there was no procedure for cleaning prior to the solid-state joining process. As the process expanded to include SRFSW, preparation of the faying, crown, and root surfaces were implemented to overcome the ROD. Although the solid-state process is not expected to reach temperatures high enough for dissociation of the native oxide layer, concern remained regarding the redeposition of the native oxide layer within the stir zone. NASA has previously established the allowable time at 48 hours between preweld cleaning and a SRFSW process. The effect of potential 2 contamination resulting from an extended delay to 188 hours was subsequently evaluated for SRFSWs using tensile testing and metallographic imaging. Tensile specimens were tested at room temperature (RT), and at cryogenic conditions of liquid nitrogen (LN2) and liquid hydrogen. No detrimental effect on weld quality, as determined by weld strength, was reported for cleaning delays of 48, 120, 168, 240 or 288 hours. While no trends were established in this study, which extended the delay from 48 to 188 hours, there were a few outliers in terms of ultimate tensile strength (UTS). According to M. Fisher's 2014 Boeing Company Memo no. EYBF-MAF-14-029, all outliers were above the minimum acceptance criteria, but out of family with respect to the average values. As the robustness and reliability of any process ultimately depends on the average values as well as the outliers, an understanding of the cause of these outliers will ultimately improve the process. This report examines those outliers and their possible causes.
Schneider, J. A.↗
ESCA Study of Poly (Vinylidene Fluoride) Tetrafluoroethylene - Ethylene Copolymer and Polyethylene Exposed to Atomic Oxygen
The ESCA (electron spectroscopy for chemical analysis) spectra of films of poly(vinylidene fluoride) (PVDF), tetrafluoroethylene-ethylene copolymer (TFE/ET) and polyethylene (PE) exposed to atomic oxygen (O(P-3)), in or out of the glow of a radio-frequency O2 plasma, were compared. ESCA spectra of PE films exposed to (O(P-3)) in low Earth orbit (LEO) on the STS-8 Space Shuttle were also examined. Apart from O(P-3)-induced surface recession (etching), the various polymer films exhibited surface oxidation, which proceeded towards equilibrium saturation oxygen levels. The maximum surface oxygen uptakes for in-glow or out-of-glow exposures were in the order: PE greater than TFE/ET greater than PVDF; for PE itself, the oxygen uptakes were in the order: in glow greater than out of glow greater than LEO. Given prior ESCA data on poly(vinyl fluoride) and polytetrafluoroethylene films exposed to O(P-3), the extent of surface oxidation is seen to decrease regularly with increase in fluorine substitution in a family of ethylene-type polymers. (Keywords: ESCA; poly(vinylidene fluoride); tetrafluoroethylene ethylene copolymer; polyethylene; atomic oxygen; radio-frequency oxygen plasma; low Earth orbit)
Golub, Morton A.↗