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At least 235 records · Page 13

Enhancing the Electrochemical Performance of Aqueous Processed Li-Ion Cathodes with Silicon Oxide Coatings

Lithium-ion battery cathode materials suffer from bulk and interfacial degradation issues, which negatively affect their electrochemical performance. Oxide coatings can mitigate some of these problems and improve electrochemical performance. However, current coating strategies have low throughput, are expensive, and have limited applicability. In this article, we describe a low-cost and scalable strategy for applying oxide coatings on cathode materials. Here, we report synergistic effects of these oxide coatings on the performance of aqueously processed cathodes in cells. The SiO 2 coating strategy developed herein improved mechanical, chemical, and electrochemical performance of aqueously processed Ni-, Mn- and Co-based cathodes. This strategy can be used on a variety of cathodes to improve the performance of aqueously processed Li-ion cells.

25 ENERGY STORAGE↗

Effects of High Temperature on Collector Coatings

Report reveals electroplated black chrome is good coating for concentrating collectors in which temperatures are in the 650 degrees-800 degrees F (340 degrees - 430 degrees C) range. Black chrome thermal emittance is low and solar-absorption properties are not seriously degraded at high temperatures. Black coatings are used to increase absorption of solar energy by base metal while decreasing emission of infrared energy. Coatings are intended to improve efficiency of solar collectors.

Lowery, J. R.↗

ISS Charging Hazards and Low Earth Orbit Space Weather Effects

Current collection by high voltage solar arrays on the International Space Station (ISS) drives the vehicle to negative floating potentials in the low Earth orbit daytime plasma environment. Pre-flight predictions of ISS floating potentials Phi greater than |-100 V| suggested a risk for degradation of dielectric thermal control coatings on surfaces in the U.S. sector due to arcing and an electrical shock hazard to astronauts during extravehicular activity (EVA). However, hazard studies conducted by the ISS program have demonstrated that the thermal control material degradation risk is effectively mitigated during the lifetime of the ISS vehicle by a sufficiently large ion collection area present on the vehicle to balance current collection by the solar arrays. To date, crew risk during EVA has been mitigated by operating one of two plasma contactors during EVA to control the vehicle potential within Phi less than or equal to |-40 V| with a backup process requiring reorientation of the solar arrays into a configuration which places the current collection surfaces into wake. This operation minimizes current collection by the solar arrays should the plasma contactors fail. This paper presents an analysis of F-region electron density and temperature variations at low and midlatitudes generated by space weather events to determine what range of conditions represent charging threats to ISS. We first use historical ionospheric plasma measurements from spacecraft operating at altitudes relevant to the 51.6 degree inclination ISS orbit to provide an extensive database of F-region plasma conditions over a variety of solar cycle conditions. Then, the statistical results from the historical data are compared to more recent in-situ measurements from the Floating Potential Measurement Unit (FPMU) operating on ISS in a campaign mode since its installation in August, 2006.

Minow, Joseph↗

High Temperature Resistant Organopolysiloxane Coating for Protecting and Repairing Rigid Thermal Insulation

Ceramics are protected from high temperature degradation, including high temperature, oxidative, aeroconvective degradation by a high temperature and oxidation resistant coating of a room temperature curing, hydrolyzed and partially condensed liquid polyorganosiloxane to the surface of the ceramic. The liquid polyorganosiloxane is formed by the hydrolysis and partial condensation of an alkyltrialkoxysilane with water or a mixture of an alkyltrialkoxysilane and a dialkyldialkoxysilane with water. The liquid polyorganosiloxane cures at room temperature on the surface of the ceramic to form a hard, protective, solid coating which forms a high temperature environment, and is also used as an adhesive for adhering a repair plug in major damage to the ceramic. This has been found useful for protecting and repairing porous, rigid ceramics of a type used on reentry space vehicles.

Leiser, Daniel B.↗

Atomic oxygen effects on thin film space coatings studied by spectroscopic ellipsometry, atomic force microscopy, and laser light scattering

The University of Nebraska is currently evaluating Low Earth Orbit (LEO) simulation techniques as well as a variety of thin film protective coatings to withstand atomic oxygen (AO) degradation. Both oxygen plasma ashers and an electron cyclotron resonance (ECR) source are being used for LEO simulation. Thin film coatings are characterized by optical techniques including Variable Angle Spectroscopic Ellipsometry, Optical spectrophotometry, and laser light scatterometry. Atomic Force Microscopy (AFM) is also used to characterize surface morphology. Results on diamondlike carbon (DLC) films show that DLC degrades with simulated AO exposure at a rate comparable to Kapton polyimide. Since DLC is not as susceptible to environmental factors such as moisture absorption, it could potentially provide more accurate measurements of AO fluence on short space flights.

Synowicki, R. A.↗

High temperature glass thermal control structure and coating

A high temperature stable and solar radiation stable thermal control coating is described which is useful either as such, applied directly to a member to be protected, or applied as a coating on a re-usable surface insulation (RSI). It has a base coat layer and an overlay glass layer. The base coat layer has a high emittance, and the overlay layer is formed from discrete, but sintered together glass particles to give the overlay layer a high scattering coefficient. The resulting two-layer space and thermal control coating has an absorptivity-to-emissivity ratio of less than or equal to 0.4 at room temperature, with an emittance of 0.8 at 1200 F. It is capable of exposure to either solar radiation or temperatures as high as 2000 F without significant degradation. When used as a coating on a silica substrate to give an RSI structure, the coatings of this invention show significantly less reduction in emittance after long term convective heating and less residual strain than prior art coatings for RSI structures.

Stewart, D. A.↗

Contamination control in hybrid microcircuit modules

The influence of chemical and particulate contamination upon the reliability and service life of hybrid microelectronic systems is documented. Several coating systems used include the parylene and Dow Corning silicone (DC90-711). These passivating coatings have potential for decreasing the degradation caused by particulate contaminants in hybrid systems as well as the possible deleterious effect of trapping chemical contaminants which have long term degrading influences upon the performance of the system. The reliability of a representative hybrid microcircuit is enhanced by the coating process.

Kinser, D. L.↗

Thermal barrier coating life prediction model

This is the second annual report of the first 3-year phase of a 2-phase, 5-year program. The objectives of the first phase are to determine the predominant modes of degradation of a plasma sprayed thermal barrier coating system and to develop and verify life prediction models accounting for these degradation modes. The primary TBC system consists of an air plasma sprayed ZrO-Y2O3 top coat, a low pressure plasma sprayed NiCrAlY bond coat, and a Rene' 80 substrate. Task I was to evaluate TBC failure mechanisms. Both bond coat oxidation and bond coat creep have been identified as contributors to TBC failure. Key property determinations have also been made for the bond coat and the top coat, including tensile strength, Poisson's ratio, dynamic modulus, and coefficient of thermal expansion. Task II is to develop TBC life prediction models for the predominant failure modes. These models will be developed based on the results of thermmechanical experiments and finite element analysis. The thermomechanical experiments have been defined and testing initiated. Finite element models have also been developed to handle TBCs and are being utilized to evaluate different TBC failure regimes.

Hillery, R. V.↗

Suppressing Atmospheric Degradation of Sulfide-Based Solid Electrolytes via Ultrathin Metal Oxide Layers

Sulfide-based solid-state electrolytes (SSEs) are promising materials with superior Li-ion conductivity; however, their poor atmospheric stability limits commercial manufacturing at scale. Here, we investigate the impact of ultrathin metal oxide layers deposited via atomic layer deposition (ALD) on the stability of Li 6 PS 5 Cl (LPSCl). Al 2 O 3 layers grown directly on LPSCl particles significantly stabilize the surface chemistry and Li-ion transport properties relative to uncoated material upon exposure to both an ambient atmosphere (22% relative humidity, RH) and humidified O 2 (100% RH). Detailed investigations indicate that coatings impede the surface and bulk degradation kinetics of exposed materials, even for coatings as thin as ∼1 Å. Furthermore, this suggests that stabilization is due to more than just a physical barrier. Shifts in valence band edge positions of coated LPSCl indicate that ALD coatings alter the surface electronic structure and resulting oxidation tendency of underlying LPSCl, suggesting new avenues to improving the environmental stability of sulfide SSEs.

Atmospheric chemistry↗

Science Data Report for the Optical Properties Monitor (OPM) Experiment

This science data report describes the Optical Properties Monitor (OPM) experiment and the data gathered during its 9-mo exposure on the Mir space station. Three independent optical instruments made up OPM: an integrating sphere spectral reflectometer, vacuum ultraviolet spectrometer, and a total integrated scatter instrument. Selected materials were exposed to the low-Earth orbit, and their performance monitored in situ by the OPM instruments. Coinvestigators from four NASA Centers, five International Space Station contractors, one university, two Department of Defense organizations, and the Russian space company, Energia, contributed samples to this experiment. These materials included a number of thermal control coatings, optical materials, polymeric films, nanocomposites, and other state-of-the-art materials. Degradation of some materials, including aluminum conversion coatings and Beta cloth, was greater than expected. The OPM experiment was launched aboard the Space Shuttle on mission STS-81 in January 1997 and transferred to the Mir space station. An extravehicular activity (EVA) was performed in April 1997 to attach the OPM experiment to the outside of the Mir/Shuttle Docking Module for space environment exposure. OPM was retrieved during an EVA in January 1998 and was returned to Earth on board the Space Shuttle on mission STS-89.

Wilkes, D. R.↗

UV testing of INTELSAT-7, 7A, and 8 solar cells

A 4000 hour experiment, conducted in late 1992 through mid 1993, confirmed earlier results on the ultraviolet damage effects in covered solar cells of various types being used, or proposed for use, in INTELSAT programs. Two different UV test systems were used to identify systematic errors and to study the effects of UV source-bulb age on degradation rate. After correction for contamination and UV source-bulb aging, the extrapolated degradation rates for irradiated and unirradiated INTELSAT-5, -6 single AR(SAR) coated cells and INTELSAT-7, -7A, -8 double layer AR(DAR) coated cells in both the 1993 tests confirm the following hypotheses resulting from the 1992 experiment. (a) Irradiated cells display significantly more UV degradation than do the unirradiated cells for tests exceeding 2000 hours. The new data indicates that degradation effects from electron irradiation are proportional to t(exp 2) (the square of the UV hours), at least for times less than or equal to 3000 hours. (b) This difference does not depend upon entire reflective coating, cell resistivity, or manufacturer within the sensitivity and reproducibility of the experiment. (c) There is a clear difference in degradation rate between single AR coated cells (TiO(x)) and double layer AR coated cells (SiO(x) and Al2O3?). At 100,000 hours (11.4 years) the DAR coated cells display more degradation than do the SAR coated cells, even though at 1,000 hours the DAR cells display less degradation. (d) UV degradation rates, to modern covered silicon solar cells, at the beginning of bulb life drop from approximately 2 times the average rate to near zero after 2000 hours (average end-of-life for the xenon short-arc lamps used in the tests). The effects of 1 MeV electron irradiation (10(exp 15) e(-)/sq cm) prior to UV exposure are clearly indicated in the plot of percent change in cell open circuit voltage (Voc) versus percent change in short circuit current (Isc) during the UV test and post-test cleanup of the cells. Clearly, extended UV testing produces a permanent photo-induced redegradation of previously irradiated cells. However, this photo-induced redegradation may be caused by the long-wavelength light, not the UV light.

Meulenberg, A.↗

Aging of Concrete for the Evaluation of Repair Materials to Protect the Walls of the HCAEX Tunnel at Savannah River - 20301

H-Canyon, located in the Savannah River site, is a unique facility for chemical reprocessing of plutonium, highly-enriched uranium, and other radioactive materials. The exhaust gases of the H-Canyon are sent through the H-Canyon Exhaust (HCAEX) tunnel for contamination removal. Robotic inspections of the tunnel revealed significant degradation of the reinforced concrete structure that was associated with acid attack, and could compromise the structural stability of the tunnel. Thus, the identification and evaluation of potential repair materials that could be applied on the degraded walls to mitigate and prevent further degradation is of significant interest to the Department of Energy and the Savannah River representatives. This research effort has been divided into two phases: 1) Development and evaluation of aged concrete under accelerated aging conditions (which is the focus of this paper) and 2) Evaluation of potential repair materials applied on aged and non-aged concrete under simulated aggressive conditions. In order to develop and evaluate concrete samples exposed to accelerated aging conditions in simulated aggressive environments, a literature review of the HCAEX tunnel was conducted that included 1) characterization and extent of the concrete damage, 2) environmental conditions inside the tunnel and 3) primary deterioration mechanisms. In addition, potential coatings and/or repair materials for degraded concrete surfaces exposed to aggressive environments (primarily acidic) were selected from the literature review and the most common testing and measurements for evaluating acid attack phenomena, erosion, etc. were reviewed. From the literature review findings, a preliminary bench-scale test plan for the concrete aging was developed, including accelerated aging tests with aggressive conditions (acid fumes, humidity, etc.). Concrete samples were exposed to the aging accelerated conditions (e.g. immersion in acid solutions) and visual inspection, mass loss and pH change (acid solution) were recorded over time. Correlations between the visual inspection, mass loss and pH changes results and the aging time or the aging conditions were developed. Specimens submitted to the highest acid concentration showed the fastest and most intense degradation. The type of coarse aggregate (limestone) used for the concrete seemed to be the cause of the fastest aging observed, compared to the cement paste. The research findings created the foundation for the ongoing investigation, in which new concrete samples with a mix design similar to the HCAEX tunnel will be tested and will serve as the substrate for testing the selected coatings and /or repair materials. In this paper, the literature review and preliminary results from the aging tests are provided. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Sublimation behavior of silicon nitride /Si3N4/ coated silicon germanium /SiGe/ unicouples

For the Multi-Hundred Watt (MHW) Radioisotope Thermoelectric Generator (RTG), the silicon germanium unicouples are coated with silicon nitride to minimize degradation mechanisms which are directly attributable to material sublimation effects. A program is under way to determine the effective vapor suppression of this coating as a function of temperature and gas environment. The results of weight loss experiments, using Si3N4 coated hot shoes (SiMo), operating over a temperature range from 900 C to 1200 C, are analyzed and discussed. These experiments were conducted both in high vacuum and at different pressures of carbon monoxide (CO) to determine its effect on the coating. Although the results show a favorable vapor suppression at all operating temperatures, the pressure of the CO and the thickness of the coating have a decided effect on the useful lifetime of the coating.

Stapfer, G.↗

Estimating mass-absorption cross-section of ambient black carbon aerosols: theoretical, empirical, and machine learning models

The mass-absorption cross-section of black carbon (MAC BC ) is an essential parameter to link the atmospheric concentration of black carbon (BC) with its radiative forcing. When a direct calculation of MAC BC based on observations of aerosol light absorption and BC mass concentration is impossible, we rely on modeling and simulations to estimate MAC BC , but currently, there is no consensus model that can be relied on for accurate predictions across all atmospheric environments when BC particles have different coating thicknesses. Here, we applied five MAC BC prediction models (including three light scattering theories, an empirical model based on observations of particle mass concentrations, and a machine learning model developed in our previous work) to aerosols from three Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) field campaigns. While many studies have found that increasing the complexity of the models helps to constrain biases of the estimated MAC BC , our effort is to evaluate the models based on the criteria of simplicity and accuracy. We find that our machine learning model (support vector machine for regression, SVM) generally performs well across all DOE ARM field campaign data, while the accuracy of core-shell Mie theory depends on the bias correction algorithm applied to filter-based light absorption data. Generally, the empirical model for internally-mixed particles that we considered tends to over-predict MAC BC , while Mie theory for externally-mixed particles tends to under-predict MAC BC . An examination of the influence of coating material on BC cores suggests that the performance of our current SVM model is degraded when the BC is thickly-coated (e.g., it has undergone aging and mixing with other materials in the atmosphere).

54 ENVIRONMENTAL SCIENCES↗

Effects of long term space environment exposure on optical substrates and coatings

At the time of our Second LDEF Post-Retrieval Symposium report, we had completed cleaning and measuring the post flight spectral performance of all of the samples except for the fused silica substrate with an antireflection (SiO2/TiO2) coating. As was documented in that report, after cleaning, all of the samples returned to their original pre-flight performance, with the exception of the fused silica anti-reflectance coated sample, which had significant degraded performance. All normal methods of removing the contaminant from the surface of this sample failed except for oxygen plasma etch. At the time of the previous report, we had only exposed the sample to three hours of plasma etch. We have since continued the plasma etch for a total of 32 hours, after which time, the transmission of the sample almost reached its pre-flight values. The peak areas of the transmission curves remained shifted approximately 150 nm. Of interest is the fact that the control samples, which hadn't flown, did not exhibit any spectral shifting. In summary, after the 6 yr exposure to the space environment, all of the coatings and substrates returned to their pre-flight performance after cleaning, with the exception of the antireflection coated fused silica sample. On this sample, the spectral transmission curves shifted approximately 150 nm.

Vallimont, John↗

Analysis of Thermal Radiation Effects on Temperatures in Turbine Engine Thermal Barrier Coatings

Thermal barrier coatings are important, and in some instances a necessity, for high temperature applications such as combustor liners, and turbine vanes and rotating blades for current and advanced turbine engines. Some of the insulating materials used for coatings, such as zirconia that currently has widespread use, are partially transparent to thermal radiation. A translucent coating permits energy to be transported internally by radiation, thereby increasing the total energy transfer and acting like an increase in thermal conductivity. This degrades the insulating ability of the coating. Because of the strong dependence of radiant emission on temperature, internal radiative transfer effects are increased as temperatures are raised. Hence evaluating the significance of internal radiation is of importance as temperatures are increased to obtain higher efficiencies in advanced engines.

Siegel, Robert↗

Thermochemistry of Silicates

The thermodynamic properties of vapor and condensed phases of silicates are crucial in many fields of science. These quantities address fundamental questions on the formation, stability, transformation, and physical properties of silicate minerals and silicate coating compositions. Here the thermodynamic activities of silica and other species in solid solution have been measured by the analysis of the corresponding high temperature vapors using Knudsen Effusion Mass Spectrometry (KEMS). In first set of experiments KEMS has been used to examine the volatility sequence of species (Fe, SiO, Mg, O2 and O) present in the vapor phase during heating of fosterite-rich olivine (Fo93Fa7) up to 2400 C and to measure the Fe, SiO and Mg activities in its solid solution. The data of fosterite-rich olivine are essential for thermochemical equilibrium models to predict the atmospheric and surface composition of hot, rocky exoplanets (Lava Planets). In the second set of experiments the measured thermodynamic activities of the silica in Y2O3-SiO2 and Yb2O3-SiO2 systems are used to assess their reactivity and degradation recession as environmental barrier coatings (EBCs) in combustion environments (e.g. non-moveable parts of gas turbine engine).

Silicates↗