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At least 235 records · Page 13

Dark mirror optical stack and related systems

A dark mirror optical stack, particularly a low emittance, high absorbance dark mirror optical stack is provided. The dark mirror optical stack includes a polyimide substrate containing carbon filler, an aluminum layer on the polyimide substrate, a first silicon oxide layer on the aluminum layer, a chromium layer on the first silicon oxide layer, and a second silicon oxide layer on the chromium layer. In a particularly exemplary embodiment, the aluminum layer has an average thickness of 600 to 2000 Angstroms, the first and second silicon oxide layers have average thicknesses of 500 to 1000 Angstroms, and the chromium layer has an average thickness of 40 to 100 Angstroms.

Hasegawa, Mark↗

Accelerated Cu2O Reduction by Single Pt Atoms at the Metal-Oxide Interface§

The reducibility of metal oxides, when serving as the catalyst support or the active sites themselves, plays an important role in heterogeneous catalytic reactions. Here we present an integrated experimental and theoretical study that reveals how the addition of small amounts of atomically dispersed Pt at the metal/oxide interface dramatically enhances the reducibility of a Cu2O thin film by H2. X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) results reveal that upon oxidation, a PtCu single-atom alloy (SAA) surface is covered by a thin Cu2O film and is therefore unable to dissociate H2. Despite this, in situ studies using ambient pressure (AP) XPS reveal that the presence of a small amount of Pt under the oxide layer can, at the single-atom limit, promote the reduction of Cu2O by H2 at room temperature. We build two density functional theory based surface models to better understand these experimental findings: A Cu2O/Cu(111)-like surface oxide layer, known as the ‘29’ oxide, in which Pt is alloyed into the Cu(111) surface as well as a PtCu SAA. Our calculations suggest that the increased activity is due to the presence of atomically dispersed Pt under the surface oxide layer, which weakens the Cu-O bonds in its immediate vicinity, thus making the interface between subsurface Pt and the surface oxide a nucleation site for the formation of metallic Cu. This initial step in the reduction process results in the presence of surface Pt atoms surrounded by metallic Cu patches, and the Pt atoms become active in H2 dissociation, which consequently accelerates the reduction of the oxide layer. This work demonstrates how isolated Pt atoms at the metal/oxide interface of a Cu-based catalyst accelerate the reduction of the oxide and, therefore, helps maintain the active, reduced state of the catalyst under reaction conditions, as is required for the synthesis of methanol from CO2 hydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimization of contaminated oxide inversion layer solar cell

Contaminated oxide cells have been fabricated with efficiencies of 8.6% with values of I sub sc = 120 ma, V sub oc = .54 volts, and curve factor of .73. Attempts to optimize the fabrication step to yield a higher output have not been successful. The fundamental limitation is the inadequate antireflection coating afforded by the silicon dioxide coating used to hold the contaminating ions. Coatings of SiO, therefore, were used to obtain a good antireflection coating, but the thinness of the coatings prevented a large concentration of the contaminating ions, and the cells was weak. Data of the best cell were .52 volts V sub oc, 110 ma I sub sc, .66 CFF and 6.7% efficiency.

Call, R. L.↗

Activating Layered Metal Oxide Nanomaterials via Structural Engineering as Biodegradable Nanoagents for Photothermal Cancer Therapy

Layered metal oxides including MoO 3 and WO 3 have been widely explored for biological applications owing to their excellent biocompatibility, low toxicity, and easy preparation. However, they normally exhibit weak or negligible near-infrared (NIR) absorption and thus are inefficient for photo-induced biomedical applications. Herein, the structural engineering of layered MoO 3 and WO 3 nanostructures is first reported to activate their NIR-II absorption for efficient photothermal cancer therapy in the NIR-II window. White-colored micrometre-long MoO 3 nanobelts are transformed into blue-colored short, thin, defective, interlayer gap-expanded MoO 3–x nanobelts with a strong NIR-II absorption via the simple lithium treatment. The blue MoO 3–x nanobelts exhibit a large extinction coefficient of 18.2 L g –1 cm –1 and high photothermal conversion efficiency of 46.9% at 1064 nm. After surface modification, the MoO 3–x nanobelts can be used as a robust nanoagent for photoacoustic imaging-guided photothermal therapy to achieve efficient cancer cell ablation and tumor eradication under irradiation by a 1064 nm laser. Importantly, the biodegradable MoO 3–x nanobelts can be rapidly degraded and excreted from body. We report the study highlights that the structural engineering of layered metal oxides is a powerful strategy to tune their properties and thus boost their performances in given applications.

36 MATERIALS SCIENCE↗

Understanding the TiH (2-x) /TiO y System at Elevated Temperature: A Literature Review

Titanium hydride of varying TiH stoichiometry is used in pyrotechnic compositions. In order to yield consistent performance, manufacturing processes must be developed to ensure precise and reproducible material properties, including composition and morphology. Legacy synthesis protocols are not comprehensive nor are the required apparatuses still available. To guide the development of novel production procedures, this report reviews literature on relevant chemical reactions and diffusion events occurring at elevated temperature in the TiH (2-x) /TiO y system. Titanium hydride exposed to air spontaneously forms a passivating oxide layer. Upon heating, significant hydrogen release, which is accompanied by changes to the surface oxide layer, is noted by 375–400°C. At higher temperatures (above about 500°C) the oxide layer is reported to be essentially nonexistent as a result of oxide-layer dissolution processes and, potentially, oxide-layer reduction due to water formation. Based on the reviewed literature, we hypothesize that, by 500°C, the surface layer consists of an oxyhydride phase, which is a solid solution of oxygen in titanium hydride. We believe that hydrogen release from titanium hydride is controlled by the kinetics of molecular hydrogen desorption on the oxyhydride surface. No literature data is available for corresponding activation energies of the dynamic desorption process, and the equilibrium phase diagram of this three-component system remains largely unexplored as well. These gaps in knowledge might be addressed through coordinated computational modeling and experimental efforts.

36 MATERIALS SCIENCE↗

Advanced Microscopy and Spectroscopy for Probing and Optimizing Electrode-Electrolyte Interphases in High Energy Lithium Batteries (Final Scientific/Technical Report)

The earliest developed LiCoO 2 layered oxide cathode material sparked the development of other layered cathode materials, dominating the positive electrode materials for lithium ion batteries. Within the practical operating conditions of today, the current generation layered oxide materials do not meet the future energy storage demands of 350 Wh kg -1 at cell level. Li-rich layered oxide (LRLO) materials have the potential to meet the high energy demands. Unlike the classical layered oxides, LRLO materials exhibit capacities that go beyond conventional topotactic mechanistic theoretical values. Despite its high capacities, this material has several challenges (voltage fading, structural instability, sluggish kinetics, cathode electrolyte interphase instability, etc.) that must be overcome in order to reach commercialization. In the past five years, our research group has made great progress on developing advanced characterization techniques coupled with atomic scale modeling to properly characterize the dynamic phenomena that govern the performance limitations of LRLO materials. Furthermore, our efforts have guided the material synthesis and surface modification to improve capacity retention. By carefully controlling the oxygen activities through the creation of uniform oxygen vacancies, we were able to avoid structural decomposition in LRLO. Our materials deliver a discharge capacity as high as 306 mAh g -1 with an initial coulombic efficiency of 90.6%. Furthermore, they do not exhibit obvious capacity decay with a reversible capacity over 300 mAh g -1 after 100 cycles at 0.1 C-rate. Our approach demonstrates the critical needs for advanced diagnosis and characterization. It is through the in-depth understanding of these high voltage cathode materials at atomistic and molecular level and their dynamic changes during the operation of batteries; we can successfully formulate strategies to further optimize this class of cathode materials, especially for the voltage instabilities. The diagnostic tools developed here can also be leveraged to study anode materials such as Li metal anode. The challenge of probing Li metal is the low dose tolerance (high beam sensitivity) of Li metal. We will have to apply cryogenic method (low-temperature) and low-dose electron microscopy and specialized camera to enable the characterization of the lithium metal.

25 ENERGY STORAGE↗

Investigations on the effect of current density on SiO/Si composite electrodes

An oxide layer on the surface of silicon particles is inevitable and is necessary for their application as anode materials for lithium ion batteries with high capacity and durability. However, a thick surficial oxide layer could significantly reduce the capacity of a Si anode. Here, Si nanoparticles with a thick surficial oxide layer of ~20 nm (Si@SiO x ) were fabricated through thermal oxidation and investigated electrochemically. The results revealed that very low current density is needed to activate Si@SiO x anodes during the first formation cycle. Once activated, the Si@SiO x anode can deliver reversible capacity as high as ~1000 mAh/g with low current density. Then, the Si@SiO x can be cycled at higher current densities of >700 mAh/g. Electrochemical impedance spectroscopy (EIS) shows that the lower current density results in lower charge-transfer resistance of the Si@SiO x anode, suggesting a higher degree of lithiation of the surficial oxide layer during low-current activation. EIS analysis also reveals that the lithiation of the surficial oxide is irreversible. We believe that the surface silicon oxide layer is lithiated and forms lithium silicate during the initial activation process. Lithium silicate has high conductivity and allows the lithiation/delithiation of Si core under the oxide layer during following charge and discharge.

25 ENERGY STORAGE↗

Controlling Surface Phase Transition and Chemical Reactivity of O3-Layered Metal Oxide Cathodes for High-Performance Na-Ion Batteries

O3-layered metal oxides are promising cathode materials for high-energy Na-ion batteries (SIBs); however, they suffer from fast capacity fade. In this work, we develop a high-performance O3-NaNi 0.68 Mn 0.22 Co 0.10 O 2 cathode for SIBs toward practical applications by suppressing the formation of a rock salt layer at the cathode surface with an advanced electrolyte. The cathode can deliver a high specific capacity of ~196 mAh g –1 and demonstrates >80% capacity retention over 1000 cycles. NaNi 0.68 Mn 0.22 Co 0.10 O 2 –hard carbon full-cells with practical loading (>2.5 mAh cm –2 ) and lean electrolyte (~40 μL) demonstrate ~82% capacity retention after 450 cycles. A 60 mAh single-layer pouch cell has also been fabricated and demonstrated stable performance. This work represents a significant leap in SIB development and brings new insights to the development of advanced layered metal oxide cathodes for alkaline-ion batteries.

25 ENERGY STORAGE↗

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.↗

Systems and methods for abrasive oxide removal in additive manufacturing processes

Systems and methods for removing an oxide layer in an additive manufacturing process are provided. A direct write machine may be used to create wire bonds for semiconductors. The direct write machine may deposit a conductive print material between bond pads to create interconnections. The bond pads may comprise aluminum and an aluminum oxide layer on an outer surface. The presence of an aluminum oxide layer may decrease the electrical connection between the wire bond and the aluminum substrate. To remove the aluminum oxide layer, an abrasive tool is provided to ultrasonically abrade the aluminum oxide layer while the conductive print material is being deposited. The conductive print material may include abrasive additives materials to further aid in abrading the aluminum oxide layer.

Young, Barbara D.↗

Measurement of the O-18 to O-16 isotope ratio for characterizing oxide surface layers on LDEF samples

The ratio of the density of the oxygen 18 isotope (O-18) to the density of the oxygen 16 isotope (O-16) is a strong function of altitude in the atmosphere because of the stronger gravitational attraction on the heavier isotope. It is proposed that the measurement of this ratio for oxide surface layers on LDEF samples can easily distinguish oxides formed in orbit from contaminative oxides formed during retrieval procedures. Since the satellite altitude is known as a function of time, it may be possible to use the measured ratio to determine the time of formation of oxide layers, the accuracy depending upon the stability of the atmosphere.

Sagalyn, Paul L.↗

Metal oxide semiconductor (MOS) controlled devices and methods of making the same

Metal-Oxide-Semiconductor (MOS) controlled semiconductor devices and methods of making the devices are provided. The devices include a gate which controls current flow through channel regions positioned between source/emitter and drain regions of the device. The devices include a gate oxide layer having a variable thickness. The thickness of the gate oxide layer under the edge of the gate and over the source/emitter regions is different than the thickness over the channel regions of the device. The oxide layer thickness near the edge of the gate can be greater than the oxide layer thickness over the channel regions. The source/emitter regions can be implanted to provide enhanced oxide growth during gate oxide formation. The source/emitter region can include regions that are implanted to provide enhanced oxide growth during gate oxide formation and regions which do not provide enhanced oxide growth during gate oxide formation. The devices can be SiC devices such as SiC MOSFETs and SiC IGBTs.

36 MATERIALS SCIENCE↗

Metal oxide semiconductor (MOS) controlled devices and methods of making the same

Metal-Oxide-Semiconductor (MOS) controlled semiconductor devices and methods of making the devices are provided. The devices include a gate which controls current flow through channel regions positioned between source/emitter and drain regions of the device.The devices include a gate oxide layer having a variable thickness. The thickness of the gate oxide layer under the edge of the gate and over the source/emitter regions is different than the thickness over the channel regions of the device. The oxide layer thickness near the edge of the gate can be greater than the oxide layer thickness over the channel regions. The source/emitter regions can be implanted to provide enhanced oxide growth during gate oxide formation. The source/emitter region can include regions that are implanted to provide enhanced oxide growth during gate oxide formation and regions which do not provide enhanced oxide growth during gate oxide formation. The devices can be SiC devices such as SiC MOSFETs and SiC IGBTs.

Matocha, Kevin↗

Influence of Thermally-Grown Oxide (TGO) Layer on the Driving Forces Associated with Failure in Environmental Barrier Coating (EBC) Systems

Environmental barrier coatings (EBC) is an enabling technology for the successful application of ceramic matrix composites (CMCs) in air-breathing gas turbine engines. Spallation of environmental barrier coating (EBC) induced by thermally grown oxide (TGO) layer is a key EBC failure mode. The TGO layer, resulting from steam oxidation, grows either from a silicon bond coat layer (if present) or from the silicon carbide (SiC) based substrate itself. Critical thickness of the TGO layer for failure is in the range of 20-30 microns but it can vary due to exposure temperature, microstructure etc. Current work at NASA Glenn Research Center, under the Revolutionary Tools and Methods (RTM) project is aimed at addressing associated failure modes in EBC systems and developing robust analysis tools to aid in the design/analysis of these systems. The objective of the current work is to conduct a sensitivity study to examine the influence of uniformly and non-uniformly grown oxide layers with or without damage on the associated driving forces leading to spallation of the EBC when subjected to isothermal loading. Initial results indicate that the presence of damage (vertical cracks caused by in-plane stresses) enhances the stresses that are present due to non-uniformity. However, the presence of non-uniformity itself is still the main factor influencing the magnitude of peel and shear stresses in the TGO layer.

Mital, Subodh K.↗

In-situ microstructure observation of oxidized SiC layer in surrogate TRISO fuel particles under krypton ion irradiation

In accidental scenarios of high temperature gas-cooled reactors, both oxidation of and irradiation to the SiC layer in tri-structural-isotropic (TRISO) fuel particles can change the microstructure and integrity of the fuel elements. Here, in the present study, microstructure and defect evolution in the oxidized SiC layer of surrogate TRISO fuel particles under 1.2 MeV krypton ion irradiation was observed by in-situ transmission electron microscopy. The SiC layers oxidized in water vapor at 1200 °C were irradiated azt room temperature and 800 °C and at damage levels of 0.28–11.2 dpa, respectively. SiC and SiO 2 were found to still be in their crystal structures at the damage level of 11.2 dpa at 800 °C, while SiC was observed to have been amorphized at only 0.56 dpa irradiation at room temperature. The defect number density at 800 °C was an order of magnitude lower than that in the sample irradiated at room temperature. Also, crystalline SiO 2 had higher radiation resistance compared to SiC. A defect reaction rate theory was utilized to understand the fundamental defect evolution process and irradiation resistance difference.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High temperature reactions of ceramics and metals with chlorine and oxygen

The reactions of chlorine and oxygen with solids are complex and quite dependent on material and reaction conditions. However, there are four reaction schemes that describe many of these reactions. These are direct reaction of chlorine with the oxide layer, penetration of the oxide layer by chlorine, paralinear behavior where oxidation and chlorination are of comparable rates, and finally, gas phase reactions where the volatile chlorides react with oxygen. Examples of chlorine and oxygen reactions with cobalt, nickel, chromium, molybdenum, and silicon carbide illustrate each of these four reaction schemes.

Jacobson, N. S.↗

Modeling of the Influence of a Damaged Thermally Grown Oxide (TGO) Layer in an Environmental Barrier Coating System

Environmental barrier coatings (EBC) are an enabling technology for the successful application of ceramic matrix composites (CMCs) in air-breathing gas turbine engines. EBCs are susceptible to a number of failure modes including oxidation/delamination, recessions, chemical attack and dissolution, thermomechanical degradation, erosion, and foreign object impact damage in a combustion environment. Spallation of environmental barrier coating (EBC), induced by a thermally grown oxide (TGO) layer, is a key EBC failure mode. The TGO layer, resulting from steam oxidation, grows either from a silicon bond coat layer (if present) or from a silicon carbide (SiC) based substrate itself. The TGO layer evolves (i.e., thickness increases with time) as water vapor and oxygen gradually diffuse through the EBC, and the EBC spalls off once the TGO layer reaches some critical thickness. The critical thickness of the TGO layer for failure is in the range of 20-30 microns, but it can vary due to exposure temperature, microstructure etc. Current work at NASA Glenn Research Center, under the Revolutionary Tools and Methods (RTM) subproject is aimed at addressing associated failure modes in EBC systems and developing robust analysis tools to aid in the design/analysis of these systems. The objective of the current work is to conduct a sensitivity study to examine the influence of uniformly and non-uniformly grown oxide layers on the associated driving forces leading to spallation of the EBC when subjected to isothermal loading. The effect of damage in the TGO layer on the resulting stress states is also assessed both in uniform and non-uniform TGO layers.

Mital, Subodh K.↗

Modeling of the Influence of Thermally Grown Oxide (TGO) Layers on the Driving Forces in Environmental Barrier Coating Systems

Environmental barrier coatings (EBC) are an enabling technology for the successful application of ceramic matrix composites (CMCs) in air-breathing gas turbine engines. EBCs are susceptible to several failure modes including oxidation/delamination, recession, chemical attack and dissolution, thermomechanical degradation, erosion, and foreign object impact damage in a combustion environment. Spallation of environmental barrier coating (EBC), induced by a thermally grown oxide (TGO) layer, is a key EBC failure mode. The TGO layer, resulting from steam oxidation, grows either from a silicon bond coat layer (if present) or from a silicon carbide (SiC) based substrate itself. The TGO layer evolves (i.e., thickness increases with time) as water vapor and oxygen gradually diffuse through the EBC, and the EBC spalls off once the TGO layer reaches some critical thickness. The critical thickness of the TGO layer for failure is in the range of 20-30 microns, with the actual value depending upon exposure temperature, microstructure, etc. Current work at NASA Glenn Research Center, under the Transformative Tools and Technology (TTT) subproject is aimed at addressing associated failure modes in EBC systems and developing robust analysis tools to aid in the design/analysis of these systems. The objective of the current work is to conduct a sensitivity study to examine the influence of uniformly and non-uniformly grown oxide layers on the associated driving forces leading to spallation of the EBC when subjected to isothermal loading. The effect of damage in the TGO layer on the resulting stress states is also assessed both in uniform and non-uniform TGO layers.

Coatings↗